Europaisches Patentamt

(19) 3 European Patent Office

Office europeen
een des brevets
brevets EP 0 945 485 A1

(12) E U R O P E A N PATENT A P P L I C A T I O N

(43) Date of publication: (51) |nt CI * C08K 13/02, C08L 2 7 / 0 6

29.09.1999 Bulletin 1999/39 // (C08K13/02, 3:16, 5 : 0 9 8 ,
5.37)
(21) Application number: 99302322.5

(22) Date of filing: 25.03.1999

(84) Designated Contracting States: • Adams, Paul Brian

AT BE CH CY DE DK ES Fl FR GB GR IE IT LI LU Indian Springs, Ohio 4501 1 (US)
MC NL PT SE • Norris, Gene Kelly
Designated Extension States: Cincinnati, Ohio 45249 (US)
AL LT LV MK RO SI
(74) Representative:
(30) Priority: 26.03.1998 US 48492 Bankes, Stephen Charles Digby et al
13.08.1998 US 133605 BARON & WARREN
18 South End
(71) Applicant: MORTON INTERNATIONAL, INC. Kensington
Chicago, Illinois 60606 (US) London W8 5BU (GB)

(72) Inventors:
• Duvall, Tod Charles
West Chester, Ohio 45069 (US)

(54) A latent mercaptan as a heat stabilizer

(57) Flexible, semi-rigid, and rigid vinyl chloride pol- bilizers such as zinc carboxylates and organotin carbox-
ymer compositions comprising a latent mercaptan-con- ylates and mercaptides in the polymer composition.
taining heat stabilizer are substantially free from the of- Other products of the degradation are believed to in-
fensive odour typically associated with mercaptans and clude carbocations of the blocking moiety which are sta-
are protected during processing by the degradation bilized by a molecular structure in which the electron de-
products of the latent (i.e., blocked) mercaptan which ficiency is shared by several groups. The latent mer-
include a free mercaptan. The free mercaptan thus re- captan is selected from a 2-S-(tetrahydropyranyl)-thio-
leased enhances the activity of metallic-based heat sta- alkanol, a carboxylic acid ester thereof, a 2-S-(tetrahy-
dropyranyl)-thioglycolic acid, and an ester thereof.

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 EP 0 945 485 A1

Description

FIELD OF THE INVENTION

5 [0001] This invention relates to a heat stabilized halogen-containing polymer composition normally susceptible to
heat-induced deterioration which comprises a halogen-containing polymer and the degradation products of a latent
mercaptan present during processing of the composition at an elevated temperature, said products being formed during
said processing and including a liberated mercaptan. The free mercaptan enhances the activity of metal-based heat
stabilizers such as organotin carboxylates and mercaptides in the polymer composition. It particularly relates to the
10 stabilization against heat of vinyl chloride polymer compositions and articles made thereof by a latent mercaptan se-
lected from the group consisting of 2-S-(hydroxyalkylthio)tetrahydropyran, 5-S-(hydroxyalkylthio) tetrahydrofuran, and
the carboxylic acid esters thereof in combination with very low levels of a metal-based heat stabilizer or certain Lewis
acids. Said latent mercaptans are also referred to hereinafter as 2-S-(tetrahydropyranyl)-thioalkanol, 2-S-(tetrahydro-
pyranyl)thioalkyl carboxylate, and their furanyl homologs, i.e., 5-S-(tetrahydrofuranyl)-thioalkanol and 5-S-(tetrahydro-
15 furanyl)thioalkyl carboxylate.
[0002] This invention also relates to articles of manufacture such as rigid pipe and window profile, flexible film, and
semi-rigid tubing that are prepared from such heat-stabilized vinyl chloride polymer compositions.

BACKGROUND OF THE INVENTION

20
[0003] It is well known that the physical properties of various organic polymers deteriorate and color changes take
place during processing of the polymer and during exposure of formed polymer products to certain environments.
Halogen-containing polymers are normally susceptible to heat-induced deterioration through autoxidation. The prime
examples of such polymers are the vinyl and vinylidene polymers in which the halogen is attached directly to carbon
25 atoms. Polyvinyl chloride), copolymers of vinyl chloride and vinyl acetate, and poly(vinylidene chloride), the principal
resin in self-clinging transparent food wraps, are the most familiar polymers which require stabilization for their survival
during fabrication into pipe, window casings, siding, bottles, wall covering, packaging film, and the like. When such
polymers are processed at elevated temperatures, undesirable color changes often occur within the first 5 to 10 minutes
as well as during later stages of the processing. Haziness, which sometimes accompanies the color changes, is par-
se* ticularly undesirable where clear products are needed. The addition of heat stabilizers to such polymers has been
absolutely essential to the wide-spread utility of the polymers. From a great deal of work in the development of more
and more effective heat stabilizers there has emerged two principal classes: organotin compounds and mixed metal
combinations. Organotin-based heat stabilizers are the most efficient and widely used stabilizers for rigid PVC. Syn-
ergistic combinations of alkyltin mercaptides and free mercaptans are particularly efficient heat stabilizers for rigid PVC
35 during extrusion. They have not been entirely satisfactory, however, because of several failings on the part of the
mercaptan synergist and are not used in flexible PVC. Many mercaptans give off an offensive odor even at room
temperature and the odor grows worse at PVC processing temperatures. The oxidative stability of the mercaptans is
very often very poor. Oxidation of the free mercaptans diminishes the synergism. A combination having an enhanced
synergism would be welcomed especially by the flexible PVC industry. Also, because of the end-use of articles made
40 from some polymers, many polymeric compositions require the presence of both biocides and heat stabilizers but the
use of the organotin mercaptide/mercaptan combination in such a composition is often frustrated by the tendency of
the free mercaptan to deactivate a biocide such as the much used OBPA (10, 10'-oxybisphenoxarsine).
[0004] Zinc salts in general have long been believed to be less satisfactory as heat stabilizers for halogen-containing
polymers than the organotin-based stabilizers and, indeed, have lent their name to the catastrophic degradation known
45 as zinc burn. In U.S. Patent No. 3,660,331 , Ludwig teaches the stabilization of vinyl halide resins by certain thioethers
and thioesters of tetrahydropyran. Better heat stabilizer compositions are still needed, however. The thioether/low level
metallic stabilizer combinations of this invention satisfy that need.

SUMMARY OF THE INVENTION

50
[0005] It has now been found that the activity of the 2-S-(tetrahydropyranyl)thioalkanol, the carboxylates thereof,
and their furanyl homologs as heat stabilizers in halogen-containing polymer compositions is unexpectedly higher than
that predicted on the basis of sulfur content when used in conjunction with very low levels of a metal-based stabilizer
or a Lewis acid. Zinc salts are particularly valuable as synergists of latent mercaptans in their function as heat stabilizers
55 for halogen-containing polymers. Zinc chloride, a Lewis acid, is of particular interest as such a synergist.
[0006] It is an object of this invention, therefore, to provide a heat stabilizer composition having the synergy of a
mercaptan plus improved oxidative stability.
[0007] It is another object of this invention to provide a halogen-containing polymer composition stabilized against

2
 EP 0 945 485 A1

heat by 2-S-(tetrahydropyranyl)thioalkanols, carboxylates thereof, and their furanyl homologs in combination with a
synergistic amount of a metal-based stabilizer or a Lewis acid.
[0008] It is another object of this invention to provide a PVC composition and article stabilized against heat by 2-S-
(tetrahydropyranyl) thioalkanols, carboxylates thereof, and their furanyl homologs in combination with a synergistic
5 amount of a metal-based stabilizer or a Lewis acid.
[0009] It is a related object of this invention to stabilize rigid, semi-rigid, and flexible PVC resin compositions with a
heat stabilizer composition of this invention.
[0010] It is another object of this invention to provide a latent mercaptan-containing heat stabilizer composition which
is substantially free from the offensive odor typically associated with mercaptans.
10 [0011] It is still another object of this invention to provide a flexible PVC composition and article stabilized against
heat by a 2-S-(tetrahydropyranyl)thioalkyl carboxylate, its furanyl homolog, or a mixture thereof, in combination with a
synergistic amount of a zinc salt.
[0012] These and other objects of the invention which will become apparent from the following description are
achieved by adding a 2-S-(tetrahydropyranyl)thioalkanol, a carboxylate thereof, a furanyl homolog of either or both, or
is a mixture of two or more of said alkanols and esters, and a synergistic amount of a metal-based heat stabilizer or Lewis
acid or a mixture of said metal-based heat stabilizer and Lewis acid to a halogen-containing polymer composition and
processing the composition at an elevated temperature at which the latent mercaptan degrades to liberate a free
mercaptan. The terms "latent mercaptan" and "blocked mercaptan" are used interchangeably herein.
[001 3] Other products of the degradation of the blocked mercaptan are believed to include carbocations of the block-
20 ing moiety which are stabilized by a molecular structure in which the electron deficiency is shared by several groups.
Resonance stabilization and neighboring group stabilization are two of the possible mechanisms by which the carbo-
cations may be stabilized. The carbocations act as intermediates in the formation of stable compounds early in the hot
processing of halogen-containing polymers. Although such mechanisms and the resultant carbocations are believed
to be an impetus for the liberation of the active free mercaptan, this invention is in no way limited by the foregoing
25 attempt to explain the working of the invention. Those skilled in the art will see the resonance stabilization and neigh-
boring group stabilization that are possible in the following structures of the blocked mercaptan; other mechanisms
maybe at work in other blocked mercaptans represented by these structures that also liberate an active free mercaptan
upon thermal and/or chemical degradation during processing of polymeric compositions containing such blocked mer-
captans. For the purposes of this invention, the terms "blocked mercaptan" and "latent mercaptan" are used inter-
so changeably to mean a thioether which degrades during processing of the composition at an elevated temperature to
liberate a free mercaptan.

DETAILED DESCRIPTION OF THE INVENTION

35 [0014] The term halogen-containing organic polymers as used herein means halogen-containing polymers or resins
in which the halogen is attached directly to the carbon atoms. The halogen-containing polymers which can be stabilized
according to this invention include chlorinated polyethylene having 14 to 75%, e.g. 27%, chlorine by weight, chlorinated
natural and synthetic rubber, rubber hydrochloride, chlorinated polystyrene, chlorinated polyvinyl chloride, polyvinyl
bromide, polyvinyl fluoride, and vinyl chloride polymers. The vinyl chloride polymers are made from monomers con-
40 sisting of vinyl chloride alone or a mixture of monomers comprising, preferably, at least about 70% by weight of vinyl
chloride, based on the total monomer weight. Examples of the copolymers include those made from vinyl chloride and
from about 1 to about 30% of a copolymerizable ethylenically unsaturated material such as vinyl acetate, vinyl butyrate,
vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarates and maleates, vinyl propi-
onate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl meth-
45 acrylate, butyl methacrylate and other alkyl methacrylates, methyl alpha-chloroacrylate, styrene, trichloroethylene, vinyl
ketones such as vinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-2-chloroethylene, acrylonitrile, chloroacrylonitrile,
allylidene diacetate, chloroallylidene diacetate, and vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether, vinyl
phenyl ether, and the vinyl ether prepared by the reaction of one mole of acrolein with one mole of ethylene glycol
divinyl ether. Typical copolymers include vinyl chloride-vinyl acetate (96:4 sold commercially as VYNW), vinyl chloride-
50 vinyl acetate (87:13), vinyl chloride-vinyl acetate-maleic anhydride (86:13:1), vinyl chloride-vinylidene chloride (95:5);
vinyl chloride-diethyl fumarate (95:5), and vinyl chloride 2-ethylhexyl acrylate (80:20).
[0015] As used herein, the term PVC composition means a composition comprising a halogen-containing vinyl pol-
ymer in which the halogen is attached directly to a carbon atom. A rigid PVC composition is one which does not contain
a plasticizer. A semi-rigid PVC composition is one which contains from 1 to about 25 parts of a plasticizer per 100 parts
55 by weight of the halogen-containing vinyl polymer. A flexible PVC composition contains from about 25 to about 100
parts per 100 parts by weight of the halogen-containing vinyl polymer. Alkyl esters of carboxylic acids in which there
are from 1 to 3 alkyl groups having from 8 to 12 carbon atoms are representative of the plasticizers. The alkyl group
may be n-octyl, 2-ethylhexyl, nonyl, decyl, or dodecyl. Suitable esters include phthalates, trimellitates, benzoates,

3
 EP 0 945 485 A1

adipates, glutarates, and sebacates. The plasticizer may also be a pentaerythritol or such an ester thereof. A polymeric
plasticizer is also suitable.
[0016] As used herein, a hydrocarbyl radical contains from 1 to 20 carbon atoms and may be an alkyl, cycloalkyl,
aryl, arylene, alkaryl, aralkyl, or an aralkenyl or alkenyl radical having up to 3 ethylene double bonds; likewise, said
5 radicals constitute the hydrocarbyl portion of a hydroxyhydrocarbyl radical. As used herein: a mono-valent radical has
but one valence available for combining with another radical whereas a di-valent radical may combine with two other
radicals; the term alkyl represents monovalent straight or branched chain hydrocarbon radicals ; the term alkylenyl
represents divalent, trivalent, and tetravalent straight or branched chain hydrocarbon radicals; the term oxyalkylenyl
represents a divalent radical of a polyalkylene ether molecule having a polyalkoxy chain of from 2 to 4 of such radicals,
10 wherein the alkylene moiety has 2 or 3 carbon atoms.
[0017] Also, as used herein: an acyloxyalkyl radical originates from a carboxylic acid ester of an alkyl alcohol; the
R1 radical in Formula 1 below, therefore, in the stearic acid ester of mercaptopropanol is the stearoyloxypropyl radical;
likewise, the R1 radical of the oleic acid ester of mercaptopropanol, which is one of the tallate esters of that alcohol, is
the oleoyloxypropyl radical. The R1 radical of lauryl-3-mercaptopropionate, on the other hand, is dodecyloxycarbonyl-
15 propyl.
[0018] Substantially means largely if not wholly that which is specified but so close that the difference is insignificant.
[0019] The stabilizer compositions of this invention consist essentially of from about 87.5 % to about 98.5%, prefer-
ably from about 93.5 % to about 97.5 %, by weight of a 2-S-(tetrahydropyranyl)thioalkanol, a 2-S-(tetrahydrofuranyl)
thioalkanol, a carboxylate of either or both, or a mixture of two or more of said alkanols and esters, based on the total
20 weight of the stabilizer composition, the balance comprising the metal-based stabilizer or Lewis acid. They are partic-
ularly suited to impart superior stabilization against the deteriorative effects of heat and ultra-violet light on both rigid
and flexible PVC resins in comparison with stabilizer compositions previously known in the art. They may be prepared
by blending the components thereof in any convenient manner which produces a homogeneous mixture, such as by
shaking or stirring in a container. Likewise, the stabilizer compositions of th is invention can be incorporated in a halogen-
25 containing polymer by admixing the components of the stabilizer composition and of the polymer composition, such
as, for example, in an appropriate mill or mixer or by any other of the well-known methods which provide uniform
distribution of the stabilizer throughout the polymer composition.
[0020] One of the advantages of this invention is that the offensive odor of mercaptans is masked by a blocking
group so that the latent mercaptan thus created may be put into a PVC composition or the like with little or no offense
30 to the operator with the knowledge that the free mercaptan will be released as a degradation product when the treated
composition is heated during the usual processing, e.g. extrusion.
[0021] The blocking compounds are preferably those which are capable of furnishing a stabilized carbocation having
a molecular structure in which the electron deficiency is shared by several groups. Resonance stabilization and neigh-
boring group stabilization are two of the possible mechanisms by which the carbocations may be stabilized.
35 [0022] The blocked mercaptans suitable for the purposes of this invention are represented by FORMULA 1:

40 r4 TrI

(R ) -X- -R1 FORMULA 1

Lr3J„
45

wherein a is 1, m is 0, n is 0 or 1; y is 1 or 2, and z is 1; R1 is a hydroxyalkyl group, a hydroxy(polyalkoxy)alkyl group,

so an acyloxyalkyl group, an acyloxy(hydroxyalkyl) group, acyloxy(alkoxyalkyl) group, an alkylene bis-(acyloxyalkyl)
group, a hydroxy(polyalkoxy) acylalkyl group, an acyloxy(polyalkoxy)alkyl group, an oxy[bis(alkoxyacylalkyl)] group,
an oxy[bis(polyalkoxyacylalkyl] group, a benzoyloxy(polyalkoxy)alkyl group, or a benzoyloxy(polyalkoxy)acylalkyl
group, in which the alkyl moieties have from 2 to 20 carbon atoms, and the acyloxy moiety has from 2 to 22 carbon
atoms; R2, R3, R4, and R5 are hydrogen; and either R3 or R5 is joined with R7 and O to form a heterocyclic moiety
55 having 4 or 5 ring carbons with or without an alkoxy (C-1-C4), aryloxy (C6-C10), alkaryloxy (C7-C14) orformyl substituent.
[0023] The mercaptans useful in this invention are the well-known mercaptoalkanols and mercaptocarboxylic acids
and the esters of each. They include, but are not limited to, the following compounds:

4
 EP 0 945 485 A1

HS— CH— (CH)i — R10 (MCI)

R11 R19

O OH O ((MC3)]
I II
HS— CH— (CH)
i —O—C—CH2 — —C—O— ( CH)
i —CH—SH
JL11 i n J 2 in Jn
R R R" R"

wherein R10 and R19 are independently OH, -0(C=0)R17

-(C=0)OR17, -SH, aryl, C, to C18 alkyl, and -H;

R11 is -H, aryl, or C-, to C18 alkyl;

R17 is -H, alkyl, alkenyl, aryl, aralkyl, alkaryl, cycloalkyl, or cycloalkylenyl;

wherein i=0 or an integer from 1 to 6 inclusive.

[0024] Mercaptan-containing organic compounds preferred as intermediates in the preparation of the latent mer-
captans of this invention are those compounds according to formula (MC1) where R11 is -H, R19 is -H, R10 is -0(C=0)
R17 or -(C=0)OR17, and i=1 ; and those compounds according to formula (MC3) where R11 is -H and i=1 .
[0025] Examples of mercaptan-containing compounds described by the above formulas include, but are not limited
to, the following compounds:

HSCH2CH2OH

HSCH2CH2CH2OH

HSCH2COOH

HSCH2COOC8H17

HSCH2CH2CH2CH(OH) CH2CH(OH)

HSCH2CH2OC(=0) C17H33

HSCH2CH2CH2OC(=0) C8H17

HSCH2CH2OC (=0) CH=CHC (0=) OCH2CH2SH

HSCH2CH2OC(=0) Cn\-\23

HSCH2CH2OC(=0) CH2CH2C(=0) OCH2CH2SH

 EP 0 945 485 A1

HSCH2CH2OC(=0) (CH2)4C(=0)OCH2CH2SH

HSCH2CHOC(=0) CH3

C9H19

10

CH2CH2OC ( =0 ) CH2 -C ((OH)

OH ) C ((=0)
=0 ) OCH2CH2SH
J 2
15
[0026] In general, the procedure for making the latent mercaptans which are useful in this invention comprises adding
the mercapto group of the free mercaptan across the double bonds of polarized, unsaturated compounds is as follows:
[0027] To a stirred mixture, under nitrogen atmosphere, of the mercaptan, acid catalyst, and optionally, a small per-
centage of antioxidant to inhibit radical reactions, is added dropwise to the polarized, unsaturated compound, either
20 neat or in solution, while maintaining the temperature between 10° -70° C. The mixture or solution is then heated for
between 1 and 6 hours at 35° -70° C and conversion to product is monitored by gas chromatography and iodine titration
for SH. The acid catalyst is removed by an alkaline wash and the resulting product is dried with magnesium sulfate
and filtered. The solvent, if required, is removed under reduced pressure at <50° C to yield the latent mercaptan. A
solid phase catalyst may be used and then filtered out of the reaction mixture and regenerated for use in a subsequent
25 synthesis, In this way, a wash step is eliminated.
[0028] The polarized, unsaturated compounds are exemplified by 3,4-dihydropyran; 3,4-dihydro-2-methoxy-2H-
pyran; 3,4-dihydro-2-ethoxy-2H-pyran; 3,4-dihydro-2-phenoxy-2H-pyran; 3,4-dihydro-2-formyl-2H-pyran; and 2,3-di-
hydrofuran. The 3,4-dihydro-2-formyl-2H-pyran is made by the Diels-Alderdimerization of acrolein at high temperatures
and pressures. The 3,4-dihydro-2-alkoxy-2H-pyrans and 3,4-dihydro-2-phenoxy-2H-pyran are made by the reaction
30 of the corresponding vinyl ether with acrolein in the presence of a catalytic amount of a zinc salt, e.g., zinc chloride. A
variety of 3,4-dihydro-2H-pyrans having a substituent in the 2-position can be made by similar reactions. The products
formed by the reaction of 1 and 2 moles of acrolein with the divinyl ether of an alkylene- or polyalkylene glycol are
blocking agents, also. The latent mercaptans made from the di-(3,4-dihydropyranyl) ethers also have the potential of
being chelating agents in the polymer compositions of this invention. In the case of the reaction of one mole of acrolein
35 per mole of a divinyl ether, the vinyl ether group of the resulting monomer permits the product to be incorporated into
a vinyl chloride copolymer followed by the addition of a mercaptan across the double bond of the pyran ring to yield a
latent mercaptan that is an integral stabilizer for the polymer. The reaction of one mole of acrolein with one mole of the
divinyl ether also allows for the formation of a monomeric latent mercaptan of the mercaptan/tetrahydropyran adduct
type in which the vinyl ether group of the resulting monomer permits the product to be copolymerized with one or more
40 of a wide variety of ethylenically unsaturated compounds to form polymeric latent mercaptans. The product from the
reaction of acrolein with chloroethyl vinyl ether provides a substituted 3,4-dihydropyran that can be further derivatized.
The addition of a mercaptan across the double bond of the pyran ring can be done in the presence of the zinc salt
catalyst to yield a stabilizer composition of this invention.
[0029] When 2-S-tetrahydopyranylthioethanol is prepared from 3,4-dihydropyran by said procedure, by-products
45 having the following formulas (as each relates to FORMULA 1) are also obtained:

50

55

6
 EP 0 945 485 A1

SCHICK, OH
I

a = l, m = 0, n = 0, y = 1, z = 1; X i s oxygen,
R5 and R7 j o i n to form -CH2-CH2-CH2-CH2- ; R4 i s
hydrogen, and R1 is h y d r o x y e t h y l .

SCH.CHpOH
i

a = l, m = 0 , n = 1, y = l, z = 1; Xis oxygen,
R3 and R7 j o i n to form -CH2-CH2-CH2-; R2, R4 and R5
are hydrogen, and R1 is h y d r o x y e t h y l .

J o

a = 1, m = 0, n = 0, y = i , z = l; X i s oxygen,
R5 and R7 j o i n to form -CH2-CH2-CH2-CH2- ; R4 i s
lydrogen, and R is 2 - e t h o x y t e t r a h y d r o p y r a n y l .
 EP 0 945 485 A1

a = i, m = 0, n = o, y = 1, z = 1; X i s oxygen,
R5 and R7 j o i n to form -CH2-CH2-CH2-CH2- ; R4 i s
hydrogen, and R1 is 3 - e t h o x y t e t r a h y d r o p y r a n y l
.

a = l, m = 0 , n = 1, y = l , z = l ; X i s
oxygen,
R3 and R7 j o i n to form R2, R4
-CH2-CH2-CH2- ; and R5
a r e h y d r o g e n , and 1
R i s
2-ethoxytetrahydropyranyl .

a = 1, m = 0 , n = 1, y=l, z = 1;
X is o x y g e n ,
R3 and R7 j o i n to form -CH2-CH2-CH2- ; R2 , R4 and R5
a r e h y d r o g e n , and R1 i s
3-ethoxytetrahydropyranyl .

[0030] The homologous by-products are expected when 2,3-dihydrofuran is reacted with mercaptoethanol but the
orincipal product is the 5-S-tetrahydrofuranylthioethanol shown by the following structure:

»• ,C c

c— c
i
SCH2CH2OH

[0031] When the 3,4-dihydropyran is replaced by a 3,4-dihydro-2-alkoxy-pyran; a 3,4-dihydro-2-phenoxy-pyran; or

a 3,4-dihydro-2-formyl-pyran in the above procedure, the following products are formed:

3
 EP 0 945 485 A1

SCH2CH2OH SCH2CH2OH SCH2CH2OH .

[0032] Examples of 2-S-(tetrahydropyranyl)thioalkanols that are suitable as latent mercaptans for this invention in-
clude, without limitation, 2-S-(tetrahydropyranyl)thioethanol, 2-S-(tetrahydropyranyl)thiopropanol, and 2-S-(tetrahydro-
pyranyl)-thiobutanol. The carboxylates suitable for the purposes of this invention are exemplified by 2-S-(tetrahydro-
15 pyranyl)thioethyl caprate, which also may be named 2-S-(2-decanoyloxyethylthio) tetrahydropyran, made by the reac-
tion between mercaptoethyl caprate and 3,4-dihydropyran according to the foregoing procedure and has the following
formula in relation to FORMULA 1:

I
SCH2CH2OCC9H19

wherein a = 1, m = 0, n = 0; y = 1, z is 1; X is oxygen, R5 and R7 are joined to form -CH2-CH2-CH2-CH2-; R4 is

hydrogen, and R1 is decanoyloxyethyl.
30 [0033] Homologs of the thus described compounds which are particularly useful in the stabilization of flexible PVC
compositions include the 2-S-(tetrahydropyranyl)thioalkyl carboxylates and their furanyl homologs wherein the ethyl
moiety is replaced by propyl, butyl, hexyl, and others in the series up to and including dodecyl and the capric acid
radical of said compound is replaced by other fatty acid radicals (saturated and unsaturated) or resin acid radicals
having up to and including 22 carbon atoms. The acids are exemplified by caproic, caprylic, lauric, myristic, palmitic,
35 stearic, arachidic, behenic, and the oleic and linoleic acids, as such, or as found in tall oil acids along with abietic and
pimaric acids. The mercaptoalkyl carboxylate moiety is thus exemplified by mercaptoethyl laurate, mercaptoethyl
oleate, mercaptoethyl hexanoate, mercaptoethyl octanoate, mercaptoethyl myristate, mercaptoethyl palmitate, mer-
captoethyl stearate, and the mercaptopropyl, mercaptobutyl, and mercaptooctyl homologs of each of the above. The
esters are made by the conventional method of reacting the hydroxyl group of a mercaptoalkanol with the desired
40 carboxylic acid in the presence of an acidic catalyst and removing water as it forms.
[0034] The 2-S-(tetrahydropyranyl)thioalkanols, the carboxylates thereof, and their furanyl homolgs are employed
in this invention in an amount sufficient to impart the desired resistance to heat deterioration to halogen-containing
organic polymers. It will be readily apparent to one of ordinary skill in the art, that the precise amount of stabilizer
composition used will depend upon several factors, including, but not limited to, the particular halogen-containing or-
45 ganic polymer employed, the temperature to which the polymer will be subjected, and the possible presence of other
stabilizing compounds. In general, the more severe the conditions to which the halogen-containing organic polymer is
subjected, and the longer the term required for resisting degradation, the greater will be the amount of stabilizer com-
position required. Generally, as little as about 0.20 part by weight of the latent mercaptan per hundred parts by weight
of the PVC resin will be effective. While there is no critical upper limit to the amount of latent mercaptan which can be
so employed, amounts of about 3.0 parts or less by weight per hundred parts of the PVC resin are preferred.
[0035] A 2-S-(tetrahydropyranyl)mercaptoalkyl carboxylate is more active as a heat stabilizer in flexible PVC com-
positions than the tetrahydropyranyl-blocked mercaptans derived from alkylmercaptans such as dodecanethiol when
activated according to this invention as manifest in the improved color hold properties and dynamic thermal stability
of such stabilized PVC compositions. The higher activity may be the result of the better compatibility of the ester-
55 containing latent mercaptans with a plasticized PVC. The compatibility of the corresponding homologous furan-based
latent mercaptans is similar.
[0036] Metallic-based stabilizers are defined for the purposes of this invention as metal salt stabilizers, organometallic
stabilizers. For the purposes of this invention, metal salts are defined to include oxides, hydroxides, sulfides, sulfates,

9
 EP 0 945 485 A1

chlorides, bromides, fluorides, iodides, phosphates, phenates, perchlorates, carboxylates, and carbonates. The metal
salt stabilizers are exemplified by zinc, barium, strontium, calcium, tin, magnesium, cobalt, nickel, titanium, antimony,
and aluminum salts of hydrochloric acid, sulfuric acid, phenols, aromatic carboxylic acids, fatty acids, epoxidized fatty
acids, oxalic acid, acetic acid, and carbonic acid. Calcium stearate, calcium 2-ethylhexanoate, calcium octoate, calcium
5 oleate, calcium ricinoleate, calcium myristate, calcium palmitate, calcium laurate, barium laurate, barium stearate,
barium di(nonylphenolate), magnesium stearate, zinc octoate (or caprylate), zinc 2-ethylhexanoate, zinc stearate, zinc
laurate, zinc oxide, zinc chloride, zinc hydroxide, zinc sulfide, zinc sulfate, zinc bromide, and Group I and II metal soaps
in general are examples of suitable salts along with tin stearate, aluminum stearate, and hydrotalcite. The synergistic
amount of the metallic-based stabilizer is from about 0.01 to less than 0.5%, preferably 0.02-0.4%, and more preferably
10 0.03-0. 1% by weight of the halogen containing resin. The zinc salts are much preferred because they provide not only
dynamic stability to the heat processed resin but also superior color hold properties in comparison with the other metal
salts, especially at very low concentrations such as from 0.03 to 0.1 %.
[0037] The Lewis acids are exemplified by boron trifluoride, aluminum chloride, zinc chloride and methyltin trichloride.
Thus, there is some overlap between the metal salts and Lewis acids that are useful in this invention. The synergistic
is amounts of the Lewis acids for the purposes of this invention are from about 0.005 to less than 0.5%, preferably from
about 0.01, more preferably from about 0.03, to about 0.1 % by weight of the halogen-containing resin. The Lewis
acids and the metallic-based stabilizers may be used in combination.
[0038] Conventional organometallic stabilizers include the organotin carboxylates and mercaptides. Such materials
include butyltin tris dodecyl mercaptide, dibutyltin dilaurate, dibutyltin didodecyl mercaptide, dianhydride tris dibutyls-
20 tannane diol, dihydrocarbontin salts of carboxy mercaptals such as those set forth in Hechenbleikner et al.(U.S. Pat.
No. 3,078,290). There can be included any of the vinyl chloride resin stabilizers set forth in Salyer (U.S. Pat. No.
2,985,617).
[0039] Monosulfides and/or polysulfides of the organotin mercaptides of carboxylates and/or mercaptoalkyl carbox-
ylates and of alkyl thioglycolates are also suitable as metal based stabilizers in the compositions of this invention for
25 improving the resistance of halogen-containing polymers to deterioration when heated to 350°F (177°C) during
processing. The sulfides may be made by heating stoichiometric quantities of a mercaptoalkyl ester of a carboxylic
acid or an alkyl mercaptocarboxylate and an organotin chloride having the formula:

30 R'(4-z)SnHalz II

wherein Ft' is an alkyl group having from 1 to 12 carbon atoms, Hal is a halogen having an atomic weight of from
35 to 127, preferably chlorine, and z is any number from 1 to 3; in water and ammonium hydroxide to about 30°C
(86° F), slowly adding an alkali metal mono- or polysulfide, and heating the reaction mixture further to about 45°C before
35 separating the product from said mixture.
[0040] Alternatively, the sulfide may be made by mixing a monoalkyl- or dialkyltin sulfide with an organotin mercaptide
and by other procedures well known in the stabilizer art.
[0041] The sulfides of a mercaptoalkyl ester of a carboxylic acid are characterized by an equilibrium mixture of one
or more alkyltin halides of Formula II, one or more mercaptides of Formula III and one or more alkyltin mono- or
40 polysulfides or oligomers thereof, the alkyltin mono- and polysulfides having the formula IV.

R*(4_n)-Sn-[s-Z-[OC(=0)R1*]Jn Formula III

45
wherein R* is an alkyl radical having from 1 to 12 carbon atoms; R1* is hydrogen, a hydrocarbyl radical, a hydrox-
yhydrocarbyl radical, or R2*C(=0)OR3*, wherein R2* is alkylene, hydroxyalkylene, phenylene, or -CH=CH-, and R3* is
hydrogen, a hydrocarbyl radical, a hydroxyhydrocarbyl radical, or an alkylcarboxyalkylene radical; Z is an alkylene or
hydroxyalkylene radical of at least 2 carbon atoms up to 20 carbon atoms; m is an integer from 1 to 3, n is from 2 to
50 3, and the valency of Z is m + 1.
[0042] Formula IV is representative of linear structures as well as of cyclic trimers and adamantyl rings:

[R4* (4-x)SnS(p/2)]M " [R5* (4-y)SnS(q/2)]N F°rmUla IV

55
wherein R4* and R5* are independently alkyl radicals having from 1 to 12 carbon atoms and are bonded to Sn; x
is 2 or 3; y is 2 or 3; p and q are 2 to 20, preferably 2-4; and M and N are 0-10, preferably 0-4, but M* N = 0; with the
proviso that when (4-x)=(4-y), p=q, and when (4-x)^(4-y), p#q.

10
 EP 0 945 485 A1

[0043] It should be understood that the structures of the sulfides produced by the processes mentioned above are
very complex. The reactions are believed to produce an equilibrium mixture composed of several different but related
products. As will be appreciated by those of ordinary skill in chemistry, equilibrium mixtures inherently include the
starting materials as well as the products of any reaction between them. The chemical and patent literature contain
5 numerous examples demonstrating that members of different classes of organotin compounds may react with one
another under certain conditions to yield products containing one or more tin atoms wherein at least a portion of the
tin atoms are bonded to different combinations of radicals than they were before being mixed together. Accordingly,
the sulfides are believed to include bis[monoorganotin)-bis (thioalkyl carboxylate)] monosulfides and polysulfides, bis
[(diorganotin)-mono(thioalkyl carboxylate)]monosulfides and polysulfides, and products which arise during equilibrium
10 reactions among said mono- and polysulfides, including monoalkyltin tris(thioalkyl carboxylates), dialkyltin bis(thioalkyl
carboxylates), mono- and di-organotin mono- and polysulfides, and oligomers thereof, as well as the starting materials
themselves. The sulfide of an alkyl ester of a mercaptocarboxylic acid is likewise believed to include bis[monoorgan-
otin)-bis(alkyl mercaptocarboxylate)] monosulfides and polysulfides, bis[(diorganotin)-mono(alkyl mercaptocarboxy-
late)]monosulfides and polysulfides, and products which arise during equilibrium reactions among said mono- and
is polysulfides, including monoalkyltin tris(alkyl mercaptocarboxylates), dialkyltin bis(alkyl mercaptocarboxylates), mono-
and di-organotin mono- and polysulfides, and oligomers thereof.
[0044] The polysulfides include mixtures of compounds having from 2 to 10 sulfur atoms linked together. Mixtures
of monosulfides and polysulfides having from 2 to 4 sulfur atoms are preferred.
[0045] Conventional non-metallic stabilizers and antioxidants can also be included in the PVC compositions of the
20 present invention. Thus, there can be included 0.01-0.75 %, based on the weight of the resin, of sulfur containing
compounds such as dilauryl-thiodipropionate, distearyl 3,3'-thiodipropionate, dicyclohexyl-3,3-thiodipropionate, dio-
leyl-3,3'-thiodipropionate, dibenzyl-3,3'-thiodipropionate, didecyl-3,3'-thiodipropionate, dibenzyl-3,3'-thiodipropionate,
diethyl-3,3'-thiopropionate, lauryl ester of 3-methylmercaptopropionic acid, lauryl ester of 3-butylmercaptopropionic
acid, lauryl ester of 3-lauryl mercaptopropionic acid, and phenyl ester of 3-octyl mercaptopropionic acid.
25 [0046] In addition to the stabilizer compositions of this invention, the PVC compositions of this invention may contain
plasticizers, as mentioned above in regard to flexible PVC, and conventional additives such as pigments, fillers, blowing
agents, dyes, ultraviolet light absorbing agents, antioxidants, densifying agents, biocides, and the like.
[0047] An antioxidant may be added in an amount of 0.01-10%, preferably 0.1-5% by weight of the PVC resin. Phe-
nolic antioxidants are particularly suitable and are exemplified by 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole,
30 propyl gallate, 4,4'-thiobis(6-t-butyl-m-cresol), 4,4'-cyclohexylidene diphenol, 2,5-di-t-amyl hydroquinone, 4,4'-butyli-
dene bis(6-t-butyl-m-cresol), hydroquinone monobenzyl ether, 2,2'-methylene-bis(4-methyl-6-t-butyl phenol),
2,6-butyl-4-decyloxy phenol, 2-t-butyl-4-dodecyloxy phenol, 2-t-butyl-4-dodecyloxy phenol, 2-t-butyl-4-octadecyloxy
phenol, 4,4'-methylene-bis(2,6-di-t-butyl phenol), p-amino phenol, N-lauryloxy-p-amino phenol, 4,4'-thiobis(3-methyl-
6-t-butyl phenol), bis [o-(1 ,1 ,3,3-tetramethyl butyl)phenol] sulfide, 4-acetyl-p-resorcylic acid, A-stage p-t-butylphenol-
35 formaldehyde resin, 4-dodecyloxy-2-hydroxybenzophenone, 3-hydroxy-4-(phenylcarbonyl) phenyl palmitate, n-do-
decyl ester of 3-hydroxy-4-(phenyl carbonyl) phenoxyacetic acid, and t-butyl phenol.
[0048] From 0.01 -30% by weight of an epoxy compound, based on the weight of the vinyl chloride polymer in the
PVC compositions of this invention may also be used. Examples of such epoxy compounds include epoxidized soya
bean oil, epoxidized lard oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil,
40 epoxidized corn oil, epoxidized tung oil, epoxidized cottonseed oil, epichlorhydrin/bis-phenol A resins, phenoxy-pro-
pylene oxide, butoxypropylene oxide, epoxidized neopentylene oleate, glycidyl epoxystearate, epoxidized a-olefins,
epoxidized glycidyl soyate, dicyclopentadiene dioxide, epoxidized butyl toluate, styrene oxide, dipentene dioxide, gly-
cidol, vinyl cyclo-hexene dioxide, glycidyl ether of resorcinol, glycidol ether of hydroquinone, glycidyl ether of 1,5-di-
hyroxynaphthalene, epoxidized linseed oil fatty acids, allyl glycidyl ether, butyl glycidyl ether, cyclohexane oxide, 4-
45 (2,3-epoxypropoxy) aceto-phenone, mesityl oxide epoxide, 2-ethyl-3-propyl glycidamide, glycidyl ethers of glycerine,
pentaerythritol and sorbitol, and 3,4-epoxycyclohexane-1 , 1-dimethanol bis-9, 10-epoxystearate. Likewise there can be
used organic phosphites in an amount of 0.01 to 10%, preferably 0.1-5% by weight of the vinyl chloride polymer. The
organic phosphites contain one or more, up to a total of three, aryl, alkyl, aralkyl and alkaryl groups, in any combination.
The term "trialkylaryl" is inclusive of alkyl, aryl, alkaryl and aralkyl phosphites containing any assortment of alkyl, aryl,
so alkaryl and aralkyl groups. Exemplary are triphenyl phosphite, tricresyl phosphite, tri(dimethylphenyl) phosphite, tributyl
phosphite, trioctyl phosphite, tridodecyl phosphite, octyl diphenyl phosphite, dioctyl phenyl phosphite, tri(octyl-phenyl)
phosphite, tri(nonylphenyl) phosphite, tribenzyl phosphite, butyl dicresyl phosphite, octyl di(octyl-phenyl) phosphite, tri
(2-ethyl-hexyl) phosphite, tritolyl phosphite, tri(2-cyclohexylphenyl) phosphite, tri-alpha-naphthyl phosphite, tri(phenyl-
phenyl) phosphite, and tri(2-phenylethyl) phosphite.
55 [0049] Likewise there can be included from 0.01-10% by weight of the vinyl chloride polymer of a polyol stabilizer
for vinyl chloride resins. Thus there can be included glycerol, sorbitol, pentaerythritol, mannitol and polyethers such
as diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and the like.
[0050] Nitrogen containing stabilizers such as dicyandiamide, melamine, urea, formoguanamine, dimethyl hydantoin,

11
 EP 0 945 485 A1

guanidine, thiourea, 2-phenylindoles, aminocrotonates, N-substituted maleimides, uracil, the 1,3-dialkyl-6-amino-uracil

derivatives described in German Offenlegungsschrift 19,741,778 by Ciba Specialty Chemicals Holding Inc., and the
pyrrolodiazine diones described in published Australian Patent Application No. AU-A-48232/96 by Ciba-Geigy, and the
like also can be included in amounts of 0.1-10% by weight. Of particular interest are the pyrrolodiazine diones described
by the formula:

wherein and# are independently hydrogen or C1-C4 alkyl. Examples of compounds contemplated for use
in this invention include the IH-pyrrolo[2,3-d]pyrimidine-2,4(3H,7H)-diones exemplified by Compound Nos. 103, 111,
123, 129, and 131 of said Australian Patent Application, which have the following substituents:

No. 103 1,3,6-trimethyl;

No. 111 1,3,6,7-tetramethyl;
No. 123 none;
No. 129 1,3-diethyl,6-methyl;
No. 131 1,3-di-n-butyl,6-methyl;

[0051] Said compounds may be prepared by the method described by S. Senda and K. Hirota, Chem. Pharm. Bull.,
22(7), 1459-1 467(1 974) or by the reaction of the corresponding aminouracil with molar excesses of chloroacetaldehyde
and ammonium acetate in water at about 65°C until a precipitate forms or with molar excesses of acetoxyacetone and
ammonium acetate in water at reflux for 12 hours. The German Offenlegungsschrift 19,741,778 and the Australian
Patent Application No. AU-A-48232/96 are each incorporated herein by reference.
[0052] Conventional lubricants for vinyl chloride resins such as low molecular weight polyethylene, i.e. polyethylene
wax, fatty acid amides, e.g. lauramideandstearamide, bisamides, e.g. decamethylene, bis amide, and fatty acid esters,
e.g. butyl stearate, glyceryl stearate, linseed oil, palm oil, decyloleate, corn oil, cottonseed oil, hydrogenated cottonseed
oil, stearic acid, calcium stearate, mineral oil, montan wax, oxidized polyethylene and the like can also be included.
[0053] The following examples further illustrate the preparation of blocked mercaptans of this invention, the prepa-
ration of stabilizer compositions of this invention, and the advantages of said blocked mercaptans and stabilizer com-
positions.

EXAMPLE 1 Y

[0054] 1H-NMR spectroscopy was used to determine the molecular structure of 2-S-(decanoyloxyethylthio)tetrahy-
dropyran or 2-S-(tetrahydropyranyl)thioethylcaprate which was prepared by adding 42.0 grams (0.50 mole) of 3,4-di-
hydropyran to 112.2 grams (0.50 equivalent) of mercaptoethylcaprate (14.7 % SH) in the presence of an acid catalyst
over a period of 45 minutes while maintaining a nitrogen atmosphere and a temperature below 35 °C and then heating
it to 50°C and holding that temperature for 1.5 hours. After cooling the solution, it was washed with two 200 ml portions
of a 10 % sodium bicarbonate solution in water, followed by a 200 ml wash with water. The organic layer was dried
with MgS04 to yield a light yellow liquid having an SH content of less than 0.5 percent as determined by titration with
a 0.100 N iodine solution in isopropanol. The 1H-NMR (CDCI3, 8) spectrum was: 2.3 (2H, t, -C(=0)-CH2-CH2), 2.8 (2H,
m, -S-CH2-CH2-), 4.2 (2H, m, -S-CH2CH2-0-), 4.9 (1 H, m, -0-CH(-S-CH2-)-CH2-CH2-). The total color change (dE) of
a PVC composition containing 0.13 phr of the latent mercaptan of this example was measured versus a white tile
standard using a Hunter colorimeter at one minute intervals. At one minute, it was 4.2; at five minutes, it was 8.4.

Example 2

[0055] 2-S-tetrahydropyranyl) thioethyltallate was prepared by adding 172.45 grams (2.05 equiv.) of 3,4-dihydro(2H)

12
 EP 0 945 485 A1

pyran dropwise to 760.00 grams (2.00 equiv.) of 2-mercaptoethyltallate (8.70% SH by iodometric titration) containing
0.93 gram of methanesulfonic acid (70% active) over a period of 45 minutes under a nitrogen blanket and a temperature
between 25-35°C and heating to 35-40°C for 2 hours. After cooling the solution, 3 grams of Norite carbon black was
charged and the product was vacuum filtered to yield 932 grams of yellow liquid having a SH content of less than 0.4%
as determined by titration with 0.100 N iodine solution in isopropanol. The 1H-NMR(CDC13,8) spectrum was: 2.3 (2H,
t, -C(=0)-CH2-CH2-), 2.8 (2H, m, -S-CH2-CH2-), 4.3 (2H, m,(-CC(=0)-0-CH2), 4.9 (1H, m, -0-CH(-S-CH2)-CH2-CH2-).
GC of the product (1% in ether) indicated one primary product peak at 26.3 minutes retention time (50-300°C; 10°CV
min.; split flow injector/FID).

Examples 3-11

[0056] A general flexible PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=70) 100.0 parts
Dioctyl phthalate 40.0 phr
Epoxidized soybean oil 5.0 phr
Stearic acid 2-S-(tetrahydropyranyl thioethyl tallate) 0.2 phr
Metal carboxylate at equal levels of metal See Table I

was processed on a standard horizontal two-roll mill (roll speeds 30R/40R) at 350°F with chips taken at five minute
intervals to a maximum of 60 minutes. The color properties of the chips were measured using a Hunter Labs Colorimeter
(L, a, b) and the yellowness index was selected as the measurement for comparison in Table II. The dynamic thermal
stability (DTS) of the compositions was measured on a Brabender Plasti-Corder PL-2000 at 200°C/80rpm with No. 6
roller blades and an electric head. The DTS, shown in Table III was recorded as the time in minutes before a sharp
upturn in the torque curve during processing was observed.
[0057] As the data in the tables shows, all of the compositions have good dynamic stability but those containing zinc
carboxylates have both dynamic stability and excellent color hold.

TABLE I
Example Metal Carboxylate Amount (phr)
Control None
3 Nickel stearate 0.10
4 Zinc stearate 0.09
5 Zinc Octoate 0.05
6 Tin (II) stearate 0.05
7 Barium stearate 0.05
8 Cadmium stearate 0.06
9 Lead (ll)stearate 0.03
10 Aluminum stearate 0.30
11 Calcium stearate 0.14

TABLE II
PVC Color Hold (Yellowness Index)
Minutes
Time\ 5 10 15 20 25 30 35 40 45 50 55 60
Ex.
Cntrl. 47.1 77.2 89.1 101.0 94.3 99.7 105.4 99.9 98.1 93.9 94.2 89.8

13
 EP 0 945 485 A1

TABLE II (continued)
PVC Color Hold (Yellowness Index)
Minutes
Time\ 5 10 15 20 25 30 35 40 45 50 55 60
Ex.
3 54.3 80.5 93.5 103 107.7 112.1 107.8 111.6 119.9 111.8 103.5 119.8
4 9.0 12.3 11.8 13.4 16.6 17.2 21.0 24.6 30.8 39.8 48.1 53.2
5 9.7 11.7 13.9 14.5 15.6 16.8 20.6 22.9 23.8 31.1 35.8 40.5
6 50.5 89.2 96.9 94.9 106.9 106.6 107.9 105.0 98.7 105.4 102.0 107.1
7 51.0 86.6 108.5 116.6 115.6 118.8 135.0 134.6 135.4 138.4 126.1 133.5
8 16.0 41.7 47.9 51.2 52.2 54.8 56.6 60.9 65.7 70.9 72.1 83.2
9 25.4 56.8 78.2 82.6 88.6 95.6 103.9 96.7 96.1 101.2 99.9 107.1
10 51.3 73.5 81.4 87.2 93.0 98.8 101.3 106.0 111.4 116.1 116.6 119.2
11 51.9 80.8 93.2 109.5 118.4 126.7 126.7 143.0 137.6 141.3 142.3 139.6

Table III
Dynamic Thermal Stability
Example Time/minutes
Control 43.9
3 43.8
4 40.4
5 45.0
6 51.4
7 53.5
8 48.2
9 50.5
10 45.9
11 61.6

Examples 12-15

[0058] In this example, the relationship between the compatibility of the mercaptoalkyl esters with the plasticized
vinyl chloride resin and their stabilizing power is shown.
[0059] A general flexible PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=70) 100.0 parts
Dioctyl phthalate 40.0 phr
Epoxidized soybean oil 5.0 phr
Stearic acid 0.2 phr
Zinc octoate (18% Zn) 0.05 phr
2-S-(tetrahydropyranyl
thioethylcarboxylate) See Table IV

14
 EP 0 945 485 A1

was processed on a standard horizontal two-roll mill (roll speeds 30R/40R) at 350°F with chips taken at five minute
intervals to a maximum of 60 minutes. The color properties of the chips were measured using a Hunter Labs Colorimeter
(L, a, b) and the yellowness index was selected as the measurement for comparison in Table V.

5 TABLE IV
Example Carboxylate % sulfur Amount (phr)
12 Hexanoate 12.4 1.6
13 Caprate 10.4 1.9
14 Tallate 7.6 2.6
15 Oleate 7.6 2.6
Control None (alcohol) 19.8 1.0
15
Table V
PVC Color Hold (Yellowness Index)
Minutes
5 10 15 20 25 30 35 40 45 50 55 60
12 10.5 11.1 11.8 13.5 14.7 20.5 25.5 31.0 38.1 49.8 60.5 69.5
13 10.5 11.0 10.9 13.4 14.1 16.4 20.6 24.0 30.7 32.1 44.8 57.1
14 11.2 12.4 14.1 14.9 16.5 17.9 19.0 21.8 23.9 24.5 29.5 32.1
15 10.0 11.6 12.7 13.3 14.7 14.9 16.2 19.1 22.5 25.6 33.6 40.7
Cntrl. 10.4 11.9 13.0 14.3 16.6 20.4 23.8 27.3 34.5 38.2 48.0 62.1

Examples 16-17 and Comparative Example 1

[0060] The general flexible PCV formulation of Examples 12-15, was modified as shown in Table VI, and the resulting
compositions were processed on a standard horizontal two-roll mill (roll speeds 30R/40R) at 350°F with chips taken
at five minute intervals to a maximum of 60 minutes. The color properties of the chips were measured using a Hunter
35 Labs Colorimeter (L, a, b) and the yellowness index was selected as the measurement for comparison in Table VII.
They were also processed on a Brabender Plasti-Corder PL-2000 with electric mixing heads (roller type 6) at 200°C/
80 rpm to measure their dynamic thermal stability (DTS). The DTS, shown in Table VIII, was recorded as the time in
minutes before a sharp upturn in the torque curve during processing was observed.

40 Table VI
Stabilizer Systems Evaluated
Reference phr Stabilizer ppm Metals Use Level,
Control 1 2-S-(tetrahydropyranyl)thioethyltallate none 2.05
Control 2 Zinc octoate (18% as zinc) 2,506 2.05
16 2-S-(tetrahydropyranyl)thioethyltallate — 2.00
Zinc octoate (18% as zinc) 61 0.05
2~05
17 Mark 859 706 1.00
2-S-(tetrahydropyranyl)thioethyltallate —- 1.05
Comp. Ex. 1 Mark 859 1,448 2.05

15
 EP 0 945 485 A1

Table VII
PVC Color Hold (Yellowness Index) During Processing by Two-Roll Mill @ 350°F
Minutes
5 10 15 20 25 30 35 40 45 50 55 60
C1 42.0 68.8 88.9 93.7 99.0 95.1 99.0 91.3 96.8 96.9 101.4 104.4
C2 12.2 15.4 22.6 19.4 burn
16 10.5 11.4 12.0 12.8 14.7 16.4 17.5 19.3 21.1 22.2 27.8 34.3
17 11.3 13.5 15.8 18.3 20.1 20.2 20.9 22.1 20.5 19.4 22.1 28.8
CE 10.6 11.6 11.3 11.9 13.3 15.3 18.5 23.1 30.2 35.5 49.7 49.7
C1=Control 1; C2=Control 2; CE=Comparative Example 1

Table VIII
PVC Dynamic Thermal Stability by Brabender @200°C
Control 1 52.3 minutes
Control 2 3.7 minutes
16 38.5 minutes
17 52.3 minutes
Comparative Example 1 39.3 minutes

Example 18

[0061] This example demonstrates the use of a Lewis acid such as zinc chloride in synergy with latent mercaptans.
[0062] A general flexible PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=70) 100.0 parts
Dioctyl phthalate 40.0 phr
Epoxidized soybean oil 5.0 phr
Stearic acid 0.2 phr

was modified as shown in Table IX and the resulting compositions were processed on a standard horizontal two-roll
mill (roll speeds 30R/40R) at 350°F with chips taken at five minute intervals to a maximum of 60 minutes. The color
properties of the chips were measured using a Hunter Labs Colorimeter (L, a, b) and the yellowness index was selected
as the measurement for comparison in Table X.

Table IX
Stabilizer Systems Evaluated
Reference Stabilizer Use Level, phr
Control 1 2-S-(tetrahydropyranyl)thioethyltallate 2.02
Control 2 Zinc chloride (anhydrous) 0.02
18 2-S-(tetrahydropyranyl)thioethyltallate 2.00
Zinc chloride (anhydrous) 0.02

16
 EP 0 945 485 A1

Table X
PVC Color Hold (Yellowness Index) During Processing by Two-Roll Mill @ 350°F
min/ex 5 10 15 20 25 30 35 40 45 50 55 60
C1 48.5 90.6 106.8 115.9 121.2 132.2 127.3 122.6 113.9 110.5 98.8 84.2
C2 18.3 26.7 46.1 68.8 45.2 burn — — — —
18 14.9 16.1 18.1 19.8 20.8 22.4 23.6 26.5 26.0 26.3 28.2 28.9
10
Examples 19-20 and Comparative Example 2

[0063] Whereas the surprising effect of very low levels of metallic-based stabilizers on 2-S-(tetrahydropyranyl)thio-
alkyl carboxylates in flexible PVC compositions has been shown above, the role played by the better compatibility of
a 2-S-(tetrahydropyranyl)thioalkanol in combination with such low levels of metallic-based stabilizers in a rigid PVC is
shown in the following examples.
[0064] A conventional rigid PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=65) 100.0 parts
Calcium carbonate 5.00 phr
Titanium dioxide 1.0 phr
Calcium stearate 0.6 phr
Paraffin wax 1.2 phr
Oxidized polyethylene 0.15 phr

was modified as shown in Table XI and the resulting compositions were processed on a standard horizontal two-roll
mill (roll speeds 30R/40R) at 390°F with chips taken at one minute intervals to a maximum of 12 minutes. The color
properties of the chips were measured using a Hunter Labs Colorimeter (L, a, b) and the yellowness index was selected
as the measurement for comparison in Table XII. The DTS, measured as described above but at 190°C, is shown in
Table XIII.

Table XI
Stabilizer Systems Evaluated
Reference Stabilizer Use Level, phr
Comp. Ex. 2 ADVASTAB TM-694 stabilizer* 0.40
19 2-S-(tetrahydropyranyl)thioethanol** 2.50
Zinc octoate (18% zinc)l 0.05
20 2-S-(tetrahydropyranyl)thioethyltallate 2.00
Zinc octoate (18% zinc) 0.05
Dibenzoylmethane 0.05
*ADVASTAB is a registered trademark of Morton International, Inc.
**includes minor amounts of compounds of Formulas 3-7.

so Table XII
PVC Color Hold (Yellowness Index) During Processing by Two-Roll Mill @ 390°F
min/ex 1 2 3 4 5 6 7 8 9 10 11 12
CE 2 3.0 3.9 4.5 5.1 5.8 7.2 9.3 11.5 14.2 16.8 18.6 21.5
19 4.8 7.4 7.9 7.6 7.3 7.7 7.8 9.8 12.8 16.5 20.5 24.4
20 4.3 5.9 9.0 11.9 14.0 15.9 17.1 17.4 16.4 18.3 21.9 26.3

17
 EP 0 945 485 A1

Table XIII
PVC Dynamic Thermal Stability by Brabender @190°C
Minutes
Comparative Example 2 6.3
19 18.0
20 6.1
10
Examples 21-22 and Comparative Examples 3-4

[0065] The activating effect of a Lewis acid and of a metallic-based stabilizer on a latent mercaptan according to this
invention, when used alone and in combination, is shown in this example.
15 [0066] A conventional rigid PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=65) 100.0 parts
Calcium carbonate 5.00 phr
Titanium dioxide 1.0 phr
Calcium stearate 0.6 phr
Paraffin wax 1.2 phr
Oxidized polyethylene 0.15 phr

was modified as shown in Table XIV and the resulting compositions were processed on a standard horizontal two-roll
mill (roll speeds 30R/40R) at 390°F with chips taken at one minute intervals to a maximum of 11 minutes. The color
properties of the chips were measured using a Hunter Labs Colorimeter (L, a, b) and the yellowness index was selected
as the measurement for comparison
r in Table XV.
30
Table XIV
Stabilizer Systems Evaluated
Reference Stabilizer Use Level, phr
Comp. Ex. 3 ADVASTAB TM-599T* 0.25
Comp. Ex. 4 ADVASTAB TM-599T* 0.235
Methyltin trichloride 0.015
21 2-S-(tetrahydropyranyl)thioethanol** 0.05
ADVASTAB TM-599T* 0.235
Methyltin trichloride 0.015
22 2-S-(tetrahydropyranyl)thioethanol ** 0.05
ADVASTAB TM-599T* 0.25
*ADVASTAB is a registered trademark of Morton International, Inc.
"includes minor amounts of compounds of Formulas 3-7

Table XV
SO
PVC Color Hold (Yellowness Index) During Processing by Two-Roll Mill @ 390°F
min/ex 1 2 3 4 5 6 7 8 9 10 11
CE 3 6.7 8.2 9.1 10.2 12.0 14.5 18.2 22.3 25.2 26.0 29.4
55 CE 4 4.6 5.6 6.8 8.8 12.2 16.0 19.8 23.4 24.6 27.3 29.5
21 4.0 4.1 4.6 5.7 7.2 11.4 14.0 17.9 20.8 23.3 26.4

18
 EP 0 945 485 A1

Table XV (continued)
PVC Color Hold (Yellowness Index) During Processing by Two-Roll Mill @ 390°F
min/ex 1 2 3 4 5 6 7 8 9 10 11
22 5.1 6.2 6.3 7.0 8.2 11.4 15.1 19.1 21.0 24.0 26.5

Example 23

jo Preparation of Intermediate

[0067] A mixture of 736.16 grams (8 moles) of thioglycolic acid, 848.96 grams (8 moles) of diethyleneglycol, and 1.3
grams of p-toluene sulfonic acid was heated to 80°C at a pressure of 400 Torr in a reactor equipped with a mechanical
stirrer, a thermometer, and a vacuum take-off condenser. The refluxing temperature was held for 1 hour before the
15 pressure was reduced to 120 Torr over a period of 2.5 hours to remove water formed by the esterification. The tem-
perature rose to 120°C as the pressure was further reduced to 20 Torr over a period of 0.5 hour. The total weight of
water removed was 140.92 grams. The product has an acid value of 12 and an SH content of 16.75% by weight. The
yield was 1421 . 12 grams. The product was a mixture of the diethyleneglycol mono- and diesters of thioglycolic acid (i.
e., hydroxyethyloxyethylmercaptoacetate and ethyloxyethyl dimercaptoacetate) and was satisfactory.
20
Preparation of Adduct

[0068] To the 1421 grams (7.89 equivalents) of intermediate thus produced there was added 6.38 grams of AMBER-
LYST 15 ion exchange resin and then 708.21 grams (8.42 equivalents) of 3,4-dihydro(2H)pyran (DHP) was added
25 dropwise over a period of 135 minutes under a nitrogen blanket at a temperature 40-50°C. After continued heating at
40-50°C for 2.25 hours, the %SH was 5.36. Another charge of DHP weighing 300.21 grams (about 3.5 moles) was
added during a period of 0.5 hour and the reaction mixture was held at about 55°C for 0.5 hour to reduce the %SH to
3,32. After standing overnight (about 14 hours) under nitrogen, the product had an SH content of 2.68 %.
[0069] The product was a mixture containing 2-S-(tetrahydropyranyl) hydroxyethyloxyethylthioglycolate, wherein R1
30 is hydroxyethoxyethoxyacetylmethyl, and bis-[2-S-(tetrahydropyranyl)ethyloxyethyl] thioglycolate, wherein y is 2 and
R1 is oxy[bis(ethoxyacetylmethyl)].

Example 24

35 Preparation of intermediate

[0070] A mixture of 98.23 grams (1.07 moles) of thioglycolic acid, 160.06 grams (1.07 moles) of triethyleneglycol,
and 0.2 gram of p-toluene sulfonic acid was heated to 100°C at a pressure of 250 Torr in a reactor equipped with a
mechanical stirrer, a thermometer, and a vacuum take-off condenser. The refluxing temperature was held for 25 minutes
40 before the pressure was reduced to 10 Torr over a period of 1.5 hours to remove water formed by the esterification.
The product contained the triethyleneglycol monoester (about 57% of the total weight) and the triethyleneglycol diester
of thioglycolic acid (about 20 %) and was satisfactory.

Preparation of Adduct
45
[0071] A mixture containing (2-S-tetrahydropyranyl) hydroxyethyloxyethyloxyethylthioglycolate and bis-(2-S-tetrahy-
dropyranyl)ethyloxyethyloxyethyl di-thioglycolate was prepared by cooling 100 grams (0.42 equivalent of SH) of the
thus prepared mixture of triethyleneglycol mono- and diesters of thioglycolic acid along with 0.2 gram of AMBERLYST
15 ion exchange resin to 0°C and adding 39.18 grams (0.462 mole) of DHP dropwise over a period of 30 minutes. The
so mixture was held at 0°C for 1 hour and then heated gradually to room temperature (about 22°C) and held there for 2
hours. The yield of product was 139.2 grams and the SH content was 3.5%.

Example 25

55 Preparation of Intermediate

[0072] A mixture of 92.0 grams (1 mole) of thioglycolic acid, 212.21 grams (2 moles) of diethyleneglycol, and 0.24
gram of p-toluene sulfonic acid was heated to 100°C at a pressure of 200 Torr in a reactor equipped with a mechanical

19
 EP 0 945 485 A1

stirrer, a thermometer, and a vacuum take-off condenser. The temperature was held for 0.5 hour before the pressure
was reduced to 10 Torr over a period of 1.9 hours and then held for 70 minutes to remove water formed by the ester-
ification. The temperature was raised to 110°C as the pressure was further reduced to less than 1 Torr over a period
and held for 3 hours. The diethyleneglycol monoester of thioglycolic acid constituted 85.9 % and the diester constituted
5 14.1 % of the weight of the product. The SH content of the product was 19.49% by weight, which was satisfactory.

Preparation of Adduct

[0073] A mixture of 70 grams (0.412 equivalent) of the intermediate thus produced and 0.15 gram of AMBERLYST
10 15 ion exchange resin was cooled to less than 0.5°C and then 36.52 grams (0.434 equivalent) of DHP was added
dropwise over a period of about 7 minutes and after 3 hours it was warmed to room temperature (about 22°C).

Examples 26-28 and Comparative Examples 5 & 6

is [0074] A conventional rigid PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=65) 100.0 parts
Calcium carbonate 5.00 phr
Titanium dioxide 1.0 phr
Calcium stearate 0.6* phr
Paraffin wax 1.2 phr
Oxidized polyethylene 0.15 phr
*0.45 in Comp. Ex. 4 and Ex. 28

was modified as shown in Table XVI and the resulting compositions were processed on a standard horizontal two-roll
mill (roll speeds 30R/40R) at 390°F with chips taken at one minute intervals to a maximum of 12 minutes. The color
properties of the chips were measured using a Hunter Labs Colorimeter (L, a, b) and the dE was selected as the
measurement for comparison in Table XVII. The DTS, measured as described above but at 190°C, is shown in Table
XVIII.

Table XVI
Stabilizer Systems Evaluated
Reference phr Stabilizer Use Level,
Comp. Ex. 5 ADVASTAB TM-599 stabilizer 0.45*
Comp. Ex. 6 ADVASTAB LS-203 lube & stabilizer ** 2.40
26 Product of Example 22 0.70
Zinc octoate (18% zinc)l 0. 13
27 Product of Example 23 0.70
Zinc octoate (18% zinc) 0. 13
28 Product of Example 24 0.70
Zinc octoate (18% zinc) 0. 13
*Higher than normal amount for PVC pipe
**TM-599 plus lubricant
50

Table XVII
PVC Color Hold (dE) During Processing by Two-Roll Mill @ 390°F
min/ex 1 2 3 4 5 6 7 8 9 10 11 12
CE 5 15.8 15.8 16.1 15.8 16.0 15.9 16.8 17.2 17.9 18.5 20.0 21.2
26 16.7 16.2 15.7 16.1 15.8 16.9 17.5 18.6 21.4 27.0 36.2 43.2

20
 EP 0 945 485 A1

Table XVII (continued)

PVC Color Hold (dE) During Processing by Two-Roll Mill @ 390°F
min/ex 1 2 3 4 5 6 7 8 9 10 11 12
27 16.0 15.4 15.5 15.4 16.1 16.5 18.3 24.4 28.6 40.8 46.8 48.8
CE6 11.5 11.7 12.3 13.0 12.1 13.2 14.5 14.7 15.4 16.7 18.8 19.9
28 12.3 11.5 12.1 12.7 12.2 14.3 15.7 20.5 28.9 35.9 41.5 42.8
10
Table XVIII
PVC Dynamic Thermal Stability by Brabender @190°C
Minutes
Comparative Example 5 9.6
26 9.9
27 8.6
Comparative Example 6 13.9
28 9.9

Example 29 and Comparative Example 7

25
[0075] The following examples compare the thermal stability of a semi-rigid PVC composition containing a homoge-
neous blend of zinc chloride and the latent mercaptan of this invention (Formula 2 along with the by-products shown
by Formulas 3-7) with that of a semi-rigid PVC composition containing a commercial Cd/Ba/Zn/phosphite stabilizer.
[0076] The homogeneous blend of zinc chloride and the latent mercaptan was prepared by charging dropwise a
30 solution of 16.0 grams of anhydrous zinc chloride in 50 mis of dry acetone into 333.2 grams of the latent mercaptan
with stirring at 30°C under a nitrogen blanket and then removing the acetone by heating the solution at 55°C for one
hour under a reduced pressure of 15 mm Hg. Filtration of the remaining liquid yielded a sparkling clear homogeneous
product having a zinc content of 2.1% by weight.
[0077] A conventional semi-rigid PVC composition containing:

INGREDIENT AMOUNT
PVC resin (k=70) 100.0 parts
Diisodecyl phthalate 27.0
Epoxidized soybean oil 3.0
Calcium carbonate 30.0 phr
Stearic acid 0.5 phr

was modified as shown in Table XIX and the resulting compositions were processed on a standard horizontal two-roll
45 mill (roll speeds 30R/40R) at 350°F with chips taken at five minute intervals to a maximum of 60 minutes. The color
properties of the chips were measured using a Hunter Labs Colorimeter (L, a, b) and the yellowness index was selected
as the measurement for comparison in Table XX.

Table XIX
Stabilizer Systems Evaluated
Example Stabilizer Use Level, phr
30 Product of Example 29 2.25
Comp. Ex. 7 Liquid Cd/Ba/Zn/phosphite 3.00
Solid Ba/Zn booster 0.50

21
 EP 0 945 485 A1

Table XX
PVC Color Hold (Yl) During Processing by Two-Roll Mill @ 350°F
min/ex 5 10 15 20 25 30 35 40 45 50 55 60
30 14.8 16.9 18.8 20.2 21.4 22.7 24.8 27.3 31.3 35.6 39.4 45.3
CE 7 16.7 21.1 25.2 28.5 31.7 34.0 36.4 38.6 41.4 44.2 46.0 48.3

[0078] The DTS, recorded as the point at which a sharp upturn in the torque rheometry curve occurs at 200°C on a
BRABENDER PL-2000 rheometer having an electric head and No. 6 roller blades, is shown in Table XXI.

Table XXI
PVC Dynamic Thermal Stability by Brabender @200°C, 80 rpm
30 25.4 minutes
Comparative Example 7 26.5 minutes

[0079] The preferred ratio of zinc to sulfur, as they occur in the various combinations of zinc carboxylate or zinc
chloride with the latent mercaptan of this invention to make a stabilizer for certain applications of the flexible PVC
compositions of this invention, is as shown in Table XXII:

TABLE XXII
APPLICATION % Filler Zn:S Ratio % Zn in stabilizer
Clear calender and extrusion 0.0 0.06:1 0.4
Low fill calender and extrusion; W+C <10 0.12:1 0.9
Mod. filled calender and extrusion; awning 10-25 0.18:1 1.3
Mbd. filled calender and extrusion 10-25 0.24:1 1.7
High filled calender and extrusion 25.0 0.32:1 2.2
Filled plastisol N/A 0.60:1 3.6

[0080] Articles of manufacture contemplated by this invention, e.g. packaging film, tubing, rigid pipe, and window
profile, are formed from the stabilized compositions of this invention by any of the well-known conventional techniques
for forming polymers into shaped articles.

Claims

1. A polymer composition comprising a halogen-containing polymer and degradation products of a blocked mercaptan
present during processing of the composition at an elevated temperature, said blocked mercaptan having the
structure:

r4 m
I I
(R ) a " X - -c c— -s- -R FORMULA 1

(R6)m k5 Lr5J„

22
 EP 0 945 485 A1

wherein a is 1, m is 0, n is 0 or 1; y is 1 or 2, and z is 1; R1 is a hydroxyalkyl, hydroxy(polyalkoxy) alkyl, hydroxy

(polyalkoxy)acylalkyl, acyloxyalkyl, acyloxy(hydroxyalkyl), acyloxy(alkoxyalkyl), acyloxy(polyalkoxy)alkyl, acyloxy
(polyalkoxy)acylalkyl, oxy[bis(alkoxyacylalkyl)], oxy[bis(polyalkoxyacylalkyl)], benzoyloxy(polyalkoxy)alkyl, ben-
zoyloxy(polyalkoxy)acylalkyl, or alkylene bis-(acyloxyalkyl) group in which the alkyl moieties have from 2 to 20
5 carbon atoms, the acyloxy moieties have from 2 to 22 carbon atoms; either R3 or R5 is joined with R7 and 0 to
form a heterocyclic moiety, and the rest of R2, R3, R4, and R5 are hydrogen; and between 0.005% and 0.5%, based
on the weight of the polymer, of a synergist comprising a metallic-based heat stabilizer, a Lewis acid or a mixture
thereof.

10 2. A composition according to claim 1 wherein the halogen-containing polymer is a flexible PVC composition and R1
is an acyloxyalkyl group.

3. A composition according to claim 1 wherein the halogen-containing polymer is a rigid PVC and R1 is a hydroxy
(polyalkoxy)acylalkyl group.
15
4. A composition according to claim 1 wherein the halogen-containing polymer is a rigid PVC and R1 is a hydroxyalkyl
group.

5. A composition according to any preceding claim wherein the synergist is a metallic-based stabilizer.
20
6. A composition according to any one of claims 1 to 4 wherein the synergist is a Lewis acid.

7. A composition according to any preceding claim wherein the metallic-based stabilizer is a zinc carboxylate.

25 8. A composition according to any preceding claim wherein the Lewis acid is zinc chloride.

9. A composition according to any preceding claim wherein the alkyl moieties of Formula 1 are ethyl.

10. A stabilizer composition comprising from 87.5% to 98.5%, by weight, of a blocked mercaptan having the structure:
30

35 R4 M

(R ) . - x - -s- -R FORMULA 1
<R4>. lR3J„
40

wherein a is 1, m is 0, n is 0 or 1; y is 1 or 2, and z is 1; R1 is a hydroxyalkyl, hydroxy(polyalkoxy)alkyl, hydroxy

45 (polyalkoxy)acylalkyl, acyloxyalkyl, acyloxy(hydroxyalkyl), acyloxy(alkoxyalkyl), acyloxy(polyalkoxy)alkyl, acyloxy
(polyalkoxy)acylalkyl, oxy[bis(alkoxyacylalkyl)], oxy[bis(polyalkoxyacylalkyl], benzoyloxy(polyalkoxy)alkyl, ben-
zoyloxy(polyalkoxy)acylalkyl, or alkylene bis-(acyloxyalkyl) group in which the alkyl moieties have from 2 to 20
carbon atoms, the acyloxy moieties have from 2 to 22 carbon atoms; R2, R3, R4, and R5 are hydrogen; and either
R3 or R5 is joined with R7 and O to form a heterocyclic moiety;
so the balance comprising a synergist which is a metal-based stabilizer, a Lewis acid or a mixture thereof.

11. A composition according to claim 10 wherein the metallic-based heat stabilizer is an organometal compound.

12. A composition according to claim 11 wherein the metallic-based heat stabilizer is a zinc carboxylate.
55
13. A composition according to any one of claims 10 to 12 wherein the synergist comprises a Lewis acid.

14. A composition according to claim 13 wherein the Lewis acid is zinc chloride.

23
 EP 0 945 485 A1

15. A composition according to any one of claims 10 to 14 wherein the blocked mercaptan constitutes from 93.5% to
97.5% of the total weight.

16. A composition according to anyone of claims 10 to 15 characterised further in that it is a clear, homogenous liquid.

17. A composition according to any one of claims 10 to 16 wherein the alkyl moieties of Formula 1 are ethyl.

18. A method for the preparation of a composition for stabilizing a halogen-containing polymer, said method comprising
reacting acrolein with a vinyl ether in the presence of a catalytic amount of zinc chloride to form a 3,4-dihydro-
2-substituted-2H-pyran and reacting said pyran with a mercaptan whereby the sulfhydryl group of the mercaptan
adds across the double bond of the pyran to form a latent mercaptan in admixture with the zinc chloride.

24
 EP 0 945 485 A1

J ) European Patent Application Number

EUROPEAN SEARCH REPORT
Office EP 99 30 2322

DOCUMENTS CONSIDERED TO BE RELEVANT

Category Citation of document with indication, where appropriate, Relevant CLASSIFICATIONOFTHE
of relevant passages to claim APPLICATION (lnt.CI.6)
EP 0 224 679 A (HUELS CHEMISCHE WERKE AG) 1,2,5,7. C08K13/02
10 June 1987 9-12 C08L27/06
* page 6, column 30 - page 8, column 30 * //(C08K13/02,
* page 6, column 5 - column 30 * 18 3:16,5:098,
5:37)
EP 0 260 380 A (ARGUS CHEM) 23 March 1988 1-18
* examples 13-20; tables D,E *

TECHNICALFIELDS
SEARCHED (lnt.CI.6)
C08K

The present search report has been drawn up for all ciaims
Placeofsearch Dateofcompletionofthesearch Examiner
THE HAGUE 29 June 1999 Frieden'ch, P
CATEGORYOFCITEDDOCUMENTS T:theory orprinciple underlying the invention
E: earlier patent document, but published on, or
X:particularly relevant iftaken alone after the filing date
Y: particularly relevant ifcombined with another D: document cited in the application
document of the same category L: document cited for other reasons
A:technological background
O: non-written disclosure &: memberofthe same patent family, corresponding
P: intermediate document document

25
 EP 0 945 485 A1

ANNEX TO THE EUROPEAN SEARCH REPORT

ON EUROPEAN PATENT APPLICATION NO. EP 99 30 2322

This annex lists the patent family members relating to the patent documents cited in the above-mentioned European search report.
The members are as contained in the European Patent Office EDP file on
The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information.
29-06-1999

Patent document Publication Patent family Publication

cited in search report date member(s) date
EP 0224679 10-06-1987 DE 3542862 A 11-06-1987
JP 62146942 A 30-06-1987
US 4973619 A 27-11-1990
US 4849463 A 18-07-1989

EP 0260380 23-03-1988 US 4782170 A 01- 11-1988

CA 1273951 A 11-09-1990
JP 62277394 A 02- 12-1987

For more details about this annex :see Official Journal of the European Patent Office, No. 12/82

26