CA1063791A - Stabilized vinyl halide resin compositions - Google Patents
Stabilized vinyl halide resin compositionsInfo
- Publication number
- CA1063791A CA1063791A CA223,541A CA223541A CA1063791A CA 1063791 A CA1063791 A CA 1063791A CA 223541 A CA223541 A CA 223541A CA 1063791 A CA1063791 A CA 1063791A
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/138—Phenolates
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure Vinyl halide resin compositions that are characterized by excellent heat and light stability, color, and clarity and by little tendency to plate-out are prepared by incorporating in the composition a stabilizer that contains 4.5 percent to 6.0 percent by weight of a mixture of metals comprising cadmium, stro?tium, zinc, and potassium as oil-soluble salts and 2.0 percent to 3.5 percent by weight of phosphorus as an organic phosphite.
Description
1 1I This invention relates to stabili~ers for vinyl halide
2 ~ resin compositions and to resinous compositions that contain these
3 ¦ stabilizers.
~ Vinyl halide resins deteriorate and discolor rapidly when ¦they are exposed to elevated temperatures during their compounding 6 ~ and fabrication. This deterioration can be inhibited or p~evented 7 ¦by incorporating heat stabilizers in the resinous compositions.
8 Among the most widely-used stabilizer systems for vinyl halide g resins are those that contain oil-soluble salts of barium and cadmium. There are, however, certain disadvantages to the use of the barium/cadmium stabiliz~s. Barium compounds, which are~at 12` present in short supply, are quite toxic. The barium/cadmium 13, stabilizers must be used in rather large amounts to achieve the 14 desired stabilization; such large amounts of the barium an~ ~
cadmium salts affect the clarity of the vinyl halide resin~compo-sitions and increase their viscosity, which is objectionable 1n 17 the processing of plastisols. In view of the current con¢ern 18 regarding the use of industrial chemicals that are known to be 19 toxic, it is desirable that the barium/cadmium stabilizers be 20 replaced by equally-effective stabilizers that contain less toxic 21: materials and that do not share the other disadvantages of the 22: barium/cadmium stabilizers.
23 In accordance with this invention, it has been ~ound that 24 vinyl halide resin compositions that are characterized by excellen heat and light stability, color, and clarity and by little tendenc 2~ to plate-out are obtained by incorporating in the composition a 27 stabilizer that contains from 4.5 percent to 6.0 percent by weight 28 of a mixture of metals comprising cadmium, strontium~ zinc, and 29 potassium as oil-soluble salts and from 2.0 percent to 3.5 percent 30 by weight of phosphorus as an organic phosphite.
. - 2 -: . : . ~ , , . ~ . .
37~3l These stabilizers are at least as effec-ti~e against thermal degradation as the conventional barium~cadmium stabilizers; their lower total metal content provides greater flexibility in the compounding of the stabilizers and results in improved film clarity, lower lubrication, and less plate-ou-t.
Thus, a first embodiment provides a heat and light stable xesinous composition comprising a vinyl halide resin and from 1 part to 10 parts per 100 parts by weight of said resinous composition of a stabilizer that contains a) a mixture of metal salts comprising a cadmi.um salt, a strontium salt, a potassium salt, and a zinc ~alt, said salts being selected from the group consisting of salts of alkylphenols in which the alkyl groups have from 4 to 12 carbon atoms, salts of monocarboxylic acids haying 6 to 12 carbon atoms, and mixtures ` ..
of said salts- and b) an organic phosphite seIected from the group consisting of triaryl phosphites, trialkyl phosphites, and alkyl aryl ; .
phosph.ites wh.erein each.alkyl group has from 6 to 12 carbon atoms and each.ar~l group is phenyl, hydroxyphenyl, halophenyl, ~ .
` 20 or alkylphen~l, said stabilizer containing 4.5 percent to 6.0 percent by weight of a mixture of metals comprising cadmi.um, strontium, potassium, . .
and zinc as said salts and 2.0 percent to 3.5 percent by weight ~ of phosphorus as said organic phos~phîte.
: Thus, a second embodiment proyides a stabilizer for -. vinyl halide res-in compositi.ons that comprises . a) a metal salt component compri.s:ing a cadmium salt, a ~ strontium salt, a potassium salt, and a zinc ~alt selected from th.e group consisting of salts of alkylphenols in which the alkyl ; 3Q groups have from 4 to 12 carbon atoms, salts of monocarboxylic acids having 6 to 12 carbon atoms-, and mixtures o~ said salts, ~:, and :''., ~,~ ~
.. 7 ~37~1 b) an organic phosphite selected from the group consisting of triaryl phosphites, trialkyl phosphites, and alkyl aryl phosphites wherein each alkyl group has from 6 to 12 carbon atoms and each aryl group is phenyl, hydroxyphenyl, halophenyl, or alkylphenol, said stabilizer containin~ 4.5 percent to 6.0 percent by weight .
of a mixture o~ metals comprisi.ng cadmi.um, strontium potassium and zinc as said salts and 2.0 percent to 3.5 percent by weight of phosphorus as said oryanic phosphite.
: 10 The novel stabilizers contain from about 40 percent to 55 percent by weight of a metal salt component that comprises salts o~ cadmium, strontium, zinc, and potassium and from about 30 percent to 40 percent by weight of an organic phosphite. In ~
addition, they may contain a non-polar organic sol~ent, such as ;.
toluene, naphtha, or mineral sp;ritsi a solubilizing agent, such as tall oil ~atty aci.ds; a viscosity-controlling agent, such as tripropylene glycol; and other conventional additi~es. `-The metal salt component o~ the stabilizers comprises an oil-soluble cadmi.um salt, an oi.l-soluble strontium salt, an oil-soluble zinc salt, and an oil-soluble potassium salt. The salts may be salts of alk.ylphenols in which the alkyl groups have from ~ 4 to 12 carbon atoms, salts o~ monocarboxylic aci.ds having 6 to ;.
. 12 carbon atoms, or mi.xtures o~ these salts. The al~ylphenols from which.the salts may be preparad are thos.e h.a~ing one or two straight-chain or branched-ch.ain substituents, such as n-butyl-phenol, tert.octylphenol, n-dodecylphenol, di.-tert.butylphenol, and dinonylphenol. The monocarboxyli.c acids ~rom which the salts can be prepared include aromatic acids, such.as benzoic acid and tert.butylbenzoic acid; aliphatic aci.d~, such.as hexanoic acid, octanoic acid, decanoic acid, dodecanoi.c:acid/ 2-ethylbutanoic .~ aci.d, 2-ethylhexanoic acid, isooctanoi.c acid, isononanoic acid, ~ and 2-eth.yldecanoic acid; cycloali.phati.c acids, such as cyclo--3a-~Y~
hexanoic acid~ cycloheptanoic acid, and dimethylcycloheptanoic 2 ~ acid; and mixtures of these acids. I-t is pre~erred that the metal 3 jsalt component of the stabilizers contain at least one salt of an alkylphenol and at least one salt o~ a monocarboxylic acid.
s ~Particularly good results are obtained when the metal salt com-6 ¦ponent comprises cadmium and zinc salts of monocarboxylic acids~
7 ¦1 ~or example~ cadmium benzoate, zinc benzoate, cadmium 2-ethyl-8 ¦ hexanoate, and zinc isononanoate, and strontium and potassium g ¦salts of alkylphenols, for example, strontium nonylphenate, strontium decylphenate, potassium di-tert.butylphenate, and ¦potassium nonylphenate.
12 ¦ The metal salt component of the stabilizers may contain 13 ¦ ~rom about 30 percent to 60 percent by weight of a cadmium salt, 14 125 percent to 55 percent by weight of a strontium salt, 5 percent 1; ¦to 20 percent by weight of a zinc salt, and 5 to 25 percent by 16 ¦weight of a potassium salt. It pre~erably contains 35 percent to 17 ¦50 percent by weight of a cadmium saltg 30 percent to 45 percent 18 ¦by weight o~ a strontium salt, 7 percent to 15 percent by weight 19 ¦of a zinc salt, and lOto 25 percent by weight of a potassium salt.
20 ¦ The organic phosphites that may be used in the stabilizers 21 ¦ of this invention include a wide variety of aliphatic and aromatic 22 I phosphites. Among them are trialkyl phosphites, triaryl phosphites i : 23 I and alkyl aryl phosphites. Illustrative of these phosphites are ;~ 24 ¦triphenyl phosphite, tri-(tert,butylphenyl) phosphite~ tri(nonyl-25 ¦ phenyl) phosphite, tri(isooctyl) phosphite, tridecyl phosphite, 26 ¦ tri(dipropylene glycol) phosphite, diphenyl butyl phosphite, ¦diphenyl decyl phosphite, diphenyl propylene glycol phosphite, 28 ¦ dioctyl phenyl phosphite~ di(2-ethylbutyl) phenyl phosphite, di(p-. 29 ¦ tert.octylphenyl) 2-ethylhexyl phosphite, di(nonylphenyl) 2-chloro-lethyl phosphite, di(B-chloropropyl) chlorophenyl phosphite, didecyl '~ ' I
~ I - 4 -. . . . .
1 1l phenyl phosphite, and diisodecyl pentaerythritol phosphite, The 2 ~ pre~erred phosphites are alkyl aryl phosphites in which the alkyl 3 1 groups are straight-chain or branched-chain groups having from
~ Vinyl halide resins deteriorate and discolor rapidly when ¦they are exposed to elevated temperatures during their compounding 6 ~ and fabrication. This deterioration can be inhibited or p~evented 7 ¦by incorporating heat stabilizers in the resinous compositions.
8 Among the most widely-used stabilizer systems for vinyl halide g resins are those that contain oil-soluble salts of barium and cadmium. There are, however, certain disadvantages to the use of the barium/cadmium stabiliz~s. Barium compounds, which are~at 12` present in short supply, are quite toxic. The barium/cadmium 13, stabilizers must be used in rather large amounts to achieve the 14 desired stabilization; such large amounts of the barium an~ ~
cadmium salts affect the clarity of the vinyl halide resin~compo-sitions and increase their viscosity, which is objectionable 1n 17 the processing of plastisols. In view of the current con¢ern 18 regarding the use of industrial chemicals that are known to be 19 toxic, it is desirable that the barium/cadmium stabilizers be 20 replaced by equally-effective stabilizers that contain less toxic 21: materials and that do not share the other disadvantages of the 22: barium/cadmium stabilizers.
23 In accordance with this invention, it has been ~ound that 24 vinyl halide resin compositions that are characterized by excellen heat and light stability, color, and clarity and by little tendenc 2~ to plate-out are obtained by incorporating in the composition a 27 stabilizer that contains from 4.5 percent to 6.0 percent by weight 28 of a mixture of metals comprising cadmium, strontium~ zinc, and 29 potassium as oil-soluble salts and from 2.0 percent to 3.5 percent 30 by weight of phosphorus as an organic phosphite.
. - 2 -: . : . ~ , , . ~ . .
37~3l These stabilizers are at least as effec-ti~e against thermal degradation as the conventional barium~cadmium stabilizers; their lower total metal content provides greater flexibility in the compounding of the stabilizers and results in improved film clarity, lower lubrication, and less plate-ou-t.
Thus, a first embodiment provides a heat and light stable xesinous composition comprising a vinyl halide resin and from 1 part to 10 parts per 100 parts by weight of said resinous composition of a stabilizer that contains a) a mixture of metal salts comprising a cadmi.um salt, a strontium salt, a potassium salt, and a zinc ~alt, said salts being selected from the group consisting of salts of alkylphenols in which the alkyl groups have from 4 to 12 carbon atoms, salts of monocarboxylic acids haying 6 to 12 carbon atoms, and mixtures ` ..
of said salts- and b) an organic phosphite seIected from the group consisting of triaryl phosphites, trialkyl phosphites, and alkyl aryl ; .
phosph.ites wh.erein each.alkyl group has from 6 to 12 carbon atoms and each.ar~l group is phenyl, hydroxyphenyl, halophenyl, ~ .
` 20 or alkylphen~l, said stabilizer containing 4.5 percent to 6.0 percent by weight of a mixture of metals comprising cadmi.um, strontium, potassium, . .
and zinc as said salts and 2.0 percent to 3.5 percent by weight ~ of phosphorus as said organic phos~phîte.
: Thus, a second embodiment proyides a stabilizer for -. vinyl halide res-in compositi.ons that comprises . a) a metal salt component compri.s:ing a cadmium salt, a ~ strontium salt, a potassium salt, and a zinc ~alt selected from th.e group consisting of salts of alkylphenols in which the alkyl ; 3Q groups have from 4 to 12 carbon atoms, salts of monocarboxylic acids having 6 to 12 carbon atoms-, and mixtures o~ said salts, ~:, and :''., ~,~ ~
.. 7 ~37~1 b) an organic phosphite selected from the group consisting of triaryl phosphites, trialkyl phosphites, and alkyl aryl phosphites wherein each alkyl group has from 6 to 12 carbon atoms and each aryl group is phenyl, hydroxyphenyl, halophenyl, or alkylphenol, said stabilizer containin~ 4.5 percent to 6.0 percent by weight .
of a mixture o~ metals comprisi.ng cadmi.um, strontium potassium and zinc as said salts and 2.0 percent to 3.5 percent by weight of phosphorus as said oryanic phosphite.
: 10 The novel stabilizers contain from about 40 percent to 55 percent by weight of a metal salt component that comprises salts o~ cadmium, strontium, zinc, and potassium and from about 30 percent to 40 percent by weight of an organic phosphite. In ~
addition, they may contain a non-polar organic sol~ent, such as ;.
toluene, naphtha, or mineral sp;ritsi a solubilizing agent, such as tall oil ~atty aci.ds; a viscosity-controlling agent, such as tripropylene glycol; and other conventional additi~es. `-The metal salt component o~ the stabilizers comprises an oil-soluble cadmi.um salt, an oi.l-soluble strontium salt, an oil-soluble zinc salt, and an oil-soluble potassium salt. The salts may be salts of alk.ylphenols in which the alkyl groups have from ~ 4 to 12 carbon atoms, salts o~ monocarboxylic aci.ds having 6 to ;.
. 12 carbon atoms, or mi.xtures o~ these salts. The al~ylphenols from which.the salts may be preparad are thos.e h.a~ing one or two straight-chain or branched-ch.ain substituents, such as n-butyl-phenol, tert.octylphenol, n-dodecylphenol, di.-tert.butylphenol, and dinonylphenol. The monocarboxyli.c acids ~rom which the salts can be prepared include aromatic acids, such.as benzoic acid and tert.butylbenzoic acid; aliphatic aci.d~, such.as hexanoic acid, octanoic acid, decanoic acid, dodecanoi.c:acid/ 2-ethylbutanoic .~ aci.d, 2-ethylhexanoic acid, isooctanoi.c acid, isononanoic acid, ~ and 2-eth.yldecanoic acid; cycloali.phati.c acids, such as cyclo--3a-~Y~
hexanoic acid~ cycloheptanoic acid, and dimethylcycloheptanoic 2 ~ acid; and mixtures of these acids. I-t is pre~erred that the metal 3 jsalt component of the stabilizers contain at least one salt of an alkylphenol and at least one salt o~ a monocarboxylic acid.
s ~Particularly good results are obtained when the metal salt com-6 ¦ponent comprises cadmium and zinc salts of monocarboxylic acids~
7 ¦1 ~or example~ cadmium benzoate, zinc benzoate, cadmium 2-ethyl-8 ¦ hexanoate, and zinc isononanoate, and strontium and potassium g ¦salts of alkylphenols, for example, strontium nonylphenate, strontium decylphenate, potassium di-tert.butylphenate, and ¦potassium nonylphenate.
12 ¦ The metal salt component of the stabilizers may contain 13 ¦ ~rom about 30 percent to 60 percent by weight of a cadmium salt, 14 125 percent to 55 percent by weight of a strontium salt, 5 percent 1; ¦to 20 percent by weight of a zinc salt, and 5 to 25 percent by 16 ¦weight of a potassium salt. It pre~erably contains 35 percent to 17 ¦50 percent by weight of a cadmium saltg 30 percent to 45 percent 18 ¦by weight o~ a strontium salt, 7 percent to 15 percent by weight 19 ¦of a zinc salt, and lOto 25 percent by weight of a potassium salt.
20 ¦ The organic phosphites that may be used in the stabilizers 21 ¦ of this invention include a wide variety of aliphatic and aromatic 22 I phosphites. Among them are trialkyl phosphites, triaryl phosphites i : 23 I and alkyl aryl phosphites. Illustrative of these phosphites are ;~ 24 ¦triphenyl phosphite, tri-(tert,butylphenyl) phosphite~ tri(nonyl-25 ¦ phenyl) phosphite, tri(isooctyl) phosphite, tridecyl phosphite, 26 ¦ tri(dipropylene glycol) phosphite, diphenyl butyl phosphite, ¦diphenyl decyl phosphite, diphenyl propylene glycol phosphite, 28 ¦ dioctyl phenyl phosphite~ di(2-ethylbutyl) phenyl phosphite, di(p-. 29 ¦ tert.octylphenyl) 2-ethylhexyl phosphite, di(nonylphenyl) 2-chloro-lethyl phosphite, di(B-chloropropyl) chlorophenyl phosphite, didecyl '~ ' I
~ I - 4 -. . . . .
1 1l phenyl phosphite, and diisodecyl pentaerythritol phosphite, The 2 ~ pre~erred phosphites are alkyl aryl phosphites in which the alkyl 3 1 groups are straight-chain or branched-chain groups having from
4 6 to 12 carbon atoms and the aryl groups are phenyl or substituted 1 phenyl groups in which the substituents are hydroxyl, halogen, or 6 ¦ alkyl groups. Examples of the preferred phosphites are diphenyl 7 1 decyl phosphite and didecyl phenyl phosphite.
8 ¦ The vinyl halide resins that may be present in the 9 ¦ stabilized compositions of this invention are the resinouS product, 3'~
¦ obtained by the polymerization of a vinyl halide in the presence ¦ or absence of a copolymerizable monomer. The term "vinyl halide 2 ¦ resin'r as used herein includes vinyl halide homopolymers, such as 13 j polyvinyl chloride and polyvinylidene chloride, as well as vinyl 14 ¦ halide copolymers including those formed by the polymerization of ¦ a vinyl halide with a comonomer, such as vinyl acetate, vinyl 16 ¦ propionate, vinyl butyrate, vinylidene chloride, styrene, methyl 17 ¦methacrylate~ dialkyl fumarate or maleate, and the like. The 8 ¦ vinyl halide is ordinarily the chloride, but the bromide and 19 ¦ fluoride may also be used. The copolymers contain at least 70 ¦ percent of vinyl halide units and up to 30 percent of the comonome .
21 units. The in~ention is also applicable to mixtures of vinyl 22 halide resins in a major proportion with a minor proportion o~ -~
u another synthetic resin, such as chlorinated polyethylene, poly-acrylate and polymethacrylate esters, and copolymers of acrylo-nitrile, butadiene~ and styrene.
26 In addition to the vinyl halide resin and stabilizer 7 the 27 compositions may contain plasticizers such as dioctyl phthalate, 28 dibutyl sebacate, tricresyl phosphate, and octyl diphenyl phosphat "
29 other heat and light stabilizers such as epoxidized oils, pigments dyes, extenders, solvents, and other resin additives in the amount ~- 31 ordinarily used for the purpose indi~ated.
`- 5 -: - ~ .
.: . , -,l 1063791 Only a small amount of the stabilizer need be present i~
2 ¦the vinyl halide resin compo5itions of this invention. As little 3 ~as l percent of the stabilizer, based on the weight of the compo-4 sition, will bring abou-t an appreciable improvement in the heat S and light stability of the composition. Ten percent or more can 6 be used, but these larger amounts generally do not provide further 7 improvement in the properties of the compositions and -for this 8 reason are not ordinarily used. While the amount of the stabilizer g that will provide optimum heat stability and resiStance to plate-¦out depends upon such factors as the choice of stabilizer component js ¦and the choice of vinyl halide resin, in most cases from 2 percent 2 ¦to 4 percent of the stabilizer, based on the weight o-f the vinyl 13 ¦halide resin composition, is used.
14 The stabilized vinyl halide resin compositions may be prepared by any suitable and ~onvenient procedure. It is generall~
16 preferred to blend the stabilizer or the individual stabilizer 17 components with the vinyl halide resin at ambient temperature and 8 ¦ to mill the composition on a two-roll mill at a temperature betweeI i ¦300F. and 400F. for a time sufficient to form a homogeneous sheet. The plasticizer and other ingredients may be added with 21 the stabilizer. The stabilized composition may then be removed 22 from the mill in the form of a sheet of the desired thickness 23 ¦which may be used as such or subjected to polishing or embossing 24 ¦treatment.
¦ The invention is further illustrated by the following 26 ¦e~amples. In these examples~ all parts are parts by weight and 27 ¦all percentage5 are percentages by weight.
:' . , . . ~,, .
'106~
¦ Example 1 2 ¦ A series of stabilizers was prepared ~y mixing together 3 ¦the materials llsted in Table I. For compar~tive purposes, a 4 ¦convent~onal barium/cadmium/zinc stabilizer was also prepared.
s ¦ Example 2 .
6 ¦ A mixture of lO0 parts of poly~inyl chloride (Tenneco*PVC
? ¦225), 40 parts of dioctyl phthalate, 5 parts of epoxidized soybean ~ ¦oil, 0.3 part o~` stearic acid, and 2 5 parts of one of the 9 ¦stabilizers described in Example l was blended at ambient tempera-¦ture and then charged to a two-roll, steam-heated, dif~erential ¦speed mill whose surface temperature wa~ maintained at 3S0F. The lt ~ mixture was milled until its degradation was complete as indicated ¦by its color. The dynamic heat stability ratings of the composi-tions prepared in this way are given in Table II. In this table, :
the following numerical scale is used to indicate the color of 16 the compositions:
l = Colorless 18 2-3 = Very light yellow 19 4-5 = Light yellow 6-7 = Yellow 21 8-9 = Dark yellow 2s . .
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2 iiDynamic Heat Stability of IfClear Stabilized Compositions 3 1lColor a:Eter indicated time of' 4 '¦composition containing stabilizer Il Minutes at Comparative s ¦ 3800F. ~
~ 30 8 7 7 8 ~1 1 IZ ¦ Example 3 13 ¦ A mixture of 100 parts o-f polyvinyl chloride ~Tenneco 14 ¦ PVC 225), 45 parts of dioctyl phthalate, 5 parts of epoxidized 15 ¦ soybean oil~ 0.3 part of stearic acid, 20 parts of calcium carbon-¦ ate, 2 parts of titanium dioxide, and 2.5 parts of one of the 17 ¦ stabilizers described in Example 1 was blended at ambient tempera-18 ¦ ture and then charged to a two-roll, steam-heated, dif~erential-~9 ¦speed mill whose surface temperature was maintained at 380F. The zo ¦mixture was milled until its degradation was complete as indicated 21 by its color. The dynamic heat stability ratings o-f the composi-Z2 tions prepared in this way are given in Table III. In this table, ~3 ¦ the following numerical scale is used to indicate the color of the compositions:
2S 1 = White 26 2-3 = Very slight color 27 4-5 = Very light tan 28 6-7 = Light tan 30 ~ 8-9 = Tan . ~ ' . I _ g _ ~., . ..
.
~0637~1 ~ ¦j Table III
2 1¦Dynamic Heat Stability of ~IFilled Stabilized Compositions 'IColor a~ter indicated time of 4 1¦composition containing stabilizer ll Minutes at Comparative s 380F. A B l o 1 25 6 5 ~ 7 ll 30 8 7 8 13 ¦ ~ From the data in Tables II and III, it will be seen that 14 ¦ in both clear and filled polyvinyl chloride compositions the 15 ¦ stabilizers of this invention provided heat stabilization better 16 ¦ than that obtained using a barium/cadmium/zinc stabilizer or a ~ ¦stabi1izer th t co~tained cael_iu~, s-ronti~l~, and zinc salts.
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8 ¦ The vinyl halide resins that may be present in the 9 ¦ stabilized compositions of this invention are the resinouS product, 3'~
¦ obtained by the polymerization of a vinyl halide in the presence ¦ or absence of a copolymerizable monomer. The term "vinyl halide 2 ¦ resin'r as used herein includes vinyl halide homopolymers, such as 13 j polyvinyl chloride and polyvinylidene chloride, as well as vinyl 14 ¦ halide copolymers including those formed by the polymerization of ¦ a vinyl halide with a comonomer, such as vinyl acetate, vinyl 16 ¦ propionate, vinyl butyrate, vinylidene chloride, styrene, methyl 17 ¦methacrylate~ dialkyl fumarate or maleate, and the like. The 8 ¦ vinyl halide is ordinarily the chloride, but the bromide and 19 ¦ fluoride may also be used. The copolymers contain at least 70 ¦ percent of vinyl halide units and up to 30 percent of the comonome .
21 units. The in~ention is also applicable to mixtures of vinyl 22 halide resins in a major proportion with a minor proportion o~ -~
u another synthetic resin, such as chlorinated polyethylene, poly-acrylate and polymethacrylate esters, and copolymers of acrylo-nitrile, butadiene~ and styrene.
26 In addition to the vinyl halide resin and stabilizer 7 the 27 compositions may contain plasticizers such as dioctyl phthalate, 28 dibutyl sebacate, tricresyl phosphate, and octyl diphenyl phosphat "
29 other heat and light stabilizers such as epoxidized oils, pigments dyes, extenders, solvents, and other resin additives in the amount ~- 31 ordinarily used for the purpose indi~ated.
`- 5 -: - ~ .
.: . , -,l 1063791 Only a small amount of the stabilizer need be present i~
2 ¦the vinyl halide resin compo5itions of this invention. As little 3 ~as l percent of the stabilizer, based on the weight of the compo-4 sition, will bring abou-t an appreciable improvement in the heat S and light stability of the composition. Ten percent or more can 6 be used, but these larger amounts generally do not provide further 7 improvement in the properties of the compositions and -for this 8 reason are not ordinarily used. While the amount of the stabilizer g that will provide optimum heat stability and resiStance to plate-¦out depends upon such factors as the choice of stabilizer component js ¦and the choice of vinyl halide resin, in most cases from 2 percent 2 ¦to 4 percent of the stabilizer, based on the weight o-f the vinyl 13 ¦halide resin composition, is used.
14 The stabilized vinyl halide resin compositions may be prepared by any suitable and ~onvenient procedure. It is generall~
16 preferred to blend the stabilizer or the individual stabilizer 17 components with the vinyl halide resin at ambient temperature and 8 ¦ to mill the composition on a two-roll mill at a temperature betweeI i ¦300F. and 400F. for a time sufficient to form a homogeneous sheet. The plasticizer and other ingredients may be added with 21 the stabilizer. The stabilized composition may then be removed 22 from the mill in the form of a sheet of the desired thickness 23 ¦which may be used as such or subjected to polishing or embossing 24 ¦treatment.
¦ The invention is further illustrated by the following 26 ¦e~amples. In these examples~ all parts are parts by weight and 27 ¦all percentage5 are percentages by weight.
:' . , . . ~,, .
'106~
¦ Example 1 2 ¦ A series of stabilizers was prepared ~y mixing together 3 ¦the materials llsted in Table I. For compar~tive purposes, a 4 ¦convent~onal barium/cadmium/zinc stabilizer was also prepared.
s ¦ Example 2 .
6 ¦ A mixture of lO0 parts of poly~inyl chloride (Tenneco*PVC
? ¦225), 40 parts of dioctyl phthalate, 5 parts of epoxidized soybean ~ ¦oil, 0.3 part o~` stearic acid, and 2 5 parts of one of the 9 ¦stabilizers described in Example l was blended at ambient tempera-¦ture and then charged to a two-roll, steam-heated, dif~erential ¦speed mill whose surface temperature wa~ maintained at 3S0F. The lt ~ mixture was milled until its degradation was complete as indicated ¦by its color. The dynamic heat stability ratings of the composi-tions prepared in this way are given in Table II. In this table, :
the following numerical scale is used to indicate the color of 16 the compositions:
l = Colorless 18 2-3 = Very light yellow 19 4-5 = Light yellow 6-7 = Yellow 21 8-9 = Dark yellow 2s . .
.~ 28 .
*Trade Mark A~` - 7 ~ .
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~ 8 ~ O oo O 11~ o 1~ ~ dl tS:~ d' 10 1 C~ M ~I I O ~ IO O d1 0 I N O I ~ N
l N c~ C~ N
Il l _ I
l O O oo O C~
12 I ~ O O OD ~1 0 0 ~ ..
I ~ o~ o ~ c~ o I ~ ~ o Q I C~
13 ¦ N ,I C~
I ~ -14 I . O O CO O 6 I ,_, ~d O O oo ,1 0 ~i 00 ~ d~ O ~
15 I ~.¢ 00 0 q`~ N O I d~ r-i ~i N O O I C~i 16 ~ .
i ~ î
Ia ¦ ~ ~ a~ 0o , I U~ O . -' 19 I ~ rl l ~ V
20 I _~ +~
I ~q ~ u~
21 I ~ C~ O ~ rl ~ ~ 8 I Z:( ,5~ 0 .5~ N ~
I O ~ a? ~ rl ~1 ~; rl O
22 I S~ ~ 1 ~ .
l I 1:: 0 0 ~ ,Q ~i C) ~d rl ~q I 8 ON ~ O c~ 5~ 0 23 I O ~ 1 ~ ~ L~ rl O t~
I o a~ o ~ z~ Q u~ V
24 ¦ ~ ~ o~ t~
R ~ O td I ~ s~
i ~1 O E~ 1 a) td .
~ 5 26 l ~ g ~ ~ ~ ~ ;
28 l .. I
. 29 . - 8 -I , .
; l ` :: ,' : :` :: ` " ` `
. ~',: , , ` ` ~ , ,' , ,: ' :' I l¦ Tab:Le II
2 iiDynamic Heat Stability of IfClear Stabilized Compositions 3 1lColor a:Eter indicated time of' 4 '¦composition containing stabilizer Il Minutes at Comparative s ¦ 3800F. ~
~ 30 8 7 7 8 ~1 1 IZ ¦ Example 3 13 ¦ A mixture of 100 parts o-f polyvinyl chloride ~Tenneco 14 ¦ PVC 225), 45 parts of dioctyl phthalate, 5 parts of epoxidized 15 ¦ soybean oil~ 0.3 part of stearic acid, 20 parts of calcium carbon-¦ ate, 2 parts of titanium dioxide, and 2.5 parts of one of the 17 ¦ stabilizers described in Example 1 was blended at ambient tempera-18 ¦ ture and then charged to a two-roll, steam-heated, dif~erential-~9 ¦speed mill whose surface temperature was maintained at 380F. The zo ¦mixture was milled until its degradation was complete as indicated 21 by its color. The dynamic heat stability ratings o-f the composi-Z2 tions prepared in this way are given in Table III. In this table, ~3 ¦ the following numerical scale is used to indicate the color of the compositions:
2S 1 = White 26 2-3 = Very slight color 27 4-5 = Very light tan 28 6-7 = Light tan 30 ~ 8-9 = Tan . ~ ' . I _ g _ ~., . ..
.
~0637~1 ~ ¦j Table III
2 1¦Dynamic Heat Stability of ~IFilled Stabilized Compositions 'IColor a~ter indicated time of 4 1¦composition containing stabilizer ll Minutes at Comparative s 380F. A B l o 1 25 6 5 ~ 7 ll 30 8 7 8 13 ¦ ~ From the data in Tables II and III, it will be seen that 14 ¦ in both clear and filled polyvinyl chloride compositions the 15 ¦ stabilizers of this invention provided heat stabilization better 16 ¦ than that obtained using a barium/cadmium/zinc stabilizer or a ~ ¦stabi1izer th t co~tained cael_iu~, s-ronti~l~, and zinc salts.
Z9 ~
3D i ' I
:. ' - 10 -~. ~
: .. :,,, `. : - - . . : ' , - .: : . , , ~ . .. ., , , : . : .
' : ' ' . : ' ' ' ., :' . ' ' .' ' ' ' ' .' ` .
: ~ , - , . ~
Claims (18)
1. A heat and light stable resinous composition comprising a vinyl halide resin and from 1 part to 10 parts per 100 parts by weight of said resinous composition of a stabilizer that contains a) a mixture of metal salts comprising a cadmium salt, a strontium salt, a potassium salt, and a zinc salt, said salts being selected from the group consisting of salts of alkylphenols in which the alkyl groups have from 4 to 12 carbon atoms, salts of monocarboxylic acids having 6 to 12 carbon atoms, and mixtures of said salts and b) an organic phosphite selected from the group consisting of triaryl phosphites, trialkyl phosphites, and alkyl aryl phosphites wherein each alkyl group has from 6 to 12 carbon atoms and each aryl group is phenyl, hydroxyphenyl, halo-phenyl, or alkylphenyl, said stabilizer containing 4.5 percent to 6.0 percent by weight of a mixture of metals comprising cadmium, strontium, potassium, and zinc as said salts and 2.0 percent to 3.5 percent by weight of phosphorus as said organic phosphite.
2. A heat and light stable resinous composition as defined in Claim 1 that contains from 2 parts to 4 parts by weight of said stabilizer per 100 parts by weight of said resinous composition.
3. A heat and light stable resinous composition as defined in Claim 1 wherein the vinyl halide resin is polyvinyl chloride.
4. A heat and light stable resinous composition as defined in Claim 1 wherein the mixture of metal salts contains 30 percent to 60 percent by weight of a cadmium salt, 25 percent to 55 percent by weight of a strontium salt, 5 percent to 20 percent by weight of a zinc salt, and 5 to 25 percent by weight of a potassium salt.
5. A heat and light stable resinous composition as defined in Claim 1 wherein the mixture of metal salts contains 35 percent to 50 percent by weight of a cadmium salt, 30 percent to 45 percent by weight of a strontium salt, 7 percent to 15 percent by weight of a zinc salt, and 10 to 25 percent by weight of a potassium salt.
6. A heat and light stable resinous composition as defined in Claim 1 wherein the cadmium salt and zinc salt are salts of monocarboxylic acids and the strontium salt and potassium salt are salts of alkylphenols.
7. A heat and light stable resinous composition as defined in Claim 6 wherein the mixture of metal salts contains cadmium benzoate, zinc benzoate, strontium nonylphenate, and potassium nonylphenate.
8. A heat and light stable resinous composition as defined in Claim 1 wherein the organic phosphite in the stabilizer is diphenyl decyl phosphite.
9. A heat and light stable resinous composition as defined in Claim 1 that contains 40 percent to 55 percent by weight of said mixture of metal salts and 30 percent to 40 percent by weight of said organic phosphite.
10. A stabilizer for vinyl halide resin compositions that comprises a) a metal salt component comprising a cadmium salt, a strontium salt, a potassium salt, and a zinc salt selected from the group consisting of salts of alkyl-phenols in which the alkyl groups have from 4 to 12 carbon atoms, salts of monocarboxylic acids having 6 to 12 carbon atoms, and mixtures of said salts and b) an organic phosphite selected from the group consisting of triaryl phosphites, trialkyl phosphites, and alkyl aryl phosphites wherein each alkyl group has from 6 to 12 carbon atoms and each aryl group is phenyl, hydroxyphenyl, halophenyl, or alkylphenol, said stabilizer containing 4.5 percent to 6.0 percent by weight of a mixture of metals comprising cadmium, strontium potassium and zinc as said salts and 2.0 percent to 3.5 percent by weight of phosphorus as said organic phosphite.
11. A stabilizer as defined in Claim 10 wherein the metal salt component contains 30 percent to 60 percent by weight of a cadmium salt, 25 percent to 55 percent by weight of a strontium salt, 5 percent to 20 percent by weight of a zinc salt, and 5 to 25 percent by weight of a potassium salt.
12. A stabilizer as defined in Claim 10 wherein the metal salt component contains 35 percent to 55 percent by weight of a cadmium salt, 30 percent to 45 percent by weight of a strontium salt, 7 percent to 15 percent by weight of a zinc salt, and 5 to 25 percent by weight of a potassium salt.
13. A stabilizer as defined in Claim 10 wherein the cadmium salt and zinc salt are salts of monocarboxylic acids and the strontium salt and potassium salt are salts of alkylphenols.
14. A stabilizer as defined in Claim 10 wherein the cadmium salt and zinc salts are cadmium benzoate and zinc benzoate.
15. A stabilizer as defined in Claim 10 wherein the strontium salt and potassium salt are strontium nonylphenate and potassium nonylphenate.
16. A stabilizer as defined in Claim 10 wherein the organic phosphite is an alkyl aryl phosphite.
17. A stabilizer as defined in Claim 16 wherein the organic phosphite is diphenyl decyl phosphite.
18. A stabilizer as defined in Claim 10 that contains 40 percent to 55 percent by weight of said metal salt component and 30 percent to 40 percent by weight of said organic phosphite.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45981374A | 1974-04-10 | 1974-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1063791A true CA1063791A (en) | 1979-10-09 |
Family
ID=23826245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA223,541A Expired CA1063791A (en) | 1974-04-10 | 1975-04-01 | Stabilized vinyl halide resin compositions |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5743571B2 (en) |
| CA (1) | CA1063791A (en) |
| DE (1) | DE2515377A1 (en) |
| DK (1) | DK140075A (en) |
| FR (1) | FR2274648A1 (en) |
| GB (1) | GB1481281A (en) |
| IT (1) | IT1035161B (en) |
| NO (1) | NO751226L (en) |
| SE (1) | SE400781B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09506917A (en) * | 1993-12-22 | 1997-07-08 | チバ−ガイギー アクチエンゲゼルシャフト | Method for stabilizing a PVDC-containing polyolefin mixture and stabilizer mixture for a PVDC-containing polyolefin mixture |
-
1975
- 1975-03-26 GB GB12751/75A patent/GB1481281A/en not_active Expired
- 1975-04-01 CA CA223,541A patent/CA1063791A/en not_active Expired
- 1975-04-02 DK DK140075A patent/DK140075A/da unknown
- 1975-04-02 IT IT48906/75A patent/IT1035161B/en active
- 1975-04-08 JP JP50041930A patent/JPS5743571B2/ja not_active Expired
- 1975-04-08 SE SE7504022A patent/SE400781B/en unknown
- 1975-04-08 NO NO751226A patent/NO751226L/no unknown
- 1975-04-09 FR FR7511121A patent/FR2274648A1/en active Granted
- 1975-04-09 DE DE19752515377 patent/DE2515377A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DK140075A (en) | 1975-10-11 |
| FR2274648B1 (en) | 1979-03-09 |
| SE7504022L (en) | 1975-10-13 |
| SE400781B (en) | 1978-04-10 |
| JPS5743571B2 (en) | 1982-09-16 |
| DE2515377A1 (en) | 1975-10-23 |
| JPS50141644A (en) | 1975-11-14 |
| NO751226L (en) | 1975-10-13 |
| FR2274648A1 (en) | 1976-01-09 |
| GB1481281A (en) | 1977-07-27 |
| IT1035161B (en) | 1979-10-20 |
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