CA1257439A - Process of thermal stabilization of halogeno-vinyl polymers and the resines so stabilized - Google Patents
Process of thermal stabilization of halogeno-vinyl polymers and the resines so stabilizedInfo
- Publication number
- CA1257439A CA1257439A CA000460174A CA460174A CA1257439A CA 1257439 A CA1257439 A CA 1257439A CA 000460174 A CA000460174 A CA 000460174A CA 460174 A CA460174 A CA 460174A CA 1257439 A CA1257439 A CA 1257439A
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- Prior art keywords
- mercapto
- polyol
- ester
- acid
- resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a process for the thermal stabilization of a halogeno-vinyl resin, which comprises incorporating into the resin (a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mercapto alkonoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, esterified by a sulfur-free organic acid; (b) at least one stabilizing metal compound whose metal is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of the Elements, and (c) at least one alkaline earth metal organic compound.
Disclosed is a process for the thermal stabilization of a halogeno-vinyl resin, which comprises incorporating into the resin (a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mercapto alkonoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, esterified by a sulfur-free organic acid; (b) at least one stabilizing metal compound whose metal is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of the Elements, and (c) at least one alkaline earth metal organic compound.
Description
~:S~3~
The present invention relates -to the thermal stabilization oE halogeno-vinyl polymers and in particular polyvinyl chloride. More particularly, the invention relates to a process for the thermal stabilization of a halogeno-vinyl resin, which process comprises lncorporating into the polymer, a mixture additives which reduce the harmful effects of heat on the polymer.
Current at-tempts to make halogeno-vinyl polymers subject as little as possible to alteration due to thermal effects constitute a permanent interest of the industries which produce or utilize these materials. As regards polyvinyl chloride, the most important of the products of this type, it has been -the object of research in relation to its thermal stabilization for more than 50 years; as its manuEacture takes place in the hot, generally between 150 and 200C, decomposition reactions with the loss of HCl, scission of the macromolecular chains and others reduce the mechanical, rheological and electrical properties of the product with discolouration which can rapidly a-t-tain a black colour. Also, Eor half a century, various additives have been utilized to reduce this troublesome process. Among the first stabilizers were alkaline earth soaps and lead compounds, par-ticularly the silicates. Other metal derivatives were applied subsequen-tly; then s-tep-by-step, stabilization was perEected by the addition of a second compound or co-stabilizer, such as for example an epoxide, phosphite, phenol anti-oxidant, organic thio-compound etc.
During the past decade, substantial progress has been made by the use of systems comprising both a Cd salt and a Ba or Ca salt; since 1970, more -than 80 products of this type have been on the market, under various trade names, such as "Advastab", "Ferro Mark", "Synpron", e-tc. (Modern Plastics Encyclopaedia, 1970-1971, pages 870-875). However, 7~39
The present invention relates -to the thermal stabilization oE halogeno-vinyl polymers and in particular polyvinyl chloride. More particularly, the invention relates to a process for the thermal stabilization of a halogeno-vinyl resin, which process comprises lncorporating into the polymer, a mixture additives which reduce the harmful effects of heat on the polymer.
Current at-tempts to make halogeno-vinyl polymers subject as little as possible to alteration due to thermal effects constitute a permanent interest of the industries which produce or utilize these materials. As regards polyvinyl chloride, the most important of the products of this type, it has been -the object of research in relation to its thermal stabilization for more than 50 years; as its manuEacture takes place in the hot, generally between 150 and 200C, decomposition reactions with the loss of HCl, scission of the macromolecular chains and others reduce the mechanical, rheological and electrical properties of the product with discolouration which can rapidly a-t-tain a black colour. Also, Eor half a century, various additives have been utilized to reduce this troublesome process. Among the first stabilizers were alkaline earth soaps and lead compounds, par-ticularly the silicates. Other metal derivatives were applied subsequen-tly; then s-tep-by-step, stabilization was perEected by the addition of a second compound or co-stabilizer, such as for example an epoxide, phosphite, phenol anti-oxidant, organic thio-compound etc.
During the past decade, substantial progress has been made by the use of systems comprising both a Cd salt and a Ba or Ca salt; since 1970, more -than 80 products of this type have been on the market, under various trade names, such as "Advastab", "Ferro Mark", "Synpron", e-tc. (Modern Plastics Encyclopaedia, 1970-1971, pages 870-875). However, 7~39
2.
1 the toxicity andh1gh cost of cadmium have led to a search for other means, which has produced among others systems of compounds of Ba with Zn or Ca with Zn, numerous products now being on sale, also. On the other hand, because good results have been obtained with organic Sn and Sb derivatives, attempts have been made to improve these and the addition of certain mercaptans has been found of interest, as indicated in French Published Patent Specification 2434835 and in German Patent Specification 1217609 or US Patent Specification 3063963. However, both for health reasons and for cost reasons, the present tendency is the replacement of heavy metals, both Cd as well as Sn, by completely non-toxic and less costly stabilizers. Thus, at the present time, a return to 15 alkaline earth and zinc systems is desired, by enhancing their stabilizing action by other additives. A typical example of such efforts is to be found in French published s Patent Applica-tion 2492391 (1980) and European published Patent Application 0022047 (1980), which relate to stabi-20 lizers formed by Ca and Zn compounds, improved by means of various thioglycolic esters; the second of these documen-ts also refers to the addition of a polyol.
Since the additives, of whatever nature, can only retard alterations due to heat and, if required, 25 also to visible light or other radiations, but without completely suppressing the decomposition reactions, none of the results obtained up to the present has been regarded as definitive; all research can thus expect chances to improve on the prior art.
The present invention results from research effected according to the new tendency mentioned above and it provides a clear improvement in the thermal resistance of halogeno-vinyl resins~ The unexpected character of this invention lies in the fact that the improvement in stability is obtained more economicaliy and also with less ~.25,~39 odour, by the addition to the resin of a mixture containing mercapto-alkanoic acid esters of the mixed type, due to reduction in the relative number of -S~l groups in the molecule of such esters utilized according to the prior art.
The use of mercapto-esters in general, in conjunction with stabilizing metal compounds and, in particular, with polyol mercapto-alkanoic acid esters, is known from French Patent Specification 2492391 and US Patent 3144422; the effect increases with the proportion of the stabilizer in the resin and thus the conten-t of -S~l groups.
In a surprising way, the stabilization is at least as good or even better, while providing a certain econorny, when, in accordance with the invention, use is made of mercapto-esters which contain less -SH groups with respect to their alcohol residues and, consequently, less mercapto-groups per 100 parts of resin.
The advantages of the invention lie in that it leads to plastics ma-terials which are as stable and as good in quality as materials which include Cd or Sn compounds, although i-t only utilizes additives which are less costly and non-toxic. Also, plastics materials stabilized according to the invention are free from any odour, in contrast -to those which contain thioglycolic esters according to the prior art; they have good resistance to humidity and water due to the absence of the hydroxyl-containing additives employed in the prior art mentioned above.
The process according to the invention as claimed hereinafter consists in incorporating into a halogeno-vinyl resin a mixture of:
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mercapto alkonoic acid and all -the o-ther .~ ,, .~.,i 4 - ~
hydroxyl groups of its polyol constituent, or a par-t of said other groups, esterified by a sulfur-free organic acid;
b) at least one stabilizing metal compound whose metal is selected from groups IIB, IIIA, IVA, and VA of the Periodic Classifica-tion of the Elements, and c) at least one alkaline earth metal organic compound.
Other stabilizers or additives known per se, may also be used in the mixture incorporated -to the resins, such 10 as fatty compounds, preferably oxidized.
The process according to the inven-tion is particularly effective in the case of plasticized resins.
Preferably, the metal of Groups IIB -to VA
mentioned above is zinc, but i-t can be selected from others.
15 As the alkaline earth metals, the ones most suitable are Ca, Ba and/or Sr.
The mercapto--acid ester can carry, on the same polyol residue, residues of several different acids containing -SH groups and/or several acids without -SH
20 groups.
The mercapto-acids forming the mixed esters used according to the invention can be represented generally by the formula:
(HS)n-R-(COOH)m (1) in which n has a value from 1 to 5, m = 1 or 2, R is a C1 to C35 aliphatic chain or ring, optionally branched, preferably from C2 to C17, which, for m = 1, correspond to the respective total numbers of C2 to C3~ and C3 to C18.
By way of non-limitative example, various mercapto-acid esters u-tilizable according to the invention are set out below:
'~' - 4a -a - mercaptopropionic, 1-13C-CI~-C0211 (or 2-mercaptopropionic);
Sll ~ - mercaptopropionic HSCH2CH2 C02~1 (or 3-mercapto-propi.onic);
w - mercaptoundecanoic HSCH2(CH2)9C0211, ( or ll-mercapto-undecanoic) .' ~`:
r~ ~39 5.
1 10 - mercaptoundecanoic H3C-CH(CH~)8C02H, SH
mercaptosuccinic H02C-CH-CH2C02H (or thiomalic);
SH
dimercaptosuccinic HO2C-CH-CH-CO2H;
~ 5H ~H
2 - mercapto-benzoic, ~ CO2H (or thiosalicylic) SH
As indicated above, a proportion of the -OH
groups of the polyol from which the mercapto-ester is derived are esterified by another carboxylic acid, which must not carry the -SH function. Such a carboxylic acid, of the general formula R'(CO2H)p, is preferentially a mono- or di-acid (p = 1 to 2). R' can be a straight or branched aliphatic alkyl or alkenyl or aromatic group containing at least 2 carbon atoms and, preferably, 5 to 37 and most preferably 5 to 17. While any carboxylic acid can be utilized, those preferred are the fatty acids, particularly caprylic, octanoic, cetanoic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, oleic, linoleic, linolenic, behenic and montanic. Other particularly suitable acids are succinic, adipic, glutaric, pimelic, suberic, azelaic, sebacic, dioleic, malic, tartaric or phthalic, as well as aromatic mono-acids, such as benzoic.
The polyol, from which the mixed mercapto-ester utilized according to the invention is derived, can be formed by a straight or branched carbon chain or ring, generally from C2 to C30 but preferably from C2 to C20, comprising a number of OH groups greater than or equal to 2. Various other functions can also be present, in particular ether oxide, thiol, sulphide, disulphide~
polysulphide, carboxylic acid, ester, amine. As non-limitative examples of the polyols, the following materials ~257~39 6.
1 can be mentioned:
ethylene glycol and polyethylene glycol Ho~CH2CH2OtrCH2CH2OH r = 1 to 30;
propylene glycol and polypropylene glycol HO~CH2-CH-Ots-CH2CH-OH s = 1 to 30; CH3 CH3 .
thiodiglycol, HOCH2CH2SCH2CH2OH ; pentaerythritol, C(CH2OH)4;
dipentaerythritol, (HOCH2)3C-CH2OCH2C(CH2OH)3 ; tripenta-erythritol, (HOCH2)3CCH2OCH2C~CH2OH)2CH2OCH2C(CH2OH)3 ; tri-methylolpropane, CH3CH2C(CH2OH)3 ; glycerol, HOCH2CH(OH)CH2OH;thioglycerol, HSCH2CH(OH)CH2OH or HOCH2CH(SH)CH2OH ; butane-diol-1,2, butanediol-1,3 ; pentols, hexols and the like.
While a polyol residue constitutes a necessary part of the mercapto-esters according to the invention, they can also carry mono-alcohol residues; it is in fact recommendable to decrease the molecular weight of the ester when a polyacid is being used. In this case, part of the carboxyl groups of the polyacid can advanta-geously be esterified with a mono-alcohol; the latter is generally from C1 to C20 and preferably from C2 to C8. This precaution is useful particularly when the mercapto-ester could have a molecular weight greater than 1200.
By way of non-limitative examples of the mixed esters, reference can be made to :
Pentaerythrityl tris (3-mercapto-propionate)monocaprate C(CH2OCCH2CH2SH)3 CH2OC,(CH2)8 3 O O
Pentaerythrityl mono (2-mercapto-propionate)triscaproate C(cH2occH(sH)cH3~cH2oc(cH2)4cH373 O
Pentaerythrityl tris (3-mercapto-propionate~monostearate 35 17llOcH2c(cH2occH2cH2sH)3 O O
7.
1 Pentaerythrityl bis (3-mercapto-propionate)bispelargonate (H17C8CIOCH2)C(CH2OClCH2CH2SH)2 O O
Trimethylpropane bis (3-mercaptopropionate)monooctanoate H3ccH2c(cH2ollcH2c~2sH)2(cH2oll 7 15 O O
Ethylene-glycol 3-mercapto-propionate-laurate HscH2cH2clocH2cH2olcl(cH2)lO 3 O O
Pentaerythrityl bis (thioglycolate)bispalmitate CH2C CH2) 2C/CH20C(CH2) 14CH372 O O
Glyceryl bis (3-mercapto-propionate)mono-oleate CHOC,IC 2 2 l O
CH20,C, -C17H33 Glyceryl bls(3-mercaptopropionate)monooctanoate CH2Oç(cH2)6c 3 CHOCCH2CH2SH and/or CHOC(CH2)6CH3 l O l O
O O
Thioglyceryl mono (3-mercapto-propionate)monooctanoate CH2SH C,H2SH CH2OCCH2CH,SH
CHO2C(CH2)6C 3 and/or CHO2CH2CH2SH and/or CH-SH
CHo2ccH2cH2sH CHO2(CH2)6c 3 CH2Oc(cH2)6c 3 o The fatty compound or compounds which can advantageously be present in the composition of materials stabilized according to the invention is/are in general ~'5~7~39 C1 to C12 alkyl esters of ylycol and/or glycerol with one or more C8 to C24 Eatty acids, preferably unsaturated, which have undergone epoxidation. I-t is sui-table -to utilize for this purpose a natural oil, such as linseed, soya or Eish oil, which has been epoxidised.
The minimum molecular weigh-t oE the mixed mercapto-ester is 178, corresponding to the lightest acids, mercapto-acetic and acetic, and the lightest polyol, ethylene glycol; this "rninimal" mixed ester is:
Hs-cil2coo-cH2cH2-oocH3 The preferred minimum is 206, corresponding to ethylene 1-mercaptopropionate-2-propionate:
As regards a "heavy" ester, reference can be made for example to a mixed fatty mercapto-ester of a sugar, in particular glucose tris-Lmercatosteara-te~bis-stearate.
(~IS-C17 ~134coo~3 ~
~ C5H6CHO M=1608 (Cl7H3scOo)2 As regards the molecular weights of the mercapto-esters utilized, they can range from 178 to abou-t 2000 and preferably from 200 to 1000. Thus for example, pentaerythrityl bis-(mercapto-propiona-te)bis-octanoate, which gives excellent results, has a molecular weight oE
564.
The mixed ester used in the process of the invention must have at least one of the -OH groups of its polyol constituent es-terified by an organic acid not 3g - 8a -carrying an --S~-l group, while all or part of -the other -011 groups are esterified by a mercapto-acid. Conversely, mixed esters in which the molecule carries a single mercapto-acid are suitable for stabilization, where the o~her acid or acids is/are free from -Sll. In the commonest case of esters derived ~2~i7 9.
1 from polyols having 2 to 6 -O~ groups, there can be respectively 1 mercapto-acid residue per 1 to 5 acid residues without -S~ or reciprocally 1 non-mercapto-acid residue per 1 to 5 mercapto-acid residues.
Among the organic compounds of alkaline earth metals and various compounds of zinc, mention can be made particularly of the carboxylates, mercaptides and ZnC12.
Among the carboxylates, mention can be made in a non-limitative manner of the caproate, 2-ethyl-hexanoate, octanoate, perlargonate, laurate, palmitate, stearate, oleate, benzoate, phenate, alkyl-phenate, naph-thenate and neoalkanoate. Among the mercaptides, reference can be made to those derived from aliphatic mercaptans, mercapto-acid esters or mercaptoalkyl esters.
However, a certain number of derivatives such as the carbonate, oxide, hydroxide, sulphate, halide, (chloride, bromide) can also be used advantageously.
The invention, which applies to various halogeno-vinyl polymers and copolymers, particularly poly-vinyl chloride, polyvinylidene chloride, polyvinylacetochloride and superchlorinated polyvinyl chloride and chlorofluorovinyl resins etc, has, in particular, much importance for plastics materials based on polyvinyl chloride. As in the known art, the proportion of the primary stabilizer, which here is an alkaline earth metal organic compound jointly with a zinc organic compound, is generally from 0.01 to 6% by weight and most preferably from 0.05 to 3%, with respect to the resin to be stabilized.
When the mixed mercapto-ester according to the invention is employed as a co-stabilizer, i-ts proportion is within the same limits, without having to be equal to that of the primary stabilizer.
The Process is applied to plasticized poly-vinyl ch~o~ide containing an epoxidised oil, characterized ~z~ 9 - 9a -in that, by weight of resin, 0,1 to 3% of a mixed mercapto-ester is incorporated in conjunction with 0,005 to 1,5% of an organic Ca, Mg, Ba compound and 0,005 to 2,5% of a Zn compound.
In the particular case of polyvinyl chloride plasticized by the addition of a plasticizer constituted by an ~5~ r~ rl~
lt).
1 sehacate, azelate, phosphate or a polyester, the proportions per 100 parts by weight of the resin are preferably:
5 to 70 parts of plasticiser, 1 to 10 parts of fatty compounds, 0.1 to 2 parts of the al~aline earth metal organic compound, 0.05 to 1.5 parts of the Zn organic compound, 0.1 to 3 parts of the mixed mercapto-ester.
The ratio between the alkaline earth and zinc compounds is preferably from 1 to 6 moles of the first per 1 mole of the second. In the case of calci~, the best ratio ranges from 1 to 4 atoms Ca per 1 Zn.
In the non-limitative Examples which follow, samples of polyvinyl chloride stabilized with an additive according to the invention are subjected to discolouration tests on heating. For this, the various compositions are kneaded for 5 minutes at 160C on a roller mixer. The sheets obtained have a thickness of about 1 mm. The thermal test per se is effected in a furnace of the "SIGMA"
type manufactured by METRASTAT SA. Its principle is based upon evidence of the gradual change in the colour resulting from the thermal decomposition of long test pieces, in the Z5 form of strips 25 cm long, cut from the above-mentioned sheets and exposed temporarily to heat in a furnace maintained at a constant temperature~
Outside the thermal enclosure, the apparatus comprises an electromechanical system ensuring the transfer of a movable sample-carrying plate, leaving the furnace at a predetermined constant speed; an electronic assembly regulates the speed of the plate and also regulates the temperature of the furnace.
The discolouration of the resin is observed for a given furnace temperature and sample discharge ~5~3~
11 .
1 speed. For each test, the "stability time" is recorded, which is the time at which the resin becomes black or when the evolution of the yellow index is recorded. The compositions subjected to the tests comprise:
100 parts by weight of polyvinyl chloride known under the trade name "LACQVYI. S 111" having index K=67, and 40 parts by weight of dioctyl phthalate, (tr~ade name - PALATINOL AH) .
EXAMPLES 1 to 5 The tests fox thermal resistance are effected at 190C, the speed of discharge of the samples being regulated to 30 minutes.
In the results table below, the percentages indicate the proportions of additives incorporated in the samples, before passage through the furnace.
Example No 1 2 3 4 5 Pentaerythrityl tetrakis (3-mercapto-propionate) ... 0 0.4% 0 0 0 20 Pentaerythrityl bis (3-mercapto-propionat,e) bis octanoate ... 0 0 0.4~ 0 0.4%
Epoxidised soya oil ... 0 0 0 4% 4%
Yellow index after 2D minutes ...160 135127 155 90 The first conclusion given by these results is that the mixed mercapto-ester of Example 3 (bis-bis), despite its -SH content of only half that of the corres-ponding tetrakis (Example 2), has an effectiveness at least as good as the latter or even slightly better; the yellow index is 127 as against 135. The use of this mixed compound is thus more economical.
The second interesting result obtained from Example 4 and 5 is that, in the presence of epoxidised soya oil, the mixed mercapto-ester (Example 5) acts strongly 13~
12, 1 to reduce the yellow index from 150 to 90.
EXAMPLES 6 to 10 Association of a mixed mercapto-ester with standard stabilizers based on metal compounds. Tests at 5 190C.
Example No. 6 7 3 9 10 -Sample discharge speed, mn ......... 30 30 30 60 60 Zn octanoate % ..Ø08 0.08 0.08 0.08 0.08 Ba octanoate % ... - - - 0.80 0.80 10 Pentaerythrityl tetrakis (3-mercapto-propionate) ... - 0.4 Pentaerythrityl bis (3-mercapto-propionate)-bis octanoate ... _ 0.4 _ 0,4 Stability time, mn ...15 18 18 43 53 As in the foregoing tests, the mixed mercapto-ester (bis-bis) of Examples 8 and 10 proves to be more effective than the mercapto-ester (tetrakis) of Example 7, although it contains half the number of -SH groups of the latter.
Association of the mixed compound with standard Ba and Zn stabilizers (Examples 9 to 10), shows an improvement in the stability of (53-43):43 = 23.2 which is very appreciable.
EXAMPLES 11 to l9 Operation is as in the foregoing Examples, but a proportion of plasticizer, dioctyl phthalate, is used which is 50 parts by weight per 100 parts of resin, the latter containing 5% of epoxidised soya oil, 0.3%
of Ca stearate and 0.15% of Zn stearate. The stabilities at 190C in minutes have been found by the addition of various mercapto-esters.
13 .
1 EXAMPLE ADDITIVE Stahility ~ ~ constitution mn 11 Nil 160 12 0.5 Pentaerythrityl tetra (3-mercapto-propionate) 203 13 1.0 " " 227 14 1.0 Pentaerythrityl bis (3-mercapto-propionate)bis-octanoate 226 1.0 Pentaerythrityl tetra (11-mercapto-undecanoate) 225 16 1.0 Pentaerythrityl tris (11-mercapto-undecanoate) mono-undecanoate 226 15 171.0 Propyleneglycol bis-mercapto-acetate 189 181.0 Propyleneglycol mercapto-acetate-hexanoate 194 191.0 Ethyl ll-Mercapto-undecanoate 176 20These tests show the possibility of increasing the stability by about 30% (from 160 to 226) by using in conjunction a mixed mercapto-ester with a standard stabilizer system which comprises an epoxidised oil and Ca and Zn stearates.
The foregoing results confirm the surprising advantage of the mixed mercapto ester over an ordinary mercapto-ester. Thus Example 14 (mixed ester) gives a result as good as that of Example 13, mercapto alone, despite its lower -SH content. As the latter is less than half that of the compound of Example 13, it would be better to compare Example 14 with 12 which contains 0.5%
of the mercapto-ester; however the stability in th~s case is 203 minutes as against 226 for the additive according to the invention (Example 14).
The same conclusion can be drawn on the sub~ect 14.
1 of the respective Examples 15-16 and 17-18; it is to be noted in passing that the mercapto-acetate of the prior art (Example 17) gives an odour to the resin.
Example 19 shows that a mercapto-ester of a mono- alcohol is less efficient than mercapto-esters of polyols.
EXAMPLES 20 to 23 By applying the technique of the foregoing Examples to the same composition of polyvinyl chloride with 50% of dioctyl phthalate and 5~ of epoxidised soya oil, the nature and proportions of the stabilizers have been varied. Examples 20 to 22 show the use of Ca and Zn compounds, while Example 23 utilizes stab.ilisers of the prior art based on Cd and Ba, considered to be particularly effective.
Example No 20 21 2~ 23 _ Stabilisers additive ~
Ca Laurate 0.6 - - -Ca Stearate ~0.30 0-30 Zn Stearate 0.15 0.15 - -Zn Mercaptide Zn(scH2cH2coo~l C12H25)2 0.15 Cd Stearate 25 Ba Stearate - ~ , 1.50 Pentaerythrityl bis ~3-mercapto-propionate)bis-octanoate 0.501.0 0.2 Stability in minutes 241226 230 250 These results demonstrate that, due to the addition of the mercapto-ester, a stabilization equivalent to that provided by the known Cd, Ba system is attained;
plus the advantage of avoiding all toxicity due to heavy metals together with a much lower cost.
i7~a39 I!L ~
15.
1 EX~MPLES 24 $o 26 .
The resin composition comprising, per 100 parts of polyvinyl chloride, 50 parts of dioctyl phthalate and 5 parts of epoxidised soya oil is utilized with; 0.6% of Ba laurate and 0.15% of Zn steaxate as standard stabilizers.
The furnace was regulated to 190 C with a sample discharge speed of 180 minutes. The following stabilities are found with each of the co-stabilizers employed for 3 different concentrations of the latter.
Example No % O 0.1 0.2 0.5 24 Pentaerythrityl bis (3-mercapto-propionate) bis-pelargonate 105 119 124 139 Pentaerythrityl bis (3-mercapto-propionate) bis-octanoate 105 117 131 153 26 Pentaerythrityl tetra (3-mercapto-propionate) 105 108 122 131 _ Thus, with 0.5% of the co-stabilizer in Example 24, there is an increase in stability of 139-105 = 34 or (34:105)100 = 32.3%
and in Example 25 153-105 = 48 or (48:105)100 = 45.7%
as against 131-105 = 26 or (26:105)100 = 24.8% only, with the normal mercapto-ester of Example 26.
Examples 8 and 10 are repeated with ZnC12 in place oE Zn octanoate. In practice, the same results are obtained.
EXAMPLES 28 and 29 As in the foregoing Examples, mixtures are used of 100 parts of the same polyvinyl chloride with 50 ~5 :16.
1 parts of dioctyl phthalate, 5 parts of epoxidised soya oil, 0.6 part of Ba octanoate and 0.04 part of ZnC12.
Operating at 190C, the samples are discharged in 180 minutes. Stability times found:
S Example 28 without other additive 84 mn Example 29 + 1 part of pentaerythri~yl bis(3-mercapto-propionate)-bis-octanoate 137 mn or an improvement of 60%.
Test on non-plasticized polyvinyl chloride only containing pentaerythrityl bis(3 mercapto-propionate)-bis-octanoate. The press was operated at 160C. The yellow index found: 90 against 101 for a control without additive.
1 the toxicity andh1gh cost of cadmium have led to a search for other means, which has produced among others systems of compounds of Ba with Zn or Ca with Zn, numerous products now being on sale, also. On the other hand, because good results have been obtained with organic Sn and Sb derivatives, attempts have been made to improve these and the addition of certain mercaptans has been found of interest, as indicated in French Published Patent Specification 2434835 and in German Patent Specification 1217609 or US Patent Specification 3063963. However, both for health reasons and for cost reasons, the present tendency is the replacement of heavy metals, both Cd as well as Sn, by completely non-toxic and less costly stabilizers. Thus, at the present time, a return to 15 alkaline earth and zinc systems is desired, by enhancing their stabilizing action by other additives. A typical example of such efforts is to be found in French published s Patent Applica-tion 2492391 (1980) and European published Patent Application 0022047 (1980), which relate to stabi-20 lizers formed by Ca and Zn compounds, improved by means of various thioglycolic esters; the second of these documen-ts also refers to the addition of a polyol.
Since the additives, of whatever nature, can only retard alterations due to heat and, if required, 25 also to visible light or other radiations, but without completely suppressing the decomposition reactions, none of the results obtained up to the present has been regarded as definitive; all research can thus expect chances to improve on the prior art.
The present invention results from research effected according to the new tendency mentioned above and it provides a clear improvement in the thermal resistance of halogeno-vinyl resins~ The unexpected character of this invention lies in the fact that the improvement in stability is obtained more economicaliy and also with less ~.25,~39 odour, by the addition to the resin of a mixture containing mercapto-alkanoic acid esters of the mixed type, due to reduction in the relative number of -S~l groups in the molecule of such esters utilized according to the prior art.
The use of mercapto-esters in general, in conjunction with stabilizing metal compounds and, in particular, with polyol mercapto-alkanoic acid esters, is known from French Patent Specification 2492391 and US Patent 3144422; the effect increases with the proportion of the stabilizer in the resin and thus the conten-t of -S~l groups.
In a surprising way, the stabilization is at least as good or even better, while providing a certain econorny, when, in accordance with the invention, use is made of mercapto-esters which contain less -SH groups with respect to their alcohol residues and, consequently, less mercapto-groups per 100 parts of resin.
The advantages of the invention lie in that it leads to plastics ma-terials which are as stable and as good in quality as materials which include Cd or Sn compounds, although i-t only utilizes additives which are less costly and non-toxic. Also, plastics materials stabilized according to the invention are free from any odour, in contrast -to those which contain thioglycolic esters according to the prior art; they have good resistance to humidity and water due to the absence of the hydroxyl-containing additives employed in the prior art mentioned above.
The process according to the invention as claimed hereinafter consists in incorporating into a halogeno-vinyl resin a mixture of:
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mercapto alkonoic acid and all -the o-ther .~ ,, .~.,i 4 - ~
hydroxyl groups of its polyol constituent, or a par-t of said other groups, esterified by a sulfur-free organic acid;
b) at least one stabilizing metal compound whose metal is selected from groups IIB, IIIA, IVA, and VA of the Periodic Classifica-tion of the Elements, and c) at least one alkaline earth metal organic compound.
Other stabilizers or additives known per se, may also be used in the mixture incorporated -to the resins, such 10 as fatty compounds, preferably oxidized.
The process according to the inven-tion is particularly effective in the case of plasticized resins.
Preferably, the metal of Groups IIB -to VA
mentioned above is zinc, but i-t can be selected from others.
15 As the alkaline earth metals, the ones most suitable are Ca, Ba and/or Sr.
The mercapto--acid ester can carry, on the same polyol residue, residues of several different acids containing -SH groups and/or several acids without -SH
20 groups.
The mercapto-acids forming the mixed esters used according to the invention can be represented generally by the formula:
(HS)n-R-(COOH)m (1) in which n has a value from 1 to 5, m = 1 or 2, R is a C1 to C35 aliphatic chain or ring, optionally branched, preferably from C2 to C17, which, for m = 1, correspond to the respective total numbers of C2 to C3~ and C3 to C18.
By way of non-limitative example, various mercapto-acid esters u-tilizable according to the invention are set out below:
'~' - 4a -a - mercaptopropionic, 1-13C-CI~-C0211 (or 2-mercaptopropionic);
Sll ~ - mercaptopropionic HSCH2CH2 C02~1 (or 3-mercapto-propi.onic);
w - mercaptoundecanoic HSCH2(CH2)9C0211, ( or ll-mercapto-undecanoic) .' ~`:
r~ ~39 5.
1 10 - mercaptoundecanoic H3C-CH(CH~)8C02H, SH
mercaptosuccinic H02C-CH-CH2C02H (or thiomalic);
SH
dimercaptosuccinic HO2C-CH-CH-CO2H;
~ 5H ~H
2 - mercapto-benzoic, ~ CO2H (or thiosalicylic) SH
As indicated above, a proportion of the -OH
groups of the polyol from which the mercapto-ester is derived are esterified by another carboxylic acid, which must not carry the -SH function. Such a carboxylic acid, of the general formula R'(CO2H)p, is preferentially a mono- or di-acid (p = 1 to 2). R' can be a straight or branched aliphatic alkyl or alkenyl or aromatic group containing at least 2 carbon atoms and, preferably, 5 to 37 and most preferably 5 to 17. While any carboxylic acid can be utilized, those preferred are the fatty acids, particularly caprylic, octanoic, cetanoic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, oleic, linoleic, linolenic, behenic and montanic. Other particularly suitable acids are succinic, adipic, glutaric, pimelic, suberic, azelaic, sebacic, dioleic, malic, tartaric or phthalic, as well as aromatic mono-acids, such as benzoic.
The polyol, from which the mixed mercapto-ester utilized according to the invention is derived, can be formed by a straight or branched carbon chain or ring, generally from C2 to C30 but preferably from C2 to C20, comprising a number of OH groups greater than or equal to 2. Various other functions can also be present, in particular ether oxide, thiol, sulphide, disulphide~
polysulphide, carboxylic acid, ester, amine. As non-limitative examples of the polyols, the following materials ~257~39 6.
1 can be mentioned:
ethylene glycol and polyethylene glycol Ho~CH2CH2OtrCH2CH2OH r = 1 to 30;
propylene glycol and polypropylene glycol HO~CH2-CH-Ots-CH2CH-OH s = 1 to 30; CH3 CH3 .
thiodiglycol, HOCH2CH2SCH2CH2OH ; pentaerythritol, C(CH2OH)4;
dipentaerythritol, (HOCH2)3C-CH2OCH2C(CH2OH)3 ; tripenta-erythritol, (HOCH2)3CCH2OCH2C~CH2OH)2CH2OCH2C(CH2OH)3 ; tri-methylolpropane, CH3CH2C(CH2OH)3 ; glycerol, HOCH2CH(OH)CH2OH;thioglycerol, HSCH2CH(OH)CH2OH or HOCH2CH(SH)CH2OH ; butane-diol-1,2, butanediol-1,3 ; pentols, hexols and the like.
While a polyol residue constitutes a necessary part of the mercapto-esters according to the invention, they can also carry mono-alcohol residues; it is in fact recommendable to decrease the molecular weight of the ester when a polyacid is being used. In this case, part of the carboxyl groups of the polyacid can advanta-geously be esterified with a mono-alcohol; the latter is generally from C1 to C20 and preferably from C2 to C8. This precaution is useful particularly when the mercapto-ester could have a molecular weight greater than 1200.
By way of non-limitative examples of the mixed esters, reference can be made to :
Pentaerythrityl tris (3-mercapto-propionate)monocaprate C(CH2OCCH2CH2SH)3 CH2OC,(CH2)8 3 O O
Pentaerythrityl mono (2-mercapto-propionate)triscaproate C(cH2occH(sH)cH3~cH2oc(cH2)4cH373 O
Pentaerythrityl tris (3-mercapto-propionate~monostearate 35 17llOcH2c(cH2occH2cH2sH)3 O O
7.
1 Pentaerythrityl bis (3-mercapto-propionate)bispelargonate (H17C8CIOCH2)C(CH2OClCH2CH2SH)2 O O
Trimethylpropane bis (3-mercaptopropionate)monooctanoate H3ccH2c(cH2ollcH2c~2sH)2(cH2oll 7 15 O O
Ethylene-glycol 3-mercapto-propionate-laurate HscH2cH2clocH2cH2olcl(cH2)lO 3 O O
Pentaerythrityl bis (thioglycolate)bispalmitate CH2C CH2) 2C/CH20C(CH2) 14CH372 O O
Glyceryl bis (3-mercapto-propionate)mono-oleate CHOC,IC 2 2 l O
CH20,C, -C17H33 Glyceryl bls(3-mercaptopropionate)monooctanoate CH2Oç(cH2)6c 3 CHOCCH2CH2SH and/or CHOC(CH2)6CH3 l O l O
O O
Thioglyceryl mono (3-mercapto-propionate)monooctanoate CH2SH C,H2SH CH2OCCH2CH,SH
CHO2C(CH2)6C 3 and/or CHO2CH2CH2SH and/or CH-SH
CHo2ccH2cH2sH CHO2(CH2)6c 3 CH2Oc(cH2)6c 3 o The fatty compound or compounds which can advantageously be present in the composition of materials stabilized according to the invention is/are in general ~'5~7~39 C1 to C12 alkyl esters of ylycol and/or glycerol with one or more C8 to C24 Eatty acids, preferably unsaturated, which have undergone epoxidation. I-t is sui-table -to utilize for this purpose a natural oil, such as linseed, soya or Eish oil, which has been epoxidised.
The minimum molecular weigh-t oE the mixed mercapto-ester is 178, corresponding to the lightest acids, mercapto-acetic and acetic, and the lightest polyol, ethylene glycol; this "rninimal" mixed ester is:
Hs-cil2coo-cH2cH2-oocH3 The preferred minimum is 206, corresponding to ethylene 1-mercaptopropionate-2-propionate:
As regards a "heavy" ester, reference can be made for example to a mixed fatty mercapto-ester of a sugar, in particular glucose tris-Lmercatosteara-te~bis-stearate.
(~IS-C17 ~134coo~3 ~
~ C5H6CHO M=1608 (Cl7H3scOo)2 As regards the molecular weights of the mercapto-esters utilized, they can range from 178 to abou-t 2000 and preferably from 200 to 1000. Thus for example, pentaerythrityl bis-(mercapto-propiona-te)bis-octanoate, which gives excellent results, has a molecular weight oE
564.
The mixed ester used in the process of the invention must have at least one of the -OH groups of its polyol constituent es-terified by an organic acid not 3g - 8a -carrying an --S~-l group, while all or part of -the other -011 groups are esterified by a mercapto-acid. Conversely, mixed esters in which the molecule carries a single mercapto-acid are suitable for stabilization, where the o~her acid or acids is/are free from -Sll. In the commonest case of esters derived ~2~i7 9.
1 from polyols having 2 to 6 -O~ groups, there can be respectively 1 mercapto-acid residue per 1 to 5 acid residues without -S~ or reciprocally 1 non-mercapto-acid residue per 1 to 5 mercapto-acid residues.
Among the organic compounds of alkaline earth metals and various compounds of zinc, mention can be made particularly of the carboxylates, mercaptides and ZnC12.
Among the carboxylates, mention can be made in a non-limitative manner of the caproate, 2-ethyl-hexanoate, octanoate, perlargonate, laurate, palmitate, stearate, oleate, benzoate, phenate, alkyl-phenate, naph-thenate and neoalkanoate. Among the mercaptides, reference can be made to those derived from aliphatic mercaptans, mercapto-acid esters or mercaptoalkyl esters.
However, a certain number of derivatives such as the carbonate, oxide, hydroxide, sulphate, halide, (chloride, bromide) can also be used advantageously.
The invention, which applies to various halogeno-vinyl polymers and copolymers, particularly poly-vinyl chloride, polyvinylidene chloride, polyvinylacetochloride and superchlorinated polyvinyl chloride and chlorofluorovinyl resins etc, has, in particular, much importance for plastics materials based on polyvinyl chloride. As in the known art, the proportion of the primary stabilizer, which here is an alkaline earth metal organic compound jointly with a zinc organic compound, is generally from 0.01 to 6% by weight and most preferably from 0.05 to 3%, with respect to the resin to be stabilized.
When the mixed mercapto-ester according to the invention is employed as a co-stabilizer, i-ts proportion is within the same limits, without having to be equal to that of the primary stabilizer.
The Process is applied to plasticized poly-vinyl ch~o~ide containing an epoxidised oil, characterized ~z~ 9 - 9a -in that, by weight of resin, 0,1 to 3% of a mixed mercapto-ester is incorporated in conjunction with 0,005 to 1,5% of an organic Ca, Mg, Ba compound and 0,005 to 2,5% of a Zn compound.
In the particular case of polyvinyl chloride plasticized by the addition of a plasticizer constituted by an ~5~ r~ rl~
lt).
1 sehacate, azelate, phosphate or a polyester, the proportions per 100 parts by weight of the resin are preferably:
5 to 70 parts of plasticiser, 1 to 10 parts of fatty compounds, 0.1 to 2 parts of the al~aline earth metal organic compound, 0.05 to 1.5 parts of the Zn organic compound, 0.1 to 3 parts of the mixed mercapto-ester.
The ratio between the alkaline earth and zinc compounds is preferably from 1 to 6 moles of the first per 1 mole of the second. In the case of calci~, the best ratio ranges from 1 to 4 atoms Ca per 1 Zn.
In the non-limitative Examples which follow, samples of polyvinyl chloride stabilized with an additive according to the invention are subjected to discolouration tests on heating. For this, the various compositions are kneaded for 5 minutes at 160C on a roller mixer. The sheets obtained have a thickness of about 1 mm. The thermal test per se is effected in a furnace of the "SIGMA"
type manufactured by METRASTAT SA. Its principle is based upon evidence of the gradual change in the colour resulting from the thermal decomposition of long test pieces, in the Z5 form of strips 25 cm long, cut from the above-mentioned sheets and exposed temporarily to heat in a furnace maintained at a constant temperature~
Outside the thermal enclosure, the apparatus comprises an electromechanical system ensuring the transfer of a movable sample-carrying plate, leaving the furnace at a predetermined constant speed; an electronic assembly regulates the speed of the plate and also regulates the temperature of the furnace.
The discolouration of the resin is observed for a given furnace temperature and sample discharge ~5~3~
11 .
1 speed. For each test, the "stability time" is recorded, which is the time at which the resin becomes black or when the evolution of the yellow index is recorded. The compositions subjected to the tests comprise:
100 parts by weight of polyvinyl chloride known under the trade name "LACQVYI. S 111" having index K=67, and 40 parts by weight of dioctyl phthalate, (tr~ade name - PALATINOL AH) .
EXAMPLES 1 to 5 The tests fox thermal resistance are effected at 190C, the speed of discharge of the samples being regulated to 30 minutes.
In the results table below, the percentages indicate the proportions of additives incorporated in the samples, before passage through the furnace.
Example No 1 2 3 4 5 Pentaerythrityl tetrakis (3-mercapto-propionate) ... 0 0.4% 0 0 0 20 Pentaerythrityl bis (3-mercapto-propionat,e) bis octanoate ... 0 0 0.4~ 0 0.4%
Epoxidised soya oil ... 0 0 0 4% 4%
Yellow index after 2D minutes ...160 135127 155 90 The first conclusion given by these results is that the mixed mercapto-ester of Example 3 (bis-bis), despite its -SH content of only half that of the corres-ponding tetrakis (Example 2), has an effectiveness at least as good as the latter or even slightly better; the yellow index is 127 as against 135. The use of this mixed compound is thus more economical.
The second interesting result obtained from Example 4 and 5 is that, in the presence of epoxidised soya oil, the mixed mercapto-ester (Example 5) acts strongly 13~
12, 1 to reduce the yellow index from 150 to 90.
EXAMPLES 6 to 10 Association of a mixed mercapto-ester with standard stabilizers based on metal compounds. Tests at 5 190C.
Example No. 6 7 3 9 10 -Sample discharge speed, mn ......... 30 30 30 60 60 Zn octanoate % ..Ø08 0.08 0.08 0.08 0.08 Ba octanoate % ... - - - 0.80 0.80 10 Pentaerythrityl tetrakis (3-mercapto-propionate) ... - 0.4 Pentaerythrityl bis (3-mercapto-propionate)-bis octanoate ... _ 0.4 _ 0,4 Stability time, mn ...15 18 18 43 53 As in the foregoing tests, the mixed mercapto-ester (bis-bis) of Examples 8 and 10 proves to be more effective than the mercapto-ester (tetrakis) of Example 7, although it contains half the number of -SH groups of the latter.
Association of the mixed compound with standard Ba and Zn stabilizers (Examples 9 to 10), shows an improvement in the stability of (53-43):43 = 23.2 which is very appreciable.
EXAMPLES 11 to l9 Operation is as in the foregoing Examples, but a proportion of plasticizer, dioctyl phthalate, is used which is 50 parts by weight per 100 parts of resin, the latter containing 5% of epoxidised soya oil, 0.3%
of Ca stearate and 0.15% of Zn stearate. The stabilities at 190C in minutes have been found by the addition of various mercapto-esters.
13 .
1 EXAMPLE ADDITIVE Stahility ~ ~ constitution mn 11 Nil 160 12 0.5 Pentaerythrityl tetra (3-mercapto-propionate) 203 13 1.0 " " 227 14 1.0 Pentaerythrityl bis (3-mercapto-propionate)bis-octanoate 226 1.0 Pentaerythrityl tetra (11-mercapto-undecanoate) 225 16 1.0 Pentaerythrityl tris (11-mercapto-undecanoate) mono-undecanoate 226 15 171.0 Propyleneglycol bis-mercapto-acetate 189 181.0 Propyleneglycol mercapto-acetate-hexanoate 194 191.0 Ethyl ll-Mercapto-undecanoate 176 20These tests show the possibility of increasing the stability by about 30% (from 160 to 226) by using in conjunction a mixed mercapto-ester with a standard stabilizer system which comprises an epoxidised oil and Ca and Zn stearates.
The foregoing results confirm the surprising advantage of the mixed mercapto ester over an ordinary mercapto-ester. Thus Example 14 (mixed ester) gives a result as good as that of Example 13, mercapto alone, despite its lower -SH content. As the latter is less than half that of the compound of Example 13, it would be better to compare Example 14 with 12 which contains 0.5%
of the mercapto-ester; however the stability in th~s case is 203 minutes as against 226 for the additive according to the invention (Example 14).
The same conclusion can be drawn on the sub~ect 14.
1 of the respective Examples 15-16 and 17-18; it is to be noted in passing that the mercapto-acetate of the prior art (Example 17) gives an odour to the resin.
Example 19 shows that a mercapto-ester of a mono- alcohol is less efficient than mercapto-esters of polyols.
EXAMPLES 20 to 23 By applying the technique of the foregoing Examples to the same composition of polyvinyl chloride with 50% of dioctyl phthalate and 5~ of epoxidised soya oil, the nature and proportions of the stabilizers have been varied. Examples 20 to 22 show the use of Ca and Zn compounds, while Example 23 utilizes stab.ilisers of the prior art based on Cd and Ba, considered to be particularly effective.
Example No 20 21 2~ 23 _ Stabilisers additive ~
Ca Laurate 0.6 - - -Ca Stearate ~0.30 0-30 Zn Stearate 0.15 0.15 - -Zn Mercaptide Zn(scH2cH2coo~l C12H25)2 0.15 Cd Stearate 25 Ba Stearate - ~ , 1.50 Pentaerythrityl bis ~3-mercapto-propionate)bis-octanoate 0.501.0 0.2 Stability in minutes 241226 230 250 These results demonstrate that, due to the addition of the mercapto-ester, a stabilization equivalent to that provided by the known Cd, Ba system is attained;
plus the advantage of avoiding all toxicity due to heavy metals together with a much lower cost.
i7~a39 I!L ~
15.
1 EX~MPLES 24 $o 26 .
The resin composition comprising, per 100 parts of polyvinyl chloride, 50 parts of dioctyl phthalate and 5 parts of epoxidised soya oil is utilized with; 0.6% of Ba laurate and 0.15% of Zn steaxate as standard stabilizers.
The furnace was regulated to 190 C with a sample discharge speed of 180 minutes. The following stabilities are found with each of the co-stabilizers employed for 3 different concentrations of the latter.
Example No % O 0.1 0.2 0.5 24 Pentaerythrityl bis (3-mercapto-propionate) bis-pelargonate 105 119 124 139 Pentaerythrityl bis (3-mercapto-propionate) bis-octanoate 105 117 131 153 26 Pentaerythrityl tetra (3-mercapto-propionate) 105 108 122 131 _ Thus, with 0.5% of the co-stabilizer in Example 24, there is an increase in stability of 139-105 = 34 or (34:105)100 = 32.3%
and in Example 25 153-105 = 48 or (48:105)100 = 45.7%
as against 131-105 = 26 or (26:105)100 = 24.8% only, with the normal mercapto-ester of Example 26.
Examples 8 and 10 are repeated with ZnC12 in place oE Zn octanoate. In practice, the same results are obtained.
EXAMPLES 28 and 29 As in the foregoing Examples, mixtures are used of 100 parts of the same polyvinyl chloride with 50 ~5 :16.
1 parts of dioctyl phthalate, 5 parts of epoxidised soya oil, 0.6 part of Ba octanoate and 0.04 part of ZnC12.
Operating at 190C, the samples are discharged in 180 minutes. Stability times found:
S Example 28 without other additive 84 mn Example 29 + 1 part of pentaerythri~yl bis(3-mercapto-propionate)-bis-octanoate 137 mn or an improvement of 60%.
Test on non-plasticized polyvinyl chloride only containing pentaerythrityl bis(3 mercapto-propionate)-bis-octanoate. The press was operated at 160C. The yellow index found: 90 against 101 for a control without additive.
Claims (15)
1. A process for the thermal stabilization of a halo-geno-vinyl resin, which comprises incorporating into the resin a mixture of:
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mercapto alkonoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups,este-rified by a sulfur-free organic acid;
b) at least one stabilizing metal compound whose metal is selected from groups IIB, IIIA, IVA, and VA of the Periodic Classification of the Elements, and c) at least one alkaline earth metal organic compound.
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mercapto alkonoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups,este-rified by a sulfur-free organic acid;
b) at least one stabilizing metal compound whose metal is selected from groups IIB, IIIA, IVA, and VA of the Periodic Classification of the Elements, and c) at least one alkaline earth metal organic compound.
2. The process of claim 1, wherein the mercapto-alka-noic acid from which the mixed ester is derived, is of the for-mula (HS)n- R-(COOH)m where n has a value from 1 to 5, m = 1 or 2, R is a C1 to C35 aliphatic chain or a ring.
3. The process of claim 2, wherein the sulfur-free organic acid from which the mixed ester is derived is a mo-no- or di-acid of the formula:
R' (CO2H)p where p is 1 or 2 and R' is an alkyl or alkenyl group containing at least 2 carbon atoms or an aromatic group.
R' (CO2H)p where p is 1 or 2 and R' is an alkyl or alkenyl group containing at least 2 carbon atoms or an aromatic group.
4. The process of claim 3, wherein R' contains from 5 to 37 carbon atoms.
5. The process of claim 4, wherein that the sulfur-free organic acid is a C6 to C18 fatty acid.
6. The process of claim 1, 2 or 3, wherein the polyol from which the mixed ester is derived, comprises a C2 to C30 chain or ring carrying from 2 to 6 hydroxyl groups.
7. The process of claim 1, 2 or 3, characterized in that the mixed ester contains one residue of mercapto-alkanoic acid per one to five residue(s) of sulfur-free organic acid.
8. The process of claim 1, 2 or 3, wherein the mixed ester contains one residue of sulfur-free organic acid per one to five residues of mercapto-alkanoic acid.
9. The process of claim 1, 2 or 3, wherein the mixed ester has a molecular weight of from 178 to 2000.
10. The process of claim 1, 2 or 3, wherein the mixed mercapto-ester has a molecular weight of from 200 to 1000.
11. The process of claim 1, 2 or 3, applied to plas-ticized polyvinyl chloride containing an epoxidized oil, wherein the mixture incorporated to the resin comprises:
0.1 to 3% by resin weight of said mixed ester;
0.05 to 2.5% by Resin weight of Zn compounds as said stabilizing metal compound; and 0.05 to 1.5% by resin weight of an organic Ca, Mg, or Ba compound as said alkaline earth metal organic compound, the ratio of the alkaline earth metal in the mixture being of 1 to 3 atoms per atom of Zn.
0.1 to 3% by resin weight of said mixed ester;
0.05 to 2.5% by Resin weight of Zn compounds as said stabilizing metal compound; and 0.05 to 1.5% by resin weight of an organic Ca, Mg, or Ba compound as said alkaline earth metal organic compound, the ratio of the alkaline earth metal in the mixture being of 1 to 3 atoms per atom of Zn.
12. A process for the thermal stabilization of a halogeno-vinyl resin, which comprises incorporating into the re-sin a mixture of:
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having at least two but not all the hydroxyl groups of its polyol constituent esterified by the mercapto-alkanoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, este-rified by a sulfur-free organic acid;
b) at least one stabilizing metal compound whose metal constituent is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of the Elements; and c) at least one alkaline earth metal organic compound.
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having at least two but not all the hydroxyl groups of its polyol constituent esterified by the mercapto-alkanoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, este-rified by a sulfur-free organic acid;
b) at least one stabilizing metal compound whose metal constituent is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of the Elements; and c) at least one alkaline earth metal organic compound.
13. A process for the thermal stabilization of an ha-logeno-vinyl resin, which comprises incorporating into the resin a mixture of:
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mer-capto-alkanoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, esterified by a sulfur-free organic acid, with the proviso that said polyol constituent is not ethylene glycol, diethylene glycol and gly-cerol;
b) at least one stabilizing metal compound whose metal constituent is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of Elements; and c) at least one alkaline earth mental organic compound
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having one part only of the hydroxyl groups of its polyol constituent esterified by the mer-capto-alkanoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, esterified by a sulfur-free organic acid, with the proviso that said polyol constituent is not ethylene glycol, diethylene glycol and gly-cerol;
b) at least one stabilizing metal compound whose metal constituent is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of Elements; and c) at least one alkaline earth mental organic compound
14. A process for the thermal stabilization of a halogeno-vinyl resin, which comprises incorporating into the resin a mixture of:
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having at least two but not all the hydroxyl groups of its polyol constituent esteri-fied by the mercapto-alkanoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, esterified by a sulfur-free organic acid, with the proviso that said polyol constituent is not ethylene glycol, diethylene glycol and glycerol;
b) at least one stabilizing metal compound whose metal constituent is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of the Elements; and c) at least one alkaline earth metal organic compound.
a) at least one polyol mercapto-alkanoic acid ester of the mixed type, said mixed ester having at least two but not all the hydroxyl groups of its polyol constituent esteri-fied by the mercapto-alkanoic acid and all the other hydroxyl groups of its polyol constituent, or a part of said other groups, esterified by a sulfur-free organic acid, with the proviso that said polyol constituent is not ethylene glycol, diethylene glycol and glycerol;
b) at least one stabilizing metal compound whose metal constituent is selected from groups IIB, IIIA, IVA and VA of the Periodic Classification of the Elements; and c) at least one alkaline earth metal organic compound.
15. The process of claim 12, 13 or 14, applied to plasticized polyvinyl chloride containing an epoxidized oil, wherein the mixture incorporated to the resin comprises:
0.1 to 3% by resin weight of said mixed ester;
0.05 to 2.5% by resin weight of a Zn compound as said stabilizing metal compound; and 0.05 to 1.5% by resin weight of an organic Ca, Mg, or Ba compound as said alkaline earth metal organic compound, the ratio of alkaline earth metal in the mixture being of 1 to 3 atoms per atom of Zn.
0.1 to 3% by resin weight of said mixed ester;
0.05 to 2.5% by resin weight of a Zn compound as said stabilizing metal compound; and 0.05 to 1.5% by resin weight of an organic Ca, Mg, or Ba compound as said alkaline earth metal organic compound, the ratio of alkaline earth metal in the mixture being of 1 to 3 atoms per atom of Zn.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8312691A FR2550213B1 (en) | 1983-08-02 | 1983-08-02 | PROCESS FOR THE THERMAL STABILIZATION OF HALOGENO-VINYL POLYMERS AND RESINS THUS STABILIZED |
| FR8312691 | 1983-08-02 | ||
| FR8411347A FR2567898B2 (en) | 1984-07-18 | 1984-07-18 | PROCESS FOR THE THERMAL STABILIZATION OF HALOGENO-VINYL POLYMERS AND RESINS THUS STABILIZED |
| FR8411347 | 1984-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1257439A true CA1257439A (en) | 1989-07-11 |
Family
ID=26223544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000460174A Expired CA1257439A (en) | 1983-08-02 | 1984-08-01 | Process of thermal stabilization of halogeno-vinyl polymers and the resines so stabilized |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0133130B1 (en) |
| AR (1) | AR240465A1 (en) |
| AU (1) | AU570990B2 (en) |
| CA (1) | CA1257439A (en) |
| DE (2) | DE133130T1 (en) |
| DK (1) | DK373484A (en) |
| ES (1) | ES8600350A1 (en) |
| PT (1) | PT79011B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6462116B2 (en) | 1998-09-16 | 2002-10-08 | Morton International, Inc. | Combination of an organothio compound and a zinc mercapto ester as a heat stabilizer in PVC processing |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0365483B1 (en) * | 1988-10-20 | 1993-12-29 | Ciba-Geigy Ag | Mercaptobenzoic-acid esters used as stabilizers for chlorine-containing polymers |
| US6762231B2 (en) * | 2000-12-15 | 2004-07-13 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
| US6927247B2 (en) | 2000-12-15 | 2005-08-09 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
| US7312266B2 (en) | 2000-12-15 | 2007-12-25 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3144422A (en) * | 1962-01-03 | 1964-08-11 | Carlisle Chemical Works | Polyolefins stabilized with pentaerythritol mercapto esters |
| EP0001631A1 (en) * | 1977-10-26 | 1979-05-02 | Ciba-Geigy Ag | Mercaptans on solid carriers and their application in the stabilisation of synthetic thermoplastic materials that contain chlorine |
| FR2492391A1 (en) * | 1980-10-20 | 1982-04-23 | Rhone Poulenc Ind | Synergistic heat stabilisers for PVC - contg. organo-zinc cpd., organic deriv. of Gp.=IIA metal and thioglycolic acid ester |
-
1984
- 1984-07-26 DE DE1984401567 patent/DE133130T1/en active Pending
- 1984-07-26 EP EP19840401567 patent/EP0133130B1/en not_active Expired
- 1984-07-26 DE DE8484401567T patent/DE3468037D1/en not_active Expired
- 1984-07-30 ES ES534715A patent/ES8600350A1/en not_active Expired
- 1984-07-30 AU AU31284/84A patent/AU570990B2/en not_active Ceased
- 1984-08-01 DK DK373484A patent/DK373484A/en not_active Application Discontinuation
- 1984-08-01 AR AR29741684A patent/AR240465A1/en active
- 1984-08-01 CA CA000460174A patent/CA1257439A/en not_active Expired
- 1984-08-01 PT PT7901184A patent/PT79011B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6462116B2 (en) | 1998-09-16 | 2002-10-08 | Morton International, Inc. | Combination of an organothio compound and a zinc mercapto ester as a heat stabilizer in PVC processing |
Also Published As
| Publication number | Publication date |
|---|---|
| ES534715A0 (en) | 1985-10-16 |
| PT79011B (en) | 1986-08-22 |
| AR240465A1 (en) | 1990-04-30 |
| DE133130T1 (en) | 1985-08-29 |
| ES8600350A1 (en) | 1985-10-16 |
| DK373484A (en) | 1985-02-03 |
| DE3468037D1 (en) | 1988-01-21 |
| EP0133130B1 (en) | 1987-12-09 |
| AU3128484A (en) | 1985-02-07 |
| PT79011A (en) | 1984-09-01 |
| EP0133130A1 (en) | 1985-02-13 |
| DK373484D0 (en) | 1984-08-01 |
| AU570990B2 (en) | 1988-03-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |