CA2022855A1 - Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions - Google Patents
Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositionsInfo
- Publication number
- CA2022855A1 CA2022855A1 CA 2022855 CA2022855A CA2022855A1 CA 2022855 A1 CA2022855 A1 CA 2022855A1 CA 2022855 CA2022855 CA 2022855 CA 2022855 A CA2022855 A CA 2022855A CA 2022855 A1 CA2022855 A1 CA 2022855A1
- Authority
- CA
- Canada
- Prior art keywords
- motor vehicle
- diketone
- carbon atoms
- vinyl chloride
- beta
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
IMPROVING STABILITY AT MODERATE TEMPERATURES
OF MOTOR VEHICLE COMPONENTS SHAPED FROM
POLYVINYL CHLORIDE RESIN COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
Motor vehicle components are provided having an improved stability at moderate temperatures and shaped from polyvinyl chloride resin compositions, comprising a polyvinyl chloride resin, at least one heat stabilizer in a sufficient amount to impart heat processing stability, and a .beta.-diketone in a sufficient amount to provide, after forming, stability at moderate temperatures not provided by any residual heat stabilizer, as well as polyvinyl chloride resin stabilizer compositions and polyvinyl chloride resin compositions containing such heat stabilizer compositions suitable for use in forming motor vehicle components, comprising at least one heat stabilizer and a .beta.-diketone.
OF MOTOR VEHICLE COMPONENTS SHAPED FROM
POLYVINYL CHLORIDE RESIN COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
Motor vehicle components are provided having an improved stability at moderate temperatures and shaped from polyvinyl chloride resin compositions, comprising a polyvinyl chloride resin, at least one heat stabilizer in a sufficient amount to impart heat processing stability, and a .beta.-diketone in a sufficient amount to provide, after forming, stability at moderate temperatures not provided by any residual heat stabilizer, as well as polyvinyl chloride resin stabilizer compositions and polyvinyl chloride resin compositions containing such heat stabilizer compositions suitable for use in forming motor vehicle components, comprising at least one heat stabilizer and a .beta.-diketone.
Description
2 ~ 2 2 ~
SPE CIFICAT ION ~ ;
Polyvinyl chloride resins, properly formulated, can be processed by standard plastics processing techniques (including calendering, extrusion, injection and compression molding, blow molding, rotational molding, slush and dip ~ -molding, solution casting, electrostatic spray and fluidized bed ~` `
coating), to form awide variety of end products, including plastic sheeting, furniture for both indoor and outdoor use, house sidings and other building components, and motor vehicle components, such as dashboards, seat coverings, floor mats, door panels, arm and head rests, body side moldings, window trim moldings, seat corners and head liners, door and window knobs, and crash dashboards.
Compounding components such as plasticizers, ~5 stabilizers, lubricants, impact modifiers, processing aids, fillers, colorants, antistatic agents, tackifiers, flame ~, ~
retardants, fungicides, antiblocking agents, etcO make the processing into these various end use components feasible -~
without noticeable deterioration of the polymer. In the absence ;
20 o such components, the resin would degrade during heat processing, liberating hydrogen chloride, discolor and become brittle, and stick to the equipment. `~
This success in stabilizing the polymer during heat . .. .
processing has only been achieved after many years of 25 development of the heat stabilizing systems that are now ~ ',. ' 2~22~3~
widely accepted as conventional. However, as Norman L
Perry, Chapter 17, Encyclopedia of PVC, Volume 2, (Marcel Dekker, Inc. New York and Basel, 1977) has noted at page 873, satisfactoryprotection against discoloration 5 under processing temperature conditions does not necessarily ensure protection against discoloration thereafter when exposed ~ ~;
to moderately hot temperatures over a long period~
In fact, protection against discoloration at moderate temperatures over long periods is a particular problem with motor vehicle components. Depending upon their location ~ ~
in the vehicle, they may be exposed to varying amounts of ~ `
light, and also different rather high (above atmospheric) temperatures in use, and these differences can degrade motor `
vehicle components at differing rates. While normally it can 15 be expected that the heat stabilizer systems capable of protecting the resin against degradation and discoloration during heat processing will not be completely consumed during such processing, and can be expected to contribute to stabilization following the processing, in fact the available 20 heat stabilizers normally used are not sufficiently effective to prevent discoloration of motor vehicle components arising from exposure to moderate temperatures in use. It is a problem that,failing a solution, the automobile industry has had to live with ~ ~2 ~
Struber Theory and Practice of Vinyl Compounding (a publication OI Argus Chemical Corporation, 1968) recommends specific heat stabilizer systems for use in automotive upholstery and flooring compounds, to provide 5 moderate temperature aging stability in use. The organotin compounds, both mercaptides and maleate types, are effective, but relatively expensive, and also usually impart an objectionable odor that precludes their use~ Some barium/cadmium fatty `
acid salt stabilizers with high cadmium content are also 10 effective. Struber notes that generally those compounds which tend to discolor most rapidly under moderate temperature conditions have received the greatest exposure to high temperature processing, making it quite clear that reliance ~
is being placed on the residual amounts of heat stabilizers that `
are present in the composition after heat processing. The ~ ; ;
. ... .
higher temperature heat processing conditions evidently have consumed a larger proportion of such stabilizers,accounting ~ -for their lesser stability and shorter life in useO However,~ -simply increasing the amounts of heat stabilizers employed, ~;
20 even of the recommended types, has not been successful in resolving the moderate temperature ageing stability problem, particularly in motor vehicle components, and it is apparent ~
that something more is needed~ ~-In accordance with the present invention, this something ;
25 more is provided in the form of a ~ rdiketone. The invention . .- .
, . ~ . ~ ,.
SPE CIFICAT ION ~ ;
Polyvinyl chloride resins, properly formulated, can be processed by standard plastics processing techniques (including calendering, extrusion, injection and compression molding, blow molding, rotational molding, slush and dip ~ -molding, solution casting, electrostatic spray and fluidized bed ~` `
coating), to form awide variety of end products, including plastic sheeting, furniture for both indoor and outdoor use, house sidings and other building components, and motor vehicle components, such as dashboards, seat coverings, floor mats, door panels, arm and head rests, body side moldings, window trim moldings, seat corners and head liners, door and window knobs, and crash dashboards.
Compounding components such as plasticizers, ~5 stabilizers, lubricants, impact modifiers, processing aids, fillers, colorants, antistatic agents, tackifiers, flame ~, ~
retardants, fungicides, antiblocking agents, etcO make the processing into these various end use components feasible -~
without noticeable deterioration of the polymer. In the absence ;
20 o such components, the resin would degrade during heat processing, liberating hydrogen chloride, discolor and become brittle, and stick to the equipment. `~
This success in stabilizing the polymer during heat . .. .
processing has only been achieved after many years of 25 development of the heat stabilizing systems that are now ~ ',. ' 2~22~3~
widely accepted as conventional. However, as Norman L
Perry, Chapter 17, Encyclopedia of PVC, Volume 2, (Marcel Dekker, Inc. New York and Basel, 1977) has noted at page 873, satisfactoryprotection against discoloration 5 under processing temperature conditions does not necessarily ensure protection against discoloration thereafter when exposed ~ ~;
to moderately hot temperatures over a long period~
In fact, protection against discoloration at moderate temperatures over long periods is a particular problem with motor vehicle components. Depending upon their location ~ ~
in the vehicle, they may be exposed to varying amounts of ~ `
light, and also different rather high (above atmospheric) temperatures in use, and these differences can degrade motor `
vehicle components at differing rates. While normally it can 15 be expected that the heat stabilizer systems capable of protecting the resin against degradation and discoloration during heat processing will not be completely consumed during such processing, and can be expected to contribute to stabilization following the processing, in fact the available 20 heat stabilizers normally used are not sufficiently effective to prevent discoloration of motor vehicle components arising from exposure to moderate temperatures in use. It is a problem that,failing a solution, the automobile industry has had to live with ~ ~2 ~
Struber Theory and Practice of Vinyl Compounding (a publication OI Argus Chemical Corporation, 1968) recommends specific heat stabilizer systems for use in automotive upholstery and flooring compounds, to provide 5 moderate temperature aging stability in use. The organotin compounds, both mercaptides and maleate types, are effective, but relatively expensive, and also usually impart an objectionable odor that precludes their use~ Some barium/cadmium fatty `
acid salt stabilizers with high cadmium content are also 10 effective. Struber notes that generally those compounds which tend to discolor most rapidly under moderate temperature conditions have received the greatest exposure to high temperature processing, making it quite clear that reliance ~
is being placed on the residual amounts of heat stabilizers that `
are present in the composition after heat processing. The ~ ; ;
. ... .
higher temperature heat processing conditions evidently have consumed a larger proportion of such stabilizers,accounting ~ -for their lesser stability and shorter life in useO However,~ -simply increasing the amounts of heat stabilizers employed, ~;
20 even of the recommended types, has not been successful in resolving the moderate temperature ageing stability problem, particularly in motor vehicle components, and it is apparent ~
that something more is needed~ ~-In accordance with the present invention, this something ;
25 more is provided in the form of a ~ rdiketone. The invention . .- .
, . ~ . ~ ,.
3 ~ `
"','', ~:'..'.'...'.'.' ~ ~.;..
2~22~3~ -employs a conventional heat stabilizer system, particularly ~ `
and preferably one of the barium/cadmium organic acid salt ~ ;
types, in a sufficient amount to provide heat stability during heat processing, with the B-diketone serving the function of 5 providing resistance to discoloration at moderate temperatures after the composition has been put in the form of the motor vehicle component, by any appropriate forming or shaping ~ ~
procedure. Thus, the B-diketone is not serving the function ~-of a heat processing stabilizer, in the composition of the present invention, and indeed it has been demonstrated that even in the absence of the B-diketone, the compositions are stable under conventional heat processing conditions. The B-diketone provides only the desired moderate temperature stability thereafter, and this whether or not residues of the ;
heat stabilizers remain in the shaped product.
Ebel, Burger and Herrle, German patent No. 1, 073, 201, UO S~ patent NoO 3, 001, 970, disclose that polyvinyl chloride ;
or polyvinylidene chloride when combined with up to about 10% of a dibenzoylmethane of the formula~
R
o/CO\ ~ CO~
in which R is hydrogen or a hydroxyl residue, display an improved resistance to deterioration when exposed to light.
25 Additional substituents can be present on one or both benzene ;'.'~'.;''''.' `''" ',','.' 4 ~ --'''.~''' 2 ~
,`.
rings that do not impart water solubility. Dibenzoylmethane, -oxydibenzoylmethane, 2-oxy- 5-ch lorodibenzoylmethane, and 2-oxy-5-methyldibenzoylmethane, are mentioned as examples~ In Example 1, it is furthler demonstrated that the 5 dibenzoylmethane also improves resistance to deterioration at temperatures as high as 160C. These results are obtained ~ ;
with polyvinyl chloride, polyvinylidene chloride, and copolymers of vinylidene chloride and vinyl chloride with other copolymerizable monom ers.
Crochemore and Gay, U.S. patent No. 4, 102, 839, `
seemingly unaware of the contribution of the Ebel et al patent, propose compositions for stabilizing vinyl chloride polymers against thermodegradation composed of a divalent metal salt ;
of an organic carboxylic àcid, in combination with a ~-diketone 15 or a B ketoaldehyde. The latter has the formula:
R l-CO--CHRz--CO-R 3 ' , ::
in which each of Rl and R3, which may be the same or different, represent a linear or branched alkyl or alkenyl radical having from 1 to 36 carbon atoms, an aralkyl radical having from 20 7 to 36 carbon a.toms or an aryl or cycloaliphatic radical having less than 14 carbon atoms, said cycloaliphatic radical optionally containing one or more carbon-carbon double bonds, the aliphatic ; `
chains oE said radicals optionally containing one ~
O . .~
25 ~, --C~} radical; one of Rl or R3 can represent a hydrogen `~
' '. '.~ `.''.
2~2~
atom; R2 represents a hydrogen atom~ a radical of the formula ~RI, or -CO~R4, wherein R4 represents an aLkyl radical having from 1 to 36 carbon atoms or cm aryl radical if Rl and R3 are not aromatic, or a radical of the :Eormula~
/ C~R
C~R3 wherein Rl~ R3 and Rg are as defined above;
or R1 and R2 together represent a divalent radical as an aLkylene radical having from 1 to 12 carbon atoms or a cyclo aLkylene radical having less than 14 carbon atoms, these `:
radicals can be substituted by an aliphatic radical having from 1 to 18 carbon atoms;
in R" R2 and R3 the carbon atoms adjacent the indicated carbonyl groups are not doubly bonded to carbon atom and no :
more than one of said carbon atom is contained in an aromatic ring.
The R, ~nd R3 substituents may be substituted with a member selected from the group consisting of halo, aryl or cycloaliphatic groups having less than 14 carbon atoms, which . ..
~ . .
aliphatic moieties may include ~, -COO- or -C~ linkages within their chains. ~ `.
These stabilizer combinations are used to impart resistance to the high temperatures of 180 to 200C undergone by the polymer during the manufacture of various shaped articles ~ -. ~, .... ...
"','', ~:'..'.'...'.'.' ~ ~.;..
2~22~3~ -employs a conventional heat stabilizer system, particularly ~ `
and preferably one of the barium/cadmium organic acid salt ~ ;
types, in a sufficient amount to provide heat stability during heat processing, with the B-diketone serving the function of 5 providing resistance to discoloration at moderate temperatures after the composition has been put in the form of the motor vehicle component, by any appropriate forming or shaping ~ ~
procedure. Thus, the B-diketone is not serving the function ~-of a heat processing stabilizer, in the composition of the present invention, and indeed it has been demonstrated that even in the absence of the B-diketone, the compositions are stable under conventional heat processing conditions. The B-diketone provides only the desired moderate temperature stability thereafter, and this whether or not residues of the ;
heat stabilizers remain in the shaped product.
Ebel, Burger and Herrle, German patent No. 1, 073, 201, UO S~ patent NoO 3, 001, 970, disclose that polyvinyl chloride ;
or polyvinylidene chloride when combined with up to about 10% of a dibenzoylmethane of the formula~
R
o/CO\ ~ CO~
in which R is hydrogen or a hydroxyl residue, display an improved resistance to deterioration when exposed to light.
25 Additional substituents can be present on one or both benzene ;'.'~'.;''''.' `''" ',','.' 4 ~ --'''.~''' 2 ~
,`.
rings that do not impart water solubility. Dibenzoylmethane, -oxydibenzoylmethane, 2-oxy- 5-ch lorodibenzoylmethane, and 2-oxy-5-methyldibenzoylmethane, are mentioned as examples~ In Example 1, it is furthler demonstrated that the 5 dibenzoylmethane also improves resistance to deterioration at temperatures as high as 160C. These results are obtained ~ ;
with polyvinyl chloride, polyvinylidene chloride, and copolymers of vinylidene chloride and vinyl chloride with other copolymerizable monom ers.
Crochemore and Gay, U.S. patent No. 4, 102, 839, `
seemingly unaware of the contribution of the Ebel et al patent, propose compositions for stabilizing vinyl chloride polymers against thermodegradation composed of a divalent metal salt ;
of an organic carboxylic àcid, in combination with a ~-diketone 15 or a B ketoaldehyde. The latter has the formula:
R l-CO--CHRz--CO-R 3 ' , ::
in which each of Rl and R3, which may be the same or different, represent a linear or branched alkyl or alkenyl radical having from 1 to 36 carbon atoms, an aralkyl radical having from 20 7 to 36 carbon a.toms or an aryl or cycloaliphatic radical having less than 14 carbon atoms, said cycloaliphatic radical optionally containing one or more carbon-carbon double bonds, the aliphatic ; `
chains oE said radicals optionally containing one ~
O . .~
25 ~, --C~} radical; one of Rl or R3 can represent a hydrogen `~
' '. '.~ `.''.
2~2~
atom; R2 represents a hydrogen atom~ a radical of the formula ~RI, or -CO~R4, wherein R4 represents an aLkyl radical having from 1 to 36 carbon atoms or cm aryl radical if Rl and R3 are not aromatic, or a radical of the :Eormula~
/ C~R
C~R3 wherein Rl~ R3 and Rg are as defined above;
or R1 and R2 together represent a divalent radical as an aLkylene radical having from 1 to 12 carbon atoms or a cyclo aLkylene radical having less than 14 carbon atoms, these `:
radicals can be substituted by an aliphatic radical having from 1 to 18 carbon atoms;
in R" R2 and R3 the carbon atoms adjacent the indicated carbonyl groups are not doubly bonded to carbon atom and no :
more than one of said carbon atom is contained in an aromatic ring.
The R, ~nd R3 substituents may be substituted with a member selected from the group consisting of halo, aryl or cycloaliphatic groups having less than 14 carbon atoms, which . ..
~ . .
aliphatic moieties may include ~, -COO- or -C~ linkages within their chains. ~ `.
These stabilizer combinations are used to impart resistance to the high temperatures of 180 to 200C undergone by the polymer during the manufacture of various shaped articles ~ -. ~, .... ...
...................................................................... ..... -. - . -~:".'' '`'''.
2 ~
by molding, extrusion and plastic processes. These processes - -require high temperatures in order to bring the polymer to a sufficiently soft state, and the degradation in question occurs at these processing temperatures. Accordingly, the working 5 Examples test the effectiveness of the stabilizer combinations , -.
by the usual oven heat test as 10 x 20 mm test samples cut from sheets prepared by calendering at 180C. The results show that in the absence of the B-diketone the compositions have very poor heat stability under the test conditions.
Gay U.S. patent NoO 4, 123, 399 discloses similar ` ;
stabilizer compositions containing a pair of organic acid salts ;
of calcium and zinc, a polyol, and a ~-diketone of like formula to No. 4,102, 839, ~he working Examples~of the Gay patent `~
also demonstrate the important contribution of the ~-diketone ; `;
to heat stability during high temperature processing of the ~ ~
polymer chloride resin composition. ~;
- ~ ~
Minagawa, Sekiguchi and Nakazawa U.S. patent NoO 4, 221, 687 provides anti-yellowing additives for environmentally acceptable stabilized vinyl chloride polymer ~;
20 compositions from which arsenic, cadmium, lead, mercury and ~ , thallium are substantially excluded, comprising at least one basic inorganic compound of lithium, sodium, potassium, - -magnesium, calcium, strontium, barium, zinc, titanium, aluminum, zirconium or tin, and a 1, 3-diketone compound `;- -;
25 represented by the formula~
": ' '~22~
".,.~ ~ .
M(R-C--CR'-C-R")n ~: ~
O O ~
in which R is a hydrocarbon group having 1 to 18 carbon atoms, R' is a hydrogen atom, an acyl group R"'~, or a hydrocarbon O
group having 1 to 18 carbon atoms, R' is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, M is a hydrogen or one of the metals lithium, sodium, potassium,~ ~ -magnesium, calcium, strontium, barium, zinc, aluminum :
10 and antimony9 and n is the valence of the metal from 1 to 3 Minagawa, Sekiguchi and Nakazawa U.S. patent NoO 4, 244, 848 provide environmentally acceptable stabilizer compositions for enhancing the resistance to deterioration ~: . .. `
upon heating at 175C of a vinyl chloride polymer *om which ~.`
lead, cadmium, mercury, thallium and arsenic are substantially excluded, comprising at least one zinc, alkali ~ ;
. . .. . .;
metal or alkaline earth metal organic phosphate ester salt .
and at least one ~-diketone compound having from 5 to about 30 carbon atoms, which is a cyclic or open chain ~-dikelone, : ~-or a æinc, alkali metal or alkaline earth metal salt thereofO . ~
Ito, Murnajiri, Kimura and Sekiguchi U.S~ patent ` -.
No. 4, 252, 698 provide anti-yellowing additives for environmentally acceptable stabilized vinyl chloride polymer compositions from which arsenic, beryllium, cadmium, lead, mercury, and thallium are substantially excluded, comprising ~ .~ .....
:`',~'~.,."''".
., .... ~
:'- .", ., at least one overbased sulfonate or phenolate compound of ~.
lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, titanium, aluminum, zirconium, or tin, and a ~ .
1, 3-diketone compound having 5 to 30 carbon atoms, which is ;:
a cyclic or open-chain 1, 3-diketone or a lithium, sodium, ; ~
potassium, magnesium, calcium, strontium, barium, zinc, -~ ~;
aluminum, tin or zirconium salt thereof. ; ~ ~
Minagawa, Nakahara and Kitsukawa U. S. patent - ~:
NOn 4, 282,141 provide additive compositions for improving ` :
the color stability of vinyl chloride polymers stabilized with ~ .
environmentally acceptable stabilizers comprising a 1, 3- ~`
diketone or a sodium, potassium, lithium, magnesium, barium, calcium, tin or strontium salt thereof and an organic phosphite ` ;
having the formula ;~
R 1 ~ .
OR6 ;
Ra~ ORs wherein R1 is a phenyl, cycloalkyl, t-butyl, or t-amyl group, .- --R2 and R3 are each a hydrogen atom or phenyl, cycloalkyl, or an alkyl group having one to five carbon atoms, R4 is a hydrogen . -: i atom or a methyl group, and each of R5 and R6 independently is a hydrogen atom, an aLkyl group having 1 to 18 carbon atoms, - i a cycloalkyl group having 5 to 20 carbon atoms, an aryl group `~ :
having 6 to 12 carbon atoms, or an ether-substituted group having 3 to 80 carbon atoms and 1 to about 4Q ether oxygen atomsO
. . .
9 .......
~2~J~
J. Darby U. S0 patent No. 2, 669, 548 of ;
February 16, 1954 discloses halogen-containing resin compositions having improved stability containing a mixture of a zinc salt and a calcium chelate derivative of a 1, 3 5 dicarbonylic compound capable of keto-enol tautomerism~
Zinc salts can be zinc salts of organic acids and zinc salts of weak inorganic acids, for example zinc acetate, zinc propionate, zinc octanoate, zinc ricinoleate stearate, and ~ ~
zinc salts ~f carbonic, silicic, and boric acids. Calcium " ~;
chelates can be derivatives of B-diketones, ~-ketoacids, ~ ~
and the esters of B-ketoacids, for example the calcium ~ ;
chelates of ethyl acetoacetate, phenyl acetoacetate, acetoacetic acid, acetylacetone, benzoylacetone, and diac etylac etone.
LoL~ Wood UOS. patent No. 3,492, 267 of January 27, 1970 discloses zinc complexes of B-dicarbonyl compounds used as -- `
stabilizing additives for chlorine-containing polymers in general, and polyvinyl chloride in particular. The zinc complexes possess the general formula: ~ -/CH
R--C Cl--R ' O O ~ ' .` .
Zn/
2 5R~ C--R ' -CH /
- . ,. ' .' ... .......
~', ' :-: ...
~ ~ ~ 2 ~ '3 ~
wherein R and R' are the same or dli~erent and are each hydrogen or an alkyl, alkoxy, phenyl or phenoxy group.
Preferably when R represents an alkyl or alkoxy group, it contains 1 to 20 carbon atoms.
L. Weisfeld U. SO patent No. 3, 493, 536 of February 3, 1970 : .
discloses that diaroylmethane compounds of the general formula ~ : .
C6H5CO CHP~-COC6H5 wherein R is hydrogen or a monovalent hydrocarbon radical provide stabilizing action against the " ~-,. ~
sensitizing effect of bismuth or antimony compounds on chlorine~
contalning materials. -~
U. S. patent No. 3, 346, 536 of Octol~er 10, 1967 discloses a stabiliæer combination of a ketoacetic acid compound, which `
can be an ester or an acid anhydride dimer thereof, with a . :~, . .;
metal salt of an organic acicl~ The ketoacetic acid esters - ~
. -.. - . ~
15 have the formula:
(R--CI--CH2--CI{))~R ' .' . '. - . '.'`''`
O ~ ,, ,. ~ ~,, ~ , wherein R is an inert organic group having from one to `
about thirty carbon atoms, R' is an inert organic radical . ~. .
20 having from one to about thirty carbon atoms, and x is ; ~ `;
a number from one to ten. The ester molecule has a total - -of at least eight carbon atoms. - -The ketoacetic acid anhydride dimers have the formula: ;
-. .'~' 2 ~ 3 ~a) l l H (b) ll R
~CI-R or f ~ R
RJ~OJ~o R ~;
R II
5R lOOC~
R O~J=O
R s again as above and Rl is hydrogen or R'.
It i9 further disclosed that this stabilizer combination can be used with additional heat stabilizers, among which ~ ~ `
phenols and organic triphosphites and acid phosphites are ;~
preferred.
In all of these patents, the compositions are described ` `
as heat stabilizing compositions, capable of improving the resistance of the polymer to deterioration when exposed to ` `
elevated temperatures during heat processing. ~ ``
In accordance with the present invention, improved ` -resistance to deterioration of motor vehicle components made ` `
of polyvinyl chloride resin compositions is obtained b~
combining with the polyvinyl chloride resin, at least one heat 20 stabilizer other than a B-diketone or metal salt thereof in a sufficient amount to provide resistance to deterioration during heat processing, and a B-diketone in a sufficient amount to provide, after formation into a motor vehicle component, resistance to deterioration at moderate temperatures. ~ ~ ~
.- ,.,-,.-~,, 2 ~
The B-diketones in accordance with the invention ~;
have the formula:
M(R ll_CR '_CI_R ")t~ ~
O O .`:'.,''.,' When in this formula M is a hydrogen atom, the ~ -formula becomes H(R--C--CR'--C--R") O O ~. ~, :,' which is a way to indicate by a single expression that the ~ ";`
., ~, .. . . .
hydrogen atom can be linked in more than one way, as ~ `
in the tautomeric formulas I to III (i. e. formulas of compounds in readily movable equilibrium with one another) j ; `
R~ CHR'--Cl--R" ~R-C_CR'-C-R" =R-C-CR'=f`-R"
(I) (II) (m) ;`"~
the latter two of which are identical when R and R" are the same and non-identical when R and R" are different. The ~ `-relative proportions of tautomers I, II, and III in the B-diketone compounds is a function of the identity of R and R"; for example the enol content (i. e. combined; content of the C=C ~ ~ ;
containing tautomers II and III) has been reported as 76. 4% or ~`
diacetylmethane (R_R"=methyl) and 89. 2% for acetylbenzoylmethane (P~=methyl, P~'=phenyl) (see A. Gero. J. Organic ChemO 1954, vol. 19, p. 1960- 1970).
When M is a metal, the formula:
IVM(R{~ CR'-~CI-R")n n=the valence of the metal M `~
O O ~, 2~22~3~ :ï
indicates that, while numerous structural formulas canbe written differing in the location of various linkages (as ~:
illustrated for zinc acetylbenzoylmethane by formulas V to . . ;
~TIII bel~w),all are equivalent representations of a single ~ `
:. ~
compound which is better representecl as a "hybrid" of all .
formulas than by any single one. In formulas IV to VII, Ph .
represents phenyl and Me represents methyl.
Ph Ph C=O O~C ' 10 V CH Zn CH
f_o o=f ~ `
Me . Me :.
Ph Ph C--O . O--C .
15 VI CH Zn . CH ;; - ~
/~ ~ / ` "'.''".'''','~''''''`' c o o f ~ ! .. : ~ ` `
Me Me fh Ph C=O;, . O=C
VII CH Zn CH ~ ~
C--0 0--C , . ...... : ~ :
Me M~ ~ .
. . . ~ .`;,.. .:
:
2 ~
~' ':'." ~`,' Ph C~ C .,,~
D \ ~
VIIICH Zn CH
Cl--O . --I
. ..
In the formula of ~-diketone metal compounds, n is ;
the valence of the metal and the number of ~-diketone groups per metal atom, as shown: ` " `
M Ll Na K Mg Ca Sr Ba Zn Al Sb n 1 1 1 2 2 2 2 2 3 3 . .~
Hydrocarbon groups R, R', R" and R"' can be open ~ ~ .
chain or cyclic and include such aliphatic, cycloaliphatic and .
aromatic hydrocarbon groups as alkyl and alkenyl groups ~
having from 11 to 18 carbon atoms; aL~yl cycloaLkyl, alkyl cycloaLkenyl .: :
15 and aLkyl cycloaL~ylaLkylene having from 11 to 18 carbon atoms, and alkylcycloalkyl groups having from 11 to 18 carbon atoms, and ~ :
non-condensed aryl groups (including araL~cyl, cycloalkylaryl, and alkyaryl) having 6 to 18 carbon atoms, for example undecyl, - ::
dodecyl, tridecyl, pentadecyl, heptadec-3-en- 1-yl, n-octadecyl, 20 ricinoleyl, linoleyl, linolenyl, decyl cyclohexyl, hexyl cyclohexyl, cyclododecyl, phenyl, m-tolyl, p-ethylphenyl, t-butylphenyl, benzyl, cyclohexylphenyl, phenylpropyl and nonylbenzyL The aryl groups may contain one or two halogen ring substituents, such as fluorine, chlorine or bromine.
.:
2 ~ 2 2 g ~ ~
. ~. .
` ~ ' ' ' ALkoxyhydrocarbon R, R', R" and R"' groups -include n-decoxymethyl, 2-dodecoxyethyl, 2-methoxyphenyl, i and 4-n-octoxyphenylbenzyl. R, R', R" and R"' alkylene-. ~ . ~..
dioxyhydrocarbon groups include 3(ethylenedioxydodecyl) ~ - -5 and 3, 4-methylenedioxyphenyL R ' can be hydrogen, but not R and R", and only one of R and R" can be aliphatic or cycloaliphatic.
;:: . ~.: i Illustrative ~-diketone compounds that can be used include the B-diketones listed below and the aluminum, antimony, barium, calcium, lithium, magnesium, potassium, ` i sodium, strontium, and zinc derivatives thereof. `
: ~' ,.' '~' `'`~';;~
' ~'' ' ~ -.'. '''~' ~''.
'',' ':.
2 ~ 2 2 ~
.'- .- ` ` `.
. ...~ ~.....
.., ~ .. ... ..
No. 1 )odecanoyl-benzoyl~
CllH~3--C--CH---C~) methane .
O o No.2 `~ ``
~ Tride anoyl-benzoyl-C~,H"5--C--CH~--C~ me~hane - .
o o : :~
No. 3 . O~:lu~ al~oyl-b~ oyl~m~hulle `
Cl7H3s--I_CH~
O ., O .::
Nv. 4 .
lru~ ul~oyl b~ oyl~nl~lh~
.CI3H~7--ll--CH3 ~
'`' ~.''`.:
''~ . ,'`;~
17 ~: ` ;:~
2~22~3~ ;
. No. 5 /~ Pen~adecanoyl~benzoyl~
Cl,~3l --C--CH2--C~) methane No. S
Dibellzoylme~llune . `:
~C--CH~--C~
No. 7 Phenylacetyl benzoyl-methane (~C--CH2--C--CH ~) ~0. 8 ~ c9Hls Benzoyl-nonylbenzoyl-methane ~ ICl--~H~--ICl ~
'~
;'~
.
2a22,J~}s :~
``:
No. 9 ~ ~ Octylhexa hydrobenzoyl C8H,7 ~C--CH2--ICl~c8Hl7 octylbenzoyl methane No. 10 1l ~ Benzoyl-p methoxyben70yl-methane ~C--CH2--C~OCH3 -No. 11 O O A Di(p methoxybenzoyl)methane CH30~C--CH2--C~OCH3 No. i2 A 1l 1l ~ Di(p-chlorobenzoyl)methune Cl ~--C~CH2--C~CI
No. 13 -~0 0~ Di(3,4-methylenedioxybenzoyl)methane : `
CH2 ~ O O /--~ CH2 ' ': ~-O~)C--CH2--C~O . ,~
No. 14 O O
/--\ " 1,1-Dodecanoyl- 1-benzoylnonane ~C--I H--C--C
f`
;:
- 2 ~ ~ 2 ~
~
,:,.`
No. 15 O O
` "~
Alpha-dodecanoyl-alpha-~C--Cf.~ C--CllH23 benzoyl-toluene ., ~ .
5 No. 16 ~ Di(p-t-butylbenzoyl)methane t-C4Hg--~0~--C--CH2--C~t~C4H9 ~ O O -No. I7 j ; .
Il Il ~ Benzoyl-nonade~anoyl 10~C--CH~--C--Cl8H37 methane , . . ' ' ' ., ! ' . ' . . , _ . . " ' ' ' .
The polyvinyl chloride resin compositions in accordance with the invention containing a B-diketone and at least one heat stabilizer are stable without the ~-diketone under the normal heat processing conditions, as determined by the usual heat stability tests The B-diketone does not apparently contribute :.
to stability under the normal heat processing conditions, since the polyvinyl chloride resin compositions are sufficiently stable without it, but .it does impart stability under moderate temperatures after shaping in the form of the motor vehicle componeslt, ~ ~:
demonstrating that it does survive the previous heat processing, ~'.
f t ~
'; '~`~' .! -;: ~
While any known heat stabilizer for polyvinyl chloride ~, resins can be used, the preferred heat stabilizers are alkali metal and polyvalent metal salts of organic nonnitrogenous monocarboxylic acids, having from six to twenty Eour carbon atoms. The ~' 5 polyvalent metal is preferably a bivalent nontransition metal, includingbarium, calcium, cadmium, magnesium, strontium, stannous tin and zincO
i3 The aliphatic, aromatic, alicyclic and oxygen-'! containing heterocyclic organic acids are operable as a class~ ;
By the term "aliphatic acid" is meant any open chain carboxylic acid, substituted, if desired, with nonreactive groups, such as halogen, sulfur and hydroxyl. By the term "alicyclic" it will be understood that there is intended any cyclic acid in which the ring is nonaromatic and composed solely of carbon atoms, and such acids may if desired have inert, nonreactive substituents such as halogen, hydroxyl, alkyl radicals, alkenyl radicals and other carbocyclic ring structures condensed therewith. The oxygen-containing heterocyclic compounds can be aromatic or ~
non-aromatic and can include oxygen and carbon in the ring ~ -structure, such as aLkyl-substituted furoic acid~ The aromatic acids likewise can have nonreactive ring substituents such as halogen, aLt{yl and aLkenyl groups, and other saturated or aromatic rings condensed therewith.
As exemplary of the acids which can be used in the form of their metal salts there can be mentioned the following: -:
2 ~ 2 2 ~
-., hexoic acid, 2-ethylhexoic acid, n-octoic acid, isooctoic acid, 3, 5, 5-trimethyl hexoic acid, capric acid, undecyclic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, 5 chlorocaproic acid, hydroxy-capric acid, ethyl acetoacetic acid, benzoic acid, phenyl-acetic acid, butylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, hexylbenzoic acid, salicylic acid, naphthoi~ acid, 1-naphthal~ne acetic acid, orthobenzoyl benzoic acid, naphthenic acids derived from~ ~;
10 petroleum, abietic acid, dihydroabietic acid, hexahydrobenzoic acid, and methyl furoic acid, as well as partially esterified ~ `
dibasic acids such as monobutyl phthalate, isooctyl maleate, ethylene glycol maleate, and 2-ethoxy ethylmaleate.
In combination with the above metal salts of organic 15 acids, or in lieu thereof, a metal salt of a hydrocarbon-substituted phenol can be used. The hydrocarbon substituents contain from four to twenty-four carbon atoms each. The metal can be an aL~ali metal or alkaline earth metal such as sodium, potassiumO lithium, calcium, strontium, magnesium ~o and barium. Among such polyvalent metal phenolates there canbe mentioned the magnesium, barium, calcium, strontium, tin and zinc salts of n-butyl phenol, t-nonyl phenol, n-decyl ~
phenol, t-dodecyl phenol, t-octyl phenol, isohexyl phenol,~ ~ -octadecyl phenol, diisobutyl phenol, methyl propyl phenol, 25 diamyl phenol, methyl isohexyl phenol, methyl t-octyl phenol, .:
''"''~
2 ~
di-t-nonyl phenol, ortho or para phenyl phenol. The modified metal phenolates disclosed by M~ Pollock in U.SO patent No. 3, 630,979 of December 28, 1971 and by M Minagawa in U. S. patent No. 3, 733, 288 of May :15, 1973 are also suitableO ;
Mixtures of salts of various metals can be used, such as mixed zinc and tin salts with the aLkaline earth metal salts, e.gO, barium and zinc stearates, as in U.S. patent No. 2,446,976.
In lieu of but preferably in addition to the polyvalent metal salt, organic phosphites can be used.
The organic phosphite can be any organic phosphite having one or more organic radicals attached to phosphorus through oxygen. These radicals can be monovalent radicals in the case of the triphosphites, diphosphites and monophospbites, which can be defined by the formula:
R l~P~R 3 R2 '-`
in which Rl, R2 and R3 are selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, aLkaryl, araLkyl, and cycloalkyl groups having from one to about thirty carbon atoms Also included are the organic phosphites having a bivalent organic radical forming a heterocyclic ring with the phosphorus of the type:
/ O\ '~ :~
2 5 R~ P--~R
O ., in which Rq is a bivalent organic radical selected from the ~
~ ~ ~ s~
group consisting of alkylene, arylene, ara~ylene, aLkarylene and cycloaLkylene radicals having from two to about thirty carbon atoms, and R5 is a monovalent organic radical as defined above in the case of R1, R2 and R3. `~ Also useful in the compositions of the invention are mixed heterocyclic-open chain phosphites of the type: . O\ /0 ~ 0/ 0/
10 More complex phosphites are formed from trivalent organic radicals, of the type:
/O\ / O\ /O\ /OH
R~O--/ HO-R~ / ~R~ / \ OH
in which R~ is a trivalent organic radical of any of the types of Rl to R5, inclusive, as defined above, A particularly useful class of complex phosphite are the tetraoxadiphosphaspiro undecanes of the formula :
~OCH8~ ~ CH20 \
Ri~P / C\ P--~R2 where Rl and P~2 are selected from the group consisting of aryl, aLkyl, aryloxyethyl, alkyloxyethyl, aryloxyethoxyethyl, aLkyloxyethoxyethyl and aLkyloxypolyethoxyethylO
An especially preferred class of organic phosphites -have a bicyclic aromatic group attached to phosphorus through oxygen, with no or one or more pnenolic hydroxyl groups on 2~22~
either or both of the aromatic rings" These phosphites ~ ~;
are characterized by the formula: :
2 ~
by molding, extrusion and plastic processes. These processes - -require high temperatures in order to bring the polymer to a sufficiently soft state, and the degradation in question occurs at these processing temperatures. Accordingly, the working 5 Examples test the effectiveness of the stabilizer combinations , -.
by the usual oven heat test as 10 x 20 mm test samples cut from sheets prepared by calendering at 180C. The results show that in the absence of the B-diketone the compositions have very poor heat stability under the test conditions.
Gay U.S. patent NoO 4, 123, 399 discloses similar ` ;
stabilizer compositions containing a pair of organic acid salts ;
of calcium and zinc, a polyol, and a ~-diketone of like formula to No. 4,102, 839, ~he working Examples~of the Gay patent `~
also demonstrate the important contribution of the ~-diketone ; `;
to heat stability during high temperature processing of the ~ ~
polymer chloride resin composition. ~;
- ~ ~
Minagawa, Sekiguchi and Nakazawa U.S. patent NoO 4, 221, 687 provides anti-yellowing additives for environmentally acceptable stabilized vinyl chloride polymer ~;
20 compositions from which arsenic, cadmium, lead, mercury and ~ , thallium are substantially excluded, comprising at least one basic inorganic compound of lithium, sodium, potassium, - -magnesium, calcium, strontium, barium, zinc, titanium, aluminum, zirconium or tin, and a 1, 3-diketone compound `;- -;
25 represented by the formula~
": ' '~22~
".,.~ ~ .
M(R-C--CR'-C-R")n ~: ~
O O ~
in which R is a hydrocarbon group having 1 to 18 carbon atoms, R' is a hydrogen atom, an acyl group R"'~, or a hydrocarbon O
group having 1 to 18 carbon atoms, R' is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, M is a hydrogen or one of the metals lithium, sodium, potassium,~ ~ -magnesium, calcium, strontium, barium, zinc, aluminum :
10 and antimony9 and n is the valence of the metal from 1 to 3 Minagawa, Sekiguchi and Nakazawa U.S. patent NoO 4, 244, 848 provide environmentally acceptable stabilizer compositions for enhancing the resistance to deterioration ~: . .. `
upon heating at 175C of a vinyl chloride polymer *om which ~.`
lead, cadmium, mercury, thallium and arsenic are substantially excluded, comprising at least one zinc, alkali ~ ;
. . .. . .;
metal or alkaline earth metal organic phosphate ester salt .
and at least one ~-diketone compound having from 5 to about 30 carbon atoms, which is a cyclic or open chain ~-dikelone, : ~-or a æinc, alkali metal or alkaline earth metal salt thereofO . ~
Ito, Murnajiri, Kimura and Sekiguchi U.S~ patent ` -.
No. 4, 252, 698 provide anti-yellowing additives for environmentally acceptable stabilized vinyl chloride polymer compositions from which arsenic, beryllium, cadmium, lead, mercury, and thallium are substantially excluded, comprising ~ .~ .....
:`',~'~.,."''".
., .... ~
:'- .", ., at least one overbased sulfonate or phenolate compound of ~.
lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, titanium, aluminum, zirconium, or tin, and a ~ .
1, 3-diketone compound having 5 to 30 carbon atoms, which is ;:
a cyclic or open-chain 1, 3-diketone or a lithium, sodium, ; ~
potassium, magnesium, calcium, strontium, barium, zinc, -~ ~;
aluminum, tin or zirconium salt thereof. ; ~ ~
Minagawa, Nakahara and Kitsukawa U. S. patent - ~:
NOn 4, 282,141 provide additive compositions for improving ` :
the color stability of vinyl chloride polymers stabilized with ~ .
environmentally acceptable stabilizers comprising a 1, 3- ~`
diketone or a sodium, potassium, lithium, magnesium, barium, calcium, tin or strontium salt thereof and an organic phosphite ` ;
having the formula ;~
R 1 ~ .
OR6 ;
Ra~ ORs wherein R1 is a phenyl, cycloalkyl, t-butyl, or t-amyl group, .- --R2 and R3 are each a hydrogen atom or phenyl, cycloalkyl, or an alkyl group having one to five carbon atoms, R4 is a hydrogen . -: i atom or a methyl group, and each of R5 and R6 independently is a hydrogen atom, an aLkyl group having 1 to 18 carbon atoms, - i a cycloalkyl group having 5 to 20 carbon atoms, an aryl group `~ :
having 6 to 12 carbon atoms, or an ether-substituted group having 3 to 80 carbon atoms and 1 to about 4Q ether oxygen atomsO
. . .
9 .......
~2~J~
J. Darby U. S0 patent No. 2, 669, 548 of ;
February 16, 1954 discloses halogen-containing resin compositions having improved stability containing a mixture of a zinc salt and a calcium chelate derivative of a 1, 3 5 dicarbonylic compound capable of keto-enol tautomerism~
Zinc salts can be zinc salts of organic acids and zinc salts of weak inorganic acids, for example zinc acetate, zinc propionate, zinc octanoate, zinc ricinoleate stearate, and ~ ~
zinc salts ~f carbonic, silicic, and boric acids. Calcium " ~;
chelates can be derivatives of B-diketones, ~-ketoacids, ~ ~
and the esters of B-ketoacids, for example the calcium ~ ;
chelates of ethyl acetoacetate, phenyl acetoacetate, acetoacetic acid, acetylacetone, benzoylacetone, and diac etylac etone.
LoL~ Wood UOS. patent No. 3,492, 267 of January 27, 1970 discloses zinc complexes of B-dicarbonyl compounds used as -- `
stabilizing additives for chlorine-containing polymers in general, and polyvinyl chloride in particular. The zinc complexes possess the general formula: ~ -/CH
R--C Cl--R ' O O ~ ' .` .
Zn/
2 5R~ C--R ' -CH /
- . ,. ' .' ... .......
~', ' :-: ...
~ ~ ~ 2 ~ '3 ~
wherein R and R' are the same or dli~erent and are each hydrogen or an alkyl, alkoxy, phenyl or phenoxy group.
Preferably when R represents an alkyl or alkoxy group, it contains 1 to 20 carbon atoms.
L. Weisfeld U. SO patent No. 3, 493, 536 of February 3, 1970 : .
discloses that diaroylmethane compounds of the general formula ~ : .
C6H5CO CHP~-COC6H5 wherein R is hydrogen or a monovalent hydrocarbon radical provide stabilizing action against the " ~-,. ~
sensitizing effect of bismuth or antimony compounds on chlorine~
contalning materials. -~
U. S. patent No. 3, 346, 536 of Octol~er 10, 1967 discloses a stabiliæer combination of a ketoacetic acid compound, which `
can be an ester or an acid anhydride dimer thereof, with a . :~, . .;
metal salt of an organic acicl~ The ketoacetic acid esters - ~
. -.. - . ~
15 have the formula:
(R--CI--CH2--CI{))~R ' .' . '. - . '.'`''`
O ~ ,, ,. ~ ~,, ~ , wherein R is an inert organic group having from one to `
about thirty carbon atoms, R' is an inert organic radical . ~. .
20 having from one to about thirty carbon atoms, and x is ; ~ `;
a number from one to ten. The ester molecule has a total - -of at least eight carbon atoms. - -The ketoacetic acid anhydride dimers have the formula: ;
-. .'~' 2 ~ 3 ~a) l l H (b) ll R
~CI-R or f ~ R
RJ~OJ~o R ~;
R II
5R lOOC~
R O~J=O
R s again as above and Rl is hydrogen or R'.
It i9 further disclosed that this stabilizer combination can be used with additional heat stabilizers, among which ~ ~ `
phenols and organic triphosphites and acid phosphites are ;~
preferred.
In all of these patents, the compositions are described ` `
as heat stabilizing compositions, capable of improving the resistance of the polymer to deterioration when exposed to ` `
elevated temperatures during heat processing. ~ ``
In accordance with the present invention, improved ` -resistance to deterioration of motor vehicle components made ` `
of polyvinyl chloride resin compositions is obtained b~
combining with the polyvinyl chloride resin, at least one heat 20 stabilizer other than a B-diketone or metal salt thereof in a sufficient amount to provide resistance to deterioration during heat processing, and a B-diketone in a sufficient amount to provide, after formation into a motor vehicle component, resistance to deterioration at moderate temperatures. ~ ~ ~
.- ,.,-,.-~,, 2 ~
The B-diketones in accordance with the invention ~;
have the formula:
M(R ll_CR '_CI_R ")t~ ~
O O .`:'.,''.,' When in this formula M is a hydrogen atom, the ~ -formula becomes H(R--C--CR'--C--R") O O ~. ~, :,' which is a way to indicate by a single expression that the ~ ";`
., ~, .. . . .
hydrogen atom can be linked in more than one way, as ~ `
in the tautomeric formulas I to III (i. e. formulas of compounds in readily movable equilibrium with one another) j ; `
R~ CHR'--Cl--R" ~R-C_CR'-C-R" =R-C-CR'=f`-R"
(I) (II) (m) ;`"~
the latter two of which are identical when R and R" are the same and non-identical when R and R" are different. The ~ `-relative proportions of tautomers I, II, and III in the B-diketone compounds is a function of the identity of R and R"; for example the enol content (i. e. combined; content of the C=C ~ ~ ;
containing tautomers II and III) has been reported as 76. 4% or ~`
diacetylmethane (R_R"=methyl) and 89. 2% for acetylbenzoylmethane (P~=methyl, P~'=phenyl) (see A. Gero. J. Organic ChemO 1954, vol. 19, p. 1960- 1970).
When M is a metal, the formula:
IVM(R{~ CR'-~CI-R")n n=the valence of the metal M `~
O O ~, 2~22~3~ :ï
indicates that, while numerous structural formulas canbe written differing in the location of various linkages (as ~:
illustrated for zinc acetylbenzoylmethane by formulas V to . . ;
~TIII bel~w),all are equivalent representations of a single ~ `
:. ~
compound which is better representecl as a "hybrid" of all .
formulas than by any single one. In formulas IV to VII, Ph .
represents phenyl and Me represents methyl.
Ph Ph C=O O~C ' 10 V CH Zn CH
f_o o=f ~ `
Me . Me :.
Ph Ph C--O . O--C .
15 VI CH Zn . CH ;; - ~
/~ ~ / ` "'.''".'''','~''''''`' c o o f ~ ! .. : ~ ` `
Me Me fh Ph C=O;, . O=C
VII CH Zn CH ~ ~
C--0 0--C , . ...... : ~ :
Me M~ ~ .
. . . ~ .`;,.. .:
:
2 ~
~' ':'." ~`,' Ph C~ C .,,~
D \ ~
VIIICH Zn CH
Cl--O . --I
. ..
In the formula of ~-diketone metal compounds, n is ;
the valence of the metal and the number of ~-diketone groups per metal atom, as shown: ` " `
M Ll Na K Mg Ca Sr Ba Zn Al Sb n 1 1 1 2 2 2 2 2 3 3 . .~
Hydrocarbon groups R, R', R" and R"' can be open ~ ~ .
chain or cyclic and include such aliphatic, cycloaliphatic and .
aromatic hydrocarbon groups as alkyl and alkenyl groups ~
having from 11 to 18 carbon atoms; aL~yl cycloaLkyl, alkyl cycloaLkenyl .: :
15 and aLkyl cycloaL~ylaLkylene having from 11 to 18 carbon atoms, and alkylcycloalkyl groups having from 11 to 18 carbon atoms, and ~ :
non-condensed aryl groups (including araL~cyl, cycloalkylaryl, and alkyaryl) having 6 to 18 carbon atoms, for example undecyl, - ::
dodecyl, tridecyl, pentadecyl, heptadec-3-en- 1-yl, n-octadecyl, 20 ricinoleyl, linoleyl, linolenyl, decyl cyclohexyl, hexyl cyclohexyl, cyclododecyl, phenyl, m-tolyl, p-ethylphenyl, t-butylphenyl, benzyl, cyclohexylphenyl, phenylpropyl and nonylbenzyL The aryl groups may contain one or two halogen ring substituents, such as fluorine, chlorine or bromine.
.:
2 ~ 2 2 g ~ ~
. ~. .
` ~ ' ' ' ALkoxyhydrocarbon R, R', R" and R"' groups -include n-decoxymethyl, 2-dodecoxyethyl, 2-methoxyphenyl, i and 4-n-octoxyphenylbenzyl. R, R', R" and R"' alkylene-. ~ . ~..
dioxyhydrocarbon groups include 3(ethylenedioxydodecyl) ~ - -5 and 3, 4-methylenedioxyphenyL R ' can be hydrogen, but not R and R", and only one of R and R" can be aliphatic or cycloaliphatic.
;:: . ~.: i Illustrative ~-diketone compounds that can be used include the B-diketones listed below and the aluminum, antimony, barium, calcium, lithium, magnesium, potassium, ` i sodium, strontium, and zinc derivatives thereof. `
: ~' ,.' '~' `'`~';;~
' ~'' ' ~ -.'. '''~' ~''.
'',' ':.
2 ~ 2 2 ~
.'- .- ` ` `.
. ...~ ~.....
.., ~ .. ... ..
No. 1 )odecanoyl-benzoyl~
CllH~3--C--CH---C~) methane .
O o No.2 `~ ``
~ Tride anoyl-benzoyl-C~,H"5--C--CH~--C~ me~hane - .
o o : :~
No. 3 . O~:lu~ al~oyl-b~ oyl~m~hulle `
Cl7H3s--I_CH~
O ., O .::
Nv. 4 .
lru~ ul~oyl b~ oyl~nl~lh~
.CI3H~7--ll--CH3 ~
'`' ~.''`.:
''~ . ,'`;~
17 ~: ` ;:~
2~22~3~ ;
. No. 5 /~ Pen~adecanoyl~benzoyl~
Cl,~3l --C--CH2--C~) methane No. S
Dibellzoylme~llune . `:
~C--CH~--C~
No. 7 Phenylacetyl benzoyl-methane (~C--CH2--C--CH ~) ~0. 8 ~ c9Hls Benzoyl-nonylbenzoyl-methane ~ ICl--~H~--ICl ~
'~
;'~
.
2a22,J~}s :~
``:
No. 9 ~ ~ Octylhexa hydrobenzoyl C8H,7 ~C--CH2--ICl~c8Hl7 octylbenzoyl methane No. 10 1l ~ Benzoyl-p methoxyben70yl-methane ~C--CH2--C~OCH3 -No. 11 O O A Di(p methoxybenzoyl)methane CH30~C--CH2--C~OCH3 No. i2 A 1l 1l ~ Di(p-chlorobenzoyl)methune Cl ~--C~CH2--C~CI
No. 13 -~0 0~ Di(3,4-methylenedioxybenzoyl)methane : `
CH2 ~ O O /--~ CH2 ' ': ~-O~)C--CH2--C~O . ,~
No. 14 O O
/--\ " 1,1-Dodecanoyl- 1-benzoylnonane ~C--I H--C--C
f`
;:
- 2 ~ ~ 2 ~
~
,:,.`
No. 15 O O
` "~
Alpha-dodecanoyl-alpha-~C--Cf.~ C--CllH23 benzoyl-toluene ., ~ .
5 No. 16 ~ Di(p-t-butylbenzoyl)methane t-C4Hg--~0~--C--CH2--C~t~C4H9 ~ O O -No. I7 j ; .
Il Il ~ Benzoyl-nonade~anoyl 10~C--CH~--C--Cl8H37 methane , . . ' ' ' ., ! ' . ' . . , _ . . " ' ' ' .
The polyvinyl chloride resin compositions in accordance with the invention containing a B-diketone and at least one heat stabilizer are stable without the ~-diketone under the normal heat processing conditions, as determined by the usual heat stability tests The B-diketone does not apparently contribute :.
to stability under the normal heat processing conditions, since the polyvinyl chloride resin compositions are sufficiently stable without it, but .it does impart stability under moderate temperatures after shaping in the form of the motor vehicle componeslt, ~ ~:
demonstrating that it does survive the previous heat processing, ~'.
f t ~
'; '~`~' .! -;: ~
While any known heat stabilizer for polyvinyl chloride ~, resins can be used, the preferred heat stabilizers are alkali metal and polyvalent metal salts of organic nonnitrogenous monocarboxylic acids, having from six to twenty Eour carbon atoms. The ~' 5 polyvalent metal is preferably a bivalent nontransition metal, includingbarium, calcium, cadmium, magnesium, strontium, stannous tin and zincO
i3 The aliphatic, aromatic, alicyclic and oxygen-'! containing heterocyclic organic acids are operable as a class~ ;
By the term "aliphatic acid" is meant any open chain carboxylic acid, substituted, if desired, with nonreactive groups, such as halogen, sulfur and hydroxyl. By the term "alicyclic" it will be understood that there is intended any cyclic acid in which the ring is nonaromatic and composed solely of carbon atoms, and such acids may if desired have inert, nonreactive substituents such as halogen, hydroxyl, alkyl radicals, alkenyl radicals and other carbocyclic ring structures condensed therewith. The oxygen-containing heterocyclic compounds can be aromatic or ~
non-aromatic and can include oxygen and carbon in the ring ~ -structure, such as aLkyl-substituted furoic acid~ The aromatic acids likewise can have nonreactive ring substituents such as halogen, aLt{yl and aLkenyl groups, and other saturated or aromatic rings condensed therewith.
As exemplary of the acids which can be used in the form of their metal salts there can be mentioned the following: -:
2 ~ 2 2 ~
-., hexoic acid, 2-ethylhexoic acid, n-octoic acid, isooctoic acid, 3, 5, 5-trimethyl hexoic acid, capric acid, undecyclic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, 5 chlorocaproic acid, hydroxy-capric acid, ethyl acetoacetic acid, benzoic acid, phenyl-acetic acid, butylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, hexylbenzoic acid, salicylic acid, naphthoi~ acid, 1-naphthal~ne acetic acid, orthobenzoyl benzoic acid, naphthenic acids derived from~ ~;
10 petroleum, abietic acid, dihydroabietic acid, hexahydrobenzoic acid, and methyl furoic acid, as well as partially esterified ~ `
dibasic acids such as monobutyl phthalate, isooctyl maleate, ethylene glycol maleate, and 2-ethoxy ethylmaleate.
In combination with the above metal salts of organic 15 acids, or in lieu thereof, a metal salt of a hydrocarbon-substituted phenol can be used. The hydrocarbon substituents contain from four to twenty-four carbon atoms each. The metal can be an aL~ali metal or alkaline earth metal such as sodium, potassiumO lithium, calcium, strontium, magnesium ~o and barium. Among such polyvalent metal phenolates there canbe mentioned the magnesium, barium, calcium, strontium, tin and zinc salts of n-butyl phenol, t-nonyl phenol, n-decyl ~
phenol, t-dodecyl phenol, t-octyl phenol, isohexyl phenol,~ ~ -octadecyl phenol, diisobutyl phenol, methyl propyl phenol, 25 diamyl phenol, methyl isohexyl phenol, methyl t-octyl phenol, .:
''"''~
2 ~
di-t-nonyl phenol, ortho or para phenyl phenol. The modified metal phenolates disclosed by M~ Pollock in U.SO patent No. 3, 630,979 of December 28, 1971 and by M Minagawa in U. S. patent No. 3, 733, 288 of May :15, 1973 are also suitableO ;
Mixtures of salts of various metals can be used, such as mixed zinc and tin salts with the aLkaline earth metal salts, e.gO, barium and zinc stearates, as in U.S. patent No. 2,446,976.
In lieu of but preferably in addition to the polyvalent metal salt, organic phosphites can be used.
The organic phosphite can be any organic phosphite having one or more organic radicals attached to phosphorus through oxygen. These radicals can be monovalent radicals in the case of the triphosphites, diphosphites and monophospbites, which can be defined by the formula:
R l~P~R 3 R2 '-`
in which Rl, R2 and R3 are selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, aLkaryl, araLkyl, and cycloalkyl groups having from one to about thirty carbon atoms Also included are the organic phosphites having a bivalent organic radical forming a heterocyclic ring with the phosphorus of the type:
/ O\ '~ :~
2 5 R~ P--~R
O ., in which Rq is a bivalent organic radical selected from the ~
~ ~ ~ s~
group consisting of alkylene, arylene, ara~ylene, aLkarylene and cycloaLkylene radicals having from two to about thirty carbon atoms, and R5 is a monovalent organic radical as defined above in the case of R1, R2 and R3. `~ Also useful in the compositions of the invention are mixed heterocyclic-open chain phosphites of the type: . O\ /0 ~ 0/ 0/
10 More complex phosphites are formed from trivalent organic radicals, of the type:
/O\ / O\ /O\ /OH
R~O--/ HO-R~ / ~R~ / \ OH
in which R~ is a trivalent organic radical of any of the types of Rl to R5, inclusive, as defined above, A particularly useful class of complex phosphite are the tetraoxadiphosphaspiro undecanes of the formula :
~OCH8~ ~ CH20 \
Ri~P / C\ P--~R2 where Rl and P~2 are selected from the group consisting of aryl, aLkyl, aryloxyethyl, alkyloxyethyl, aryloxyethoxyethyl, aLkyloxyethoxyethyl and aLkyloxypolyethoxyethylO
An especially preferred class of organic phosphites -have a bicyclic aromatic group attached to phosphorus through oxygen, with no or one or more pnenolic hydroxyl groups on 2~22~
either or both of the aromatic rings" These phosphites ~ ~;
are characterized by the formula: :
7 0~ / 7 : ~ `
0/ \0 ' ~
/ --r ~ ~ :
(HO)r"--A~p O
in which Ar is a mono or bicyclic aromatic nucleus and m is an integer of from 0 to about 5. Z is one or a plurality of : .
organic radicals as defined above for Rl to R6, taken singly ~ ~ .
or together in sufficient number to satisfy the valences of the ~;
two phosphite oxygen atoms. Z can also be hydrogen, and can include additional bicyclic aromatic groups of the type ~HO)~"-Ar, The term "organic phosphite" as used herein is inclusive of the above-described mono-, di- and triphosphites. ~i`
Usually, the phosphite will not have more than about sixty carbon atomsO
Exemplary are monophenyl di-2-ethylhexyl phosphite, diphenyl mono-2-ethylhexyl phosphite, di-isooctyl monotolyl phosphite, tri-2-ethylhexyl phosphite, phenyl dicyclohexyl phosphite, phenyl diethyl phosphite, triphenyl phosphite, ~ -tricresyl phosphite, tri(dimethylphenyl) phosphite, trioctadecyl phosphite, triisooctyl phosphite, tridodecyl phosphite, isooctyl diphenyl phosphite, diisooctyl phenyl ~ ;:
~ ,''.
` :
phosphite, tri(t-octylphenyl) phosphite, tri(t-nonylphenyl) phosphite, benzyl methyl isopropy:L phosphite, butyl dicresyl phosphite, isooctyl di(octylphenyl) phosphite, di(2-ethylhexyl) (isooctylphenyl) phosphite, tri(2-c~yclohexylphenyl) phosphite, tri-a-naphthyl phosphite, tri(phenylphenyl) phosphite, tri(2-phenyl ethyl) phosphite, monododecyl phosphite, di(p-tert-butyl phenyl) phosphite, decyl phenyl phosphite, tert-butyl~
phenyl 2-ethylhexyl phosphite, ethylene phenyl phosphite, ethylene t-butyl phosphite, ethylene isohexyl phosphite, ethylene isooctyl phosphite, ethylene cyclohexyl phosphite, 2-phenoxy- 1, 3, 2-dioxaphosphorinane, 2-butoxy- 1, 3, 2-dioxaphos-phorinane, 2-octoxy-5, 5-dimethyl~dioxaphosphorinane, 2-cyclohexyloxy-5, 5-diethyl dioxaphosphorinane, monophenyl phosphite, 2-ethylhexyl phosphite, isooctyl phosphite, cresyl phosphite, t-octylphenyl phosphite, t-butyl phosphite, diphenyl phosphite, diisooctyl phosphite, dicresyl phosphite, dioctylphenyl `:
phosphite, didodecyl phosphite, di-a-naphthyl phosphite, ethylene phosphite, butyl cresyl phosphite, phenyl-mono-2-ethylhexyl ~;
phosphite, isooctyl monotolyl phosphite and phenyl cyclohexyl phosphite~
Exemplary pentaerythrityl phosphites are 3, 9-diphenoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane (diphenyl- ~:
pentaerythritol-diphosphite), 3, 9 di(decyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(isodecyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5) -undecane, 3, 9- -: .
26 :
~ ~ x ~
di(octadecyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3-phenoxy-9-isodecyloxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(methoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(lauryloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di-p-tolyoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3-methoxyethyloxy-9- ~:~
isodecyloxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(ethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(butoxyethoxy)-2, 4, 8, 10 tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3-methoxyethoxy- .
9-butoxyethoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxyethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(butoxyethoxyethoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9 di(methoxyethoxyethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxy(polyethoxy) ethyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane :
(where the (polyethoxy)ethoxy group has an average molecular weight of 350), 3, 9-di(methoxy(polyethoxy)ethoxy)-2, 4, 8, 10- .
tetraoxa-3, 9-cliphosphaspiro-(5, 5)-undecane (where the (polyethoxy)-ethoxy group has an average molecular weight of 550).
~. - -., ~2~
Exemplary of the bis aryl phosphites are: bis(4, 4'- :
thio-bis(2-tertiary-butyl- 5-methyl-phenol)) isooctyl phosphite, mono(4, 4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)) di-phenyl phosphite, tri-(4, 4'-n-butlidene-bis(2-tertiary-butyl- :; ;
5 5-methyl-phenol)) phosphite, (4, 4'-benzylidene-bis(2-tertiary-butyl-5-methyl-phenol)) diphenyl phosphite, isooctyl 2,2'-bis(parahydroxyphenyl) propane phosphite, tridecyl 4,4'-n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol) phosphite, ` .
4, 4'-thiobis(2-tertiary-butyl-5-methylphenol) phosphite, 2- ~:
ethylhexyl-2, 2'-methylene-bis(4-methyl-6-1'-methylcyclohexyl) ~
phenol phosphite, tri(2, 2 ' -bis- (para-hydroxyphenyl) propane) ::
phosphite, tri(4, 4'-thio-bis(2-tertiary-butyl-5-methyl-phenol) ;~
phosphite, isooctyl-(2, 6-bis(2'-hydroxy-3, 5-dinonylbenzyl)-4- : ;
nonyl phenyl)) phosphite, tetratridecyl 4, 4'-n-butylidene- -~
15 bis(2-tertiary-butyl-5-methyl phenyl) diphosphite, tetra-isooctyl 4, 4'-thiobis(2-tertiary-butyl-5-methyl phenyl) diphosphite, 2, 2'~
methylene-bis(4-methyl-6-1'-methyl cyclohexyl phenyl) ~-polyphosphite, isooctyl-4, 4'-isopropylidene-bis-phenyl- - .
polyphosphite, 2-ethylhexyl-2, 2'-methylene-bis(4-methyl-6, 1'- :
20 methyl-cyclohexyl) phenyl triphosphite, tetratridecyl-4,4'-oxydiphenyl diphosphite, tetra-n-dodecyl-4, 4'-n-butylidenebis -(2-tertiary-butyl-5-methylphenyl) diphosphite, tetra-tridecyl-4, 4'-iso-propylidene bisphenyl diphosphite, hexatridecyl butane- .
1, 1, 3-tris(2'-rnethyl-5'-tertiary-butylphenyl-4') triphosphite. ~ ~
'':.
~.
::;`
2 ~
Preferred classes of additional stabilizers that can be used include the phenols, aliphatic polyhydroxy compounds;
esters, amides, and hydrazides of thioalkylenedicarboxylic acids and nitrilotrialkylenetricarboxylic acids; ketoacetic acid compounds; and organic nitrogen compounds such as the esters of betaaminocrotonic acid, diphenylthiourea, and 2-phenylindole. Phenol stabilizers can be included in amounts corresponding to 0. 01 to about 0. 2 parts per 100 parts of polymer being stabilized~ Typical phenol stabilizers are butylated hydroxy-toluene (BHT), 4, 4'-isopropylidenebisphenol, -~
and 1, 1, 3 -tris(2 ' -methyl-4 ' -hydroxy- 5' -t-butylphenyl) butaneO
The phenol stabilizers contain one or more phenolic hydro~yl groups, and one or more phenolic nuclei and can contain from about eight to about three hundred carbon atoms In addition, the phenolic nucleus can contain any oxy or thio ether group.
The a~cyl-substituted phenols and polynuclear phenols, ~ "
because of their molecular weight, have a higher boiling point, and therefore are preferred because of their lower volatility.
There can be one or a plurality of alkyl groups of one or more carbon atoms. The alkyl group or groups including any alkylene groups between phenol nuclei preferably aggregate at least four carbon atomsO The longer the alkyl or aLkylene chain, the better the compatibility with polypropylene, inasmuch as the phenolic compound then acquires more of an aliphatic ~ ~
-,'' . '' 29 ~
'`'~
hydrocarbon character, and therefore there is no upper limit on the number of aLkyl carbon atoms. Usually, from the standpoint of availability, the compound will not have more than about eighteen carbon atoms in an alkyl, alicyclidene ;
and alkylene group, and a total of not over about fifty carbon atoms. The compounds may have from one to four alkyl radicals per phenol nucleus The phenol contains at least one and preferably at least two phenolic hydroxyls, the two or more hydroxyls being in the same ring, if there is only one. In the case of bicyclic phenols, the rings can be linked by thio or oxyether groups, ~
or by alkylene, alicyclidene or arylidene groups. -The monocyclic phenols which can be employed have the structure: ;
(R),~l~(O~)x2 ;
::
R is selected from the group consisting of hydrogen;
halogen; and organic radicals containing from one to about ;~
thirty carbon atoms, such as alkyl, aryl, alkenyl, a~aryl, araLkyl, cycloalkenyl, cycloalkyl, aLkoxy, and acyl ~
R'IC-- ~ -O :'. .
where R' is aryl, alkyl or cycloa~yl. ~ -, .~. . .
x, and x2 are integers from one to four, and the sum of ~
xl and x2 does not exceed six. -,' ~''.', : :-'', The polycyclic phenol employed in the stabilizer combination is one having at least two aromatic nuclei linked ~ -by a polyvalent linking radical, as clefined by the formula:
( I r)~ Y-( I r)~l2 (OH)"~l (H)n~a wherein Y is a polyvalent linking group selected from the group consisting of oxygen; carbonyl; sulfur; sulfinyl;
aromatic, aliphatic and cycloaliphatic hydrocarbon groups;
and oxyhydrocarbon, thiohydrocarbon and heterocyclic groups.
The linking group can have from one up to twenty carbon atoms Ar is a phenolic nucleus which can be a phenyl or a polycar~oxylic group having condensed or separate phenyl rings: each Ar group contains at least one free phenolic hydroxyl group up to a total of fiveO The Ar rings can also include additional rings connected by additional linking nuclei of the type Y, for example, Ar-Y--A~Y-Ar.
ml and m2 are numbers from one to five, and n1 and -n2 are numbers of one or greater, and preferably from one ,.-....
to four.
The aromatic nucleus Ar can, in addition to phenolic hydroxyl groups, include one or more inert substituents. -Examples of such inert substituents include hydrogen, halogen atoms~ e. g. chlorine, bromine and fluorine; organic radicals containing from one to about thirty carbon atoms,~ `
25 such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl, alkoxy, aryloxy and acyloxy " ~
31 ~
~ ~ 2 r t c~ ~3 ~
R ' C-O ~ ~
O . ~
where R' is aryl, alkyl or cycloalkyl, or thiohydrocarbon ~;
groups having from one to about thirty carbon atoms, and ~ .
5 carboxyl -C~ :'' O ;~
groups. Usually, however, each aromatic nucleus will not have more than about eighteen carbon atoms in any hydrocarbon substituent groupO The Ar group can have from -:
one to four substituent groups per nucleus.
Typical aromatic nuclei include phenyl, naphthyl, phenanthryl, triphenylenyl, anthracenyl, pyrenyl, chrysenyl, ~
and fluorenyl groupsO ~ -;
When Ar is a benzene nuc leus, the polyhydric .
polycyclic phenol has the structure: -;~. ~ . : .. .~ .
~~ OH~ ~0~ :' ~ '``'' E~ YT~
~ y~ R~
wherein Rl, R2 and R3 are inert substituent groups as . ~
de~cribed in the previous paragraph, ml and m3 are integers~- .
from one to a maximum of five, m2 is an integer from one . -to a maximum of four, xl and X3 are integers from zero to ~ -four, and x2 is an integer from zero to three; Yl is an integer - .
from zero to about six and Y2 is an integer from one to five, ~:
preferably one or two 2 ?~ 2 2 ~
Preferably, the hydroxyl groups are located ortho and/
or para to Y.
Exemplary Y groups are alkylene, alkylidene, and alkenylene arylene, aLkyl arylene, arylalkylene, cycloalkylene, 5 cycloalkylidene, and oxa- and thia-substituted such groups;
carbonyl groups, tetrahydrofuranes, esters and triazino groups~
The Y groups are usually bi, tri, or tetravalent, connecting two, .:
three or four Ar groupsO However, higher valence Y groups, ``
connecting more than four Ar groups, can also be used. ` `
10 According to their constitution, the Y groups can be assigned to subgenera as follows~
. ~:
(1) Y groups where at least one carbon in a chain or cyclic arrangement connect the aromatic groups, such as --CEt~CE3r-;--(CHI~;~CH~;
~ ~ , 15 -O~OEr, ~O;-C~
~ J ~
X ' .',~' CH, C~
CH_;_C~ b~ C~_; ....
7 b~, C2~ C~3 cHr b--C~ CH~}C~
33 `~
, 1 . ' ' ' ' ' '" ' ' ' ; ~ ' ~22~5 `
,,``.
-C~C}; o_; ~ C.
o~,)~: {~C~<~
~, o~c~l :`.````.'`'`
--CH~--~ J--C}~
Y ' ,- ., 10--CH~ ~ H~ I2C~ /CEI~, --~r,c C~3-- - .
' H b c~
15-EC/I~ C~; b~
CE~ ~OH;
H3~\l/C~ /~H-- ~Ht (2) Y groups where only atoms other than carbon link . ~
the aromatic rings, such as ~ .
-O~ ~, --S- and-(S)x--O O
where x is a number from one to ten;
(3) Y groups made up of more than a single atom :
including both carbon and other atoms linking the aromatic nuclei, such as 2 ~
--C ~3:~0--i~ C H--C ~I~ O--C ~I~C
H~
~0~ ~ '.. -':` '.' --O--CH~C~I~O--;--C~Irt 8 tC}~
--C~.~ S~C~;--S--CH~ S--;--C ~ CH~
--C~C~ ~--CH~;--c--o--~c~ o--c--;
10C1--C~I~OOCC}~iC~
O O
c~ cH~a O c~c~o a C~I2C~
15N~ \N ;--C~S--; ~;
~o N
20--CH~S--CH~; a~d ¦ S ~
Although the relation of effectiveness of chemical structure `
is insufficiently understood, any of the most effective phenols have Y groups of subgenus (1), and accordingly this is preferredO Some of these phenois can be prepared by the 25 aLkylation of phenols or alkyl phenols with polyunsaturated hydrocarbons such as dicyclopentadiene or butadiene, ~.~
-` 2 ~ 2 2 ~
:: ,.. ..
. -. :`, Representative phenols include guaiacol, resorcinol ``.
monoacetate, vanillin, butyl salicylate, 2, 6-ditert-butyl-4- ` ` `
methyl phenol, 2-tert-butyl-4-methoxy phenol, 2, 4-dinonyl phenol, 2, 3, 4, 5-tetradecyl phenol, tetrahydro~ naphthol, ~ ~ ;
o-, m- and p-cresol, o-, m- and p-phenylphenol, o-, m-and p-xylenols, the carvenols, symmetrical xylenol, thymol, o-, m- and p-nonylphenol, o-, m- and p-dodecylphenol, and o-, m- and p-octyl-phenol, o- and m-tertbutyl-p-hydroxy- ~ ~ `
anisole, p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n- `. .
decyloxy-cresol, eugenol, isoeugenol, glyceryl monosalicylate, methyl-p-hydroxy-cinnamate, 4-benzyloxy-phenol, p-acetyl-am inophenol, p-stearyl-am inophenol methyl-p-hydroxybenzoate, p-di-chlorobenzoyl-aminophenol and p-hydroxysalicyl anilideO .
E~emplary polyhydric phenols are orcinol, propyl gallate, ` ~
cetechol, resorcinol, 4-octyl-resorcinol, 4-dodecyl-resorcinol, .
4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol, :
hexahydroxybenzene, 4-isohexylcatechol, 2, 6-ditertiary-butyl- ~ -resorcinol, 2, 6-diisopropyl-phloro~lucinol.
Exemplary polyhydric polycyclic phenols methylene-bis-(2, 6-ditertiarybutyl-phenol), 2, 2-bis-(4-hydroxyphenyl)-propane, methylene-bis(p-cresol), 4, 4'-benzylidenebis-(2-tertiary butyl-5-methylphenol), 4, 4'-cyclohexylidenebis-(2-tertiary butylphenol), 2, 2'-methylene-bis(4-methyl-6-(1'-methyl-cyclohexyl)-phenol), 2, 6-bis(2'-hydroxy-3'-tertiary-butyl-5'-methylbenzyl)-4-methylphenol, (2-tertiary-butyl-5-methyl-36 :
: .
~22~3~
phenol)! 2, 2'-bis(4-hydroxy-phenyl) butane, ethylenebis- i (p-cresol), 4, 4'-oxobis-phenol, 4, 4'-oxobis(3-methyl-5-isopropyl-phenol), 4, 4'-oxobis-(3-methyl-phenol), 2, 2'-oxobis-(4-dodecyl-phenol), 2, 2'-oxobis-(4-methyl-5-tertiary-butyl-phenol), 4, 4'-thio-bis-phenol; 4, 41-thio-bis-(3-methyl-6- ; ~`.tertiary-butyl-phenol), 2, 2'-thio-bis-(4-methyl-6-tertiary- ~:
butyl-phenol), 4, 4' -n-butylidene- (2- t-butyl- 5-methyl-phenol), 2, 2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-phenol), 4, 4'-cyclohexylenebis-(2-tertiary-butyl-phenol), 2, 6-bis-(2'-hydroxy-3'-t'-butyl-5'-methyl-benzyl)-4-methyl-phenol, 4, 4'-oxobis(naphthalene-1, 5-diol), 1, 3'-bis(naphthalene-2, 5-diol)propane, and 2, 2'-butylenebis-(naphthalene-2,7-diol), (3-rnethyl- 5-tert-butyl-4-hydroxyphenyl)-4'-hydroxyphenyl) ;
propane, 2, 2'-methylenebis-(4-methyl-5-isopropylphenol), 2, 2'-methyl~nebis-(5-tert-butyl-4-chlorophenol), (3, 5-di-tert- -:
butyl-4-hydroxyphenyl)-(4'-hydroxyphenyl) ethane, (2-hydroxy~
phenyl)-(3', 5'-di-tert-butyl-4', 4-hydroxyphenyl)ethane, 2, 2'-methylenebis-(4-octylphenol), 4, 4'-propylenebis-(2-tert-butyl-phenol), 2, 2'-isobutylenebis-(4-nonylphenol), 2, 4-bis-(4-hydroxy-3-t-butylphenoxy)-6-(n-octylthio)-1, 3, 5-triazine, 2, 4, 6-tris(4-hydroxy-3-t-butylphenoxy)-1, 3, 5-triazine, 2, 2'-bis-(3-t-butyl-4-hydroxyphenyl) thiazolo-(5,4-d) thiazole, 2, 2'-bis(3-methyl-5-t-butyl-4-hydroxyphenyl) thiazolo-(5, 4-d)-thiazole, 4, 4'-bis(4-hydroxy-phenyl) pentanoic acid octadecyl ester, cyclopentylene-4, 4'-bisphenol, 2-ethylbutylene-4, 4'- ~ -~
'; ~ '' 37 ~
, ~, 2~.2~
bisphenol, 4, 4'-cyclooctylenebis(2-cyclohexylphenol), B, .B-thiodiethanol-bis(3 -tert-butyl-4 -hydroxyphenoxy ac etate), 1, 4-butane-diobis(3-tert-butyl-4-hydroxyphenoxy acetate), .
pentaerythritoltetra(4-hydroxyphenol propionate), 2, 4, 4'-tri- :~
hydroxy benzophenone, bis(2-tert-butyl-3-hydroxy-5- ~ ~.
methylphenyl sulfide, bis(2-tert-butyl-4-hydroxy-5-methyl-phenyl) sulfide, bis(2-tert-butyl-4-hydroxy-5-methyl-phenyl sulfoxide), bis-(3-ethyl-5-tert-butyl-4-hydroxy benzyl) sulfide, bis(2-hydroxy-4-methyl-6-tert-butyl-phenyl) sulfide, 4, 4'-bis(4-hydroxyphenyl) pentanoic acid octadecyl thiopropionate ester, 1,1, 3-tris(2'-methyl-4'-hydroxy-5'-tert-butylphenyl) butane, 1, 1, 3-tris-(1-methyl-3-hydroxy-4-tert-butylphenyl) butane, 1, 8-bis(2-hydroxy-5- ` ~ ~:
methylbenzoyl-n-octane, 2, 2'-ethylene-bis-[4'-(3-tert-butyl-4-hydroxyphenyl)-thiazole], 1-methyl-3-(3-methyl-5-tert-butyl-4-hydroxybenzyl)-naphthalene, 2, 2'-(2-butene) `~
bis-(4-methoxy-6-tert-butyl phenol) and pentaerythritol -hydroxyphenyl propionate~
A particularly desirable class of polyhydric polycyclic phenols are the dicyclopentadiene polyphenols, which are of the type:
R~
Rl . n .
~ ~ ~ ,7 ~
in which Rl and R2 are lower a~{yl, and can be the same or different, and n is the number of the groups enclosed by the brackets, and is usually from 1 to about 5, These are described in U. S, patent NoO 3, 567, 683, dated March 2, 1971 5 to Spacht. A commercially available member of this class is Wingstay L, exemplified by the dicyclopentadiene tri(2-tert-butyl-4-methyl-phenol) of the formula:
0~: ,0~ " 0~';~ :
c(}~
H~ Er~ ~r~ ;
The polyhydric polycyclic phenols used in the invention can also be condensation products of phenol or a~yl-phenols with hydrocarbons having a bicyclic ring structure and a double bond or two or more double bonds, such as cY-pinene, B-pinene, 15 dipentene, limonene, vinylcyclohexene, dicyclopentadiene, allo-ocimene, isopreneandbutadiene. Thesecondensatlon ~ d products are usually obtained under acidic conditions in the ~ --form of more or less complex mixtures of monomeric and polymeric compounds. However, it is usually not necessary ~ -20 to isolate the individual constituentsO The entire reaction product merely freed from the acidic condensation catalyst and unchanged starting material, can be used with excellent resultsO
While the exact structure of these phenolic condensation products is uncertain, the Y groups linking the phenolic nuclei all fall into the preferred subgenus 1. For method of preparation, see, e.g., U S. patent No. 3, 124, 555, U,S. patent No.
3, 242,135, British patent No~ 961, 5040 Aliphatic polyhydroxy compounds can be included in amounts corresponding to 0.1 to about 1 part per 100 parts of polymer being stabilized. Typical aliphatic polyhydroxy compounds are glycerol, polyglycerol, monodi-, and tri-pentaerythritol, mannitol, sorbitol, and partial esters of these with saturated and unsaturated fatty acids having 6 to 22 carbon atoms.
The esters, amides, and hydrazides of thiodialkylene dicarboxylic acids and nitrilotri-aL"ylenetricarboxylic acids can be included in amounts corresponding to 0.1 to about 1 part per 100 parts of polymerO Typical of these are dimethyl thiodipropionate, dilauryl and distearyl thiodipropionates, -~
2, 2 '-thiobis(acetyl ethanolamine), 3, 3 '-thiobis(propionyl-diisopropanolamine, nitrilotriacetic acid (NTA) propylene glycol ester, NIA tris(ethylamide), NTA bis (hydroxyethyl) N-butylamide, 3, 3~-thiodipropionyldihydrazide and 6, ~
thiodihexanoyldihydrazide. ~ ;
The thiodipropionic acid ester has the following formula:
Ft lOOCCH2CH2--~CH2CH2COOY
-,'''.' in which Rl is an organic radical selected from the group ~;
consisting of hydrocarbon radicals such as aLkyl, alkenyl, aryl, cycloalkyl, mixed a~yl aryl, and mixed alkyl cycloalkyl ~`
radicals; and esters thereof with aliphatic carboxylic acids;
5 and Y is selected from the group consisting of (a) hydrogen, (b) a second R radical R2, which can be the same or different from the R, radical, (c) a polymeric chain of n thiodipropionic ~;
acid ester units:
R 1O[OCCH2CH2SCH2CH2COOXO]nOCCH2CH2-~CH2CH2COOZ ~ :
10 wherein Z is hydrogen, R2 or M; n is the number of thiodipropionic acid ester units in the chain; and X is a bivalent hydrocarbon group of the type of Rl; the value of n can range upwards from 1, but there is no upper limit on n .
except as is governed by the ratio of carbon atoms to sulfur :: .
. . .
atoms as stated below; and (d) a polyvalent metal M of .
. . .
Group II of the Periodic Table such as zinc, calcium, cadmium, barium, magnesium and strontium. ~
The molecular weights of the R and Y radicals are taken - .
such that with the remainder of the molecule, the thiodipropionic : `
20 ester has a total of from about ten to about sixty carbon atoms per sulfur atom. . `
Accordingl~, the various thiodipropionic ac id ester .: ~
species coming within the above-mentioned categories within ;.
the general formula can be defined as follows: ~
~., 41 ~`
2 ~
(a) R lOOCCH2CH2SCH2CH2COOH
(b) RlOOCCH2CH2SCH2CH2COOR2 (c) R~O[()CCH2CH2SCHzCH2COOX-O]nOCCH2CH2SCH2CH2COOZ ~ ~;
(d) [RlOOCCH2~H2ScH2cH2c0o]2M
5 In the above formulae, Rl and R2, M, X and Z are the same as before. In the polymer (c), as in the other forms of thiodipropionic acid esters, the total number of carbon atoms per sulfur atom is within the range from about ten to about sixty.
The R radical of these esters is important in furnishing compatibility with the polypropylene. The Y radical is ;
desirably a different radical, R2 or M or a polymer, where `
R is rather low in molecular weight, so as to compensate for this in obtaining the optimum compatibility and nonvolatilityO
Where Y is a metal, the thiodipropionic acid ester furnishes `
the beneficial properties of the polyvalent metal salt which is ;
described belowO
The aryl, alkyl, aL'senyl and cycloalkyl groups may, if -desired, contain inert~ nonreactive substituents such as 2û halogen and other carbocyclic and heterocyclic ring structures condensed therewithO ~-Typical R radicals are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, -~
n-octyl, isooctyl, 2-ethyl hexyl, t-octyl, decyl, dodecyl, 25 octadecyl, allyl, hexenyl, linoleyl, ricinoleyl, oleyl, phenyl, '-''''.' ' .
'.
2 ~ 2 2 ~
xylyl, tolyl, ethylphenyl, naphthyl, cyclohexyl, benzyl, cyclopentyl, methylcyclohexyl, ethylcyclohexyl, and ;
naphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl, pentaerythrityl, and polyoxyalkylene radicals such as those 5 derived from diethylene glycol, triethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, and .
polyoxypropyleneoxyethylene glycol, and esters thereof with any of the organic acids named below in the discussion of the ~.
polyvalent metal salts, including in addition those organic acids ` `
having from two to five carbon atoms, such as acetic, propionic, . `
butyric and valeric acids~ `
Typical X radicals are alkylene radicals such as ethylene, tetramethylene, he~amethylene, decamethylene, ~ ~.
alkyl- and aryl-substituted a~cylene radicals such as 1, 2- ~: .
15 propylene, CH~ ICHI CH~ snd --C:~CE--,_CH~C--CH~,~ nd--CH--;
1H1 b~
arytene radicals such as phenyIene {}' ' .`' 20 methylenephe~ylene -C~
dimethyIene phellylene, _CH~CH~
2 ~ ~ 2 ~
and alieyclene radicals such as cyclohe~ylc~e <3~
a~d cyclopentylene -~ .. ~, .
1-~ r ~
\/ .. .;
As exemplary of the thiodipropionic acid esters ~: `
which can be used, there can be mentioned the following:
monolauryl thiodipropionic acid, dilauryl thiodipropionate, ~ .
butyl stearyl thiodipropionate, di(2- ethylhexyl)- thiodipropionate, diisodecylthiodipropionate, isodecyl phenyl thiodipropionate, .: :.,:
benzyl lauryl thiodipropionate, benzyl phenyl thiodipropionate, ; :~
the diester of mixed coconut fatty alcohols and thiodipropionic . `
acid, the diester of mixed tallow fatty alcohols and thiodipropionic acid, the acid ester of mixed cottonseed oil .
fatty alcohols and thiodipropionic acid, the acid ester of mixed ~ ~`
soybean oil fatty alcohols and thiodipropionic acid, cyclohexyl ;
. .
nonyl thiodipropionate, monooleyl thiodipropionic acid, hydroxyethyl lauryl thiodipropionate, monoglyceryl thiodipropionic ~ ~`
acid, glyceryl monostearate monothiodipropionate, sorbityl isodecyl thiodipropionate, the polyester of diethylene glycol ~ ~.
and thiodipropionic acid, the polyester of triethylene glycol - ~ .
and thiodipropionic acid, the polyester of hexamethylene glycol :~
and thiodipropionic acid, the polyester of pentaerythritol and thiodipropionic acid, the polyester of octamethylene glycol and -",~
2 ~ 3 ~
~'``''~
thiodipropionic acid, the polyester of p-clibenzyl alcohol and ; -thiodipropionic acid, ethylbenzyl lauryl thiodipropionate, ~ -strontium stearyl thiodipropionate, magnesium oleyl thiodipropionate, calcium dodecylbenzyl thiodipropionate, and mono(dodecylbenzyl) 5 thiodipropionic acid.
These esters are for the most part known compounds, ~`
but where they are not available, they are readily prepared by esterification of thiodipropionic acid and the corresponding "
alcohol, Ketoacetic acid compounds that can be used with the stabilizer compositions of this invention in amounts of about 0O 05 to about 0~ 5 parts per 100 parts of polymer being stabilized include 2-ethylhexyl acetoacetate, glyceryl tris(acetoacetate) and dehydroacetic acid.
The keto acetic acid compound should be nonvolatile and stable at processing temperatures. It should also be nitrogen-free. In general, compounds having at least eight carbon atoms in the molecule fulfill these requirements. The free keto acetic acids, for some reason that is unknown, do 20 not possess the stabilizing effectiveness of the esters or of the anhydride dimers. However, metal salts of these keto acids can be used as the metal salt component of the stabilizer combination oE the invention, and in combination with the ester and/or anhydride dimer have excellent stabilizing effectiveness.
:~
~2~
The keto acetic acid esters of this invention have the following general formula:
(R-CI--CH2--Cl--O),~R ' .`.. ., o O '~
5 wherein R is an inert organic group having from one to about thirty carbon atoms, R' is an inert organic radical having from one to about thirty carbon atoms, and x is a number from on0 to ten. The ester molecule has a total of at least eight carbon atoms R and R' can be hydrocarbon groups, and can b~ allcyl, allcenyl, aryl, aLkylaryl, aryl allcyl, cycloallcyl, cycloallcenyl, and heterocyclicO The open chain groups can be straight or branched, and the cyclic and alicyclic groups can be saturated or unsaturated. The R and R' groups can also be substituted by -~
15 inert groups such as halogen (fluorine, chlorine, bromine and iodine) alkoxy or epoxy -C--C'- hydroxy OH and ether O ' `
- C~C- groups. There will not usually be more than ten of such substituents, depending of course upon the number of 20 available substituent positions in the R and R' groups.
Thus, the R' radical for example can include free hydroxyl OH groups, up to a practical maximum of ten, but generally not more than one hydroxyl group per carbon atom, and the R' raclical can carry a plurality of R-CI-CH2-C~
- -46 ~-~2~
::`..;
ester groups, up to a total of about ten, the value of x. It will `
be understood that where R' has more than one OH group, the value of x represents only an average value of the number of i;
possible ester species that may exist, dependent on the total number 5 of H groups on R'. For instance, in the case of a di-ester (x=~), where R' has three free OH groups, there can also be ~.;
pentaester, tetraester, triester and monoester species presentO .
Indeed, in such cases, x can be a decimal number, for instance, 2, 5, indicating the presence of a mixture of monoester, diester, .
triester and higher ester species in proportions to give this average value for xO Those skilled in the art will perceive the increased possibilities as x increases to ten or more.
Exemplary R and R' hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, tert-amyl, hexyl, heptyl, tert-octyl, 20ethyl hexyl, isononyl, decyl, undecyl, dodecyl, ~ ~:
palmityl, stearyl, oleyl, ricinoleyl,linoleyl, linolenyl, behenyl, tridecyl, phenyl, xylyl, tolyl, naphthyl, cyclohexyl, methyl-cyclohexyl, cyclopentyl, tetrahydrofurfuryl, cycloheptyl, isononylphenyl, iEuryl, and pyranylO :
Exemplary hydroxy-substituted R' groups include . :~
hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyamyl, 2-hydroxyamyl, 2, 2-dimethylol propyl, 2, 2-dihydroxyamyl, 1,1-methylol hydroxybutyl, 2-(di-hydroxyethyl)-butyl, ;
~ ~ 2 ~
1-(dihydroxy ethyl) propyl, 3-4 dihydroxyheptyl, 4-5 dihydroxyoctyl, `
7, 8-dihydroxyhepta-decyl, 6, 7-dihydroxytetradecyl, 1, 2, 3- ;
trimethylol octadecyl, 1, 2, 3, 4, 5, 6-hexahydroxy heptyl, 10-hydroxyeicosyl, 2, 3-dihydroxypropyl, 4-hydroxybutyl, 3, 4-dihydroxybutyl, 2, 3, 4-trihydroxybutyl, 1, 3, 4-trihydroxybutylO ~ .:
These esters are readily prepared according to known ~ ~ `
procedures by transesterification of a simple ester of the corresponding keto acetic acid, such as ethyl acetoacetate, :
with the corresponding alcohol. If the corresponding keto acetic acid is stable, direct esterification is possible If a ~ -polyhydric alcohol is used, mixed esters of the acid and : `.
alcohol are obtained, according to the molar proportions of :
each, and mixtures of the various possible esters will also be .:
present in most case. .:~
Typical esters are:
(2)Is~C,E[~ C E[2~ 5 .(3~~8 c~ o ~P~ r~
2 5 a~"GE~ p~ ;
2~2~
' ::
Q ; ;`:
5~ QE~9O~ "O'~
. O `:`
,a~--~a~ ,C~I,aO~
O ~`~`.'~'`.
~)lCH~ sC~H~ . ; ;
(~0)C~8Ht7C CE?C--O--C3H7-iso :-O ~ ~ " ~ ~ r~
. , o 11 ., ~. ., ,;, . 1 ~. , : ' , ~13) a~ r~ -, ~E~-~B~a~E
(14) ~ O~t~
CEt--I a~ o--CH, ~--QH~OE
Q3~
~i~t` [ClI~--OE~--O--GHs--37 tl6) ;- OHsll-a~ O~
pHt.--Q--CH~--O--,~ H~
tl~t ~o3~H~ ~?~
. - :
49 .::
(18) [a~7~5~ H~ 0~ ]?G~[O~
. ~ g.a~ .Q..~H,~
. ~20) [t~rt-O~H9--C--C~It~--Q 4.H~ Q~
'21`
. ~ll~a~ o~ 3-~ ~HaO~
0 (~ IQ~a~C.. eE~ a~ (CHa~H)~
s~ ~ ~ 7 : ~
.' . . O~[r~C~ Q~ -Q-~;
(2~ QH~--~Cl~ ¢.--.Q}~C--Q ¢aH~
(25) C~Ha~H--~ O~ ¢--O:EIi~--O ~35~III lso (2û) OH~C)H?--O~CHrCH~ O~C--O--OH~O:~aOE~
(~ ¢~
~a~ O~--pH~--O--OHI¢H~Q--C,HaCH~Q~
~28) OH~O:EI~[O OHa--OH~I?--0--~3HaC--OlI~11 OOH~
(2,~ [Ç~ --Q--JQ:~p~I~[QQH~q~ a ~ -~ G H O
` ~ '' ~ -\
- 2~22~
The keto acid anhydride dimers have the ormula: ~
S ~ r II. R
R~OO0~ :
~ Lo "", O ',` ` "
R is again as above and Rl is hydrogen or R'. ~;
Exemplary are dehydroacetic acid, isodehydroacetic acid, dehydropropionyl acetic acid, dehydrobenzoyl acetic acid, isodehydro-3,4-dichlorobenzoylacetic acid, and esters of isodehydroacetic acid such as the methyl, ethyl, n-butyl ;~:
2~ethyl hexyl and glyceryl esters.
Organic nitrogen compounds that can be used with the stabilizer compositions of this invention in amounts of about 0, 05 to about 0. 5 parts per 100 parts of polymer being l`
stabilized include 2-ethylhexyl 3-aminocrotonate, 1,4-butanediol bis(3-aminocrotonate) and 2, 2'-thiodiethyl 3-aminocrotonate;
thiocarbanilide and 2-phenylindole, 1, 3-dibutylthiourea, :
phenylurea, and p-ethoxyphenylureaO ~.
The stabilizer compositions of this invention are effective with any vinyl chloride polymer. The term "vinyl -.
chloride polymer" as used herein is inclusive of any polymer ~-formed at least in part of the recurring group, 2~22~
` , X .
-CH C-~1 X '","' and having a chlorine content in excess of 4û% In this group, the X groups can each be either hydrogen or chlorineO ;~
In polyvinyl chloride homopolymers, each of the ~ groups is ~ ~
hydrogen. Thus, the term includes not only polyvinyl chloride ~;
homopolymers but also after chlorinated polyvinyl chlorides as ~-a class, for example, those disclosed in British patent No. 893, 288 and also copolymers of vinyl chloride in a major proportion and other copolymerizable monomers in a minor proportion, such as copolymers of vinyl chloride and vinyl `;
acetate, copolymers of vinyl chloridewith maleic or fumaric acids or esters, and copolymers of vinyl chloride with styrene, ~5 propylene, ethylene, 1-hexene, or vinyl n-dodecyl ether. The invention also is applicable to mixtures of polyvinyl chloride in ;
a major proportion with a minor proportion of other synthetic `
resins such as chlorinated polyethylene or copolymers of acrylonitrile with butadiene and styrene.
The invention is of application to the stabilization of rigid polyvinyl chloride resin compositions, that is, resin compositions which are formulated to withstand high processing temperatures, of the order of 190C and higher, and of plasticized polyvinyl chloride resin compositions of conventional formulation where resistance to heat distortion is not a requisiteO
The respective definitions of rigid and plasticized resins are as follows. The rigid resins are those resins to which plastici~ers ~ ~ ~ 2 ~
are not added, and which are generally worked at about 190C.
The ASTM definition (1961 D-883, Part 9, page 804) is as follows: :
"a plastic which has a stiffness or apparent modulus 5 of elasticity greater than 7000 grams per square centimeter (100, 000 psi) at 23Co "
The plasticized resin would therefore have a modulus of elasticity of less than 7000 grams per square centimeter, `~
and would have added to it the plasticizer compound, i' Conventional plasticizers well known to those skilled in the art can be employed such as, for example, dioctyl phthalate, octyl diph0nyl phosphate and epoxidized soybean oil.
The preparation of the stabilized polymer composition is easily accomplished by conventional procedures. The selected stabilizer combination along with such compounding ingredients as plasticizers, colors, lubricants, antistatic agents etc. as may be needed, is blended with the polymer being stabilized, using, for instance, plastic mixing rollers, at a temperature at which the mix is fluid and thorough blending facilitated, typically at from 120 to 180C for a time sufficient to form a homogeneous sheet, five minutes, usually~ After the ~:
mass is formed, it is sheeted off in the usual way, :~
. ~ ,...-., 53 :.~
~'2~3~ :
A sufficient amount of the heat stabilizer or combination is used to improve the resistance of the synthetic polymer to deterioration in physical properties during heat processing, including, for example, discoloration, reduction in melt viscosity and embrittlementO Very small amounts are usually ~ ~
adequate, Amounts within the range from about 0O 001 to about ~`;
5% total heat stabilizers by weight of the polymer are satisfactory. Preferably, from 0.01 to 3% is employed, for optimum stabilization~
The ~-diketone is used in an amount to impart resistance to ~; -deterioration when exposed to moderate temperatures within the range from about 150 to about 215F after heat processing, including, for example, discoloration and embrittlement.
Very small amounts are usually adequate. Amounts within the ~;
range from about 0. 001 to about 5% B-diketone by weight of the polymer are satisfactoryO Preferably, from 0. 01 to 3% is ~ ~
employed, for optimum effect~ -When all components are solid$, the stabilizer systems of the invention are readily rendered in solid particulate form, comprising a blend of: `
(a) B-diketone in an amount of from about 10 to about ;~
35 parts by weight; `
(b) heat stabilizer in an amount of from about 10 to about 35 parts by weight, including, for example, (1) a polyvalent met al organic acid salt in an amount of from about 10 to about 35 parts by weight; ; -`
~`
54 ~
''`' ~2~3~
(2) a phenolic antioxidant in an amount from about ~ ... ..
lû to about 35 parts by weight;
(3) other heat or light stabilizers.
When the stabilizer is a liquid, the B-diketone can be dissolved therein, with gentle warming and agitation if necessary. Particularly preferred ~-diketones found soluble in liquid stabilizers include dibenzoylmethane and stearoylbenzoylmethaneO
The stabilizer compositions OI the invention can include any conventional polyvinyl chloride resin additives, including in addition lubricants such as stearic acid, paraffin wax, polyethylene wax, stearamide, petrolatum, and natural waxes, as well as emulsifiers, antistatic agents, flame- `
proofing agents, pigments and fillers.
The stabilizer compositions of the invention can be compounded with polyvinyl chloride resins, properly formulated, and shaped by standard plastics processing techniques (including calendering, extrusion, injection and compression ~` ;;
molding, blow molding, rotational molding, slush and dip molding, solution casting, electrostatic spray and fluidized bed coating), to form a wide variety of motor vehicle components for both interior and exterior use, such as dashboards, seat coverings, floor mats, door panels~ arm and head rests, receptacles, compartments, body side moldings, window trim ~ -moldings, seat corners and head liners, door and window knobs, `
and crash dashboards~ j . .,-~,.
,- ' ~'' , . ..
~
~22~3~
Compounding components such as plasticizers, : -stabilizers, lubricants, impact modifiers, processing aids, ~: `
fillers, colorants, antistatic agent's, tackifiers, flame retardants, fungicides, antiblocking agents, etc. can be ~ `~
5 incorporated to facilitate processing of such motor vehicle components The following Examples in the opinion of the inventors represent preferred embodiments of their invention.
2 ~ 3 ~3 Examples 1 to 5 Polyvinyl chloride resin compositions were made up having the following formulation:
Ingredient Parts by Weight ~:
:
Polyvinyl chloride homopolymer 100 ;
(Diamond 450) Dioctyl phthalate 50 : ~
Drapex 6. 8 (epoxidized soybean oil) 8 ~:
Calcium carbonate (Atomite) 20 ~.
Stearic acid 0.3 . :;~
~
Stabilizer 2. 5 ~ `
Composed of ~
~arlum non~l phenate (120 5% Ba, 21,2 approx, 5UU/o solution) .:
Zinc 2-ethyl hexoate (8. 5% Zn, 21. 2 .
50% solution) -. `
,-, ., ~:
Phenyl diisodecyl phosphite 42.6 Stearoyl benzoyl methane 0 to 5 as noted in Table I
Mineral spirits 10 to 15 to make ~:
up difference in ~::
w~ight of stearoyl .
benzoyl methane . ~ -. .
The stabilizer system, dioctyl phthalate, epoxidized .
. ~
soybean oil, calcium carbonate and stearic acid were blended ~ ~:
with the polyvinyl chloride resin on a two-roll mill, and then `
sheeted offO To determine heat processing stability, samples ..
25 were cut off from the sheets and heated in a Geer oven at 350F
and at 375F, for up to two hours. Samples were withdrawn at ' :,,.
57 .~
~ ~ ~ 2 c~ ~ ~3 fifteen minute intervals to follow the progress of any .
deterioration, as evidenced by discoloration and/or embrittlementO
Deterioration was rated according to the following scale~
Ratin~ Color 0 Unchanged ~ ;~
First perceptible discoloration ~yellow or buff) :
2 Very pale discoloration (yellow or buff) 3 Pale yellow or buff .
4 Light yellow or buff Yellow ~ ~
6 Deep yellow ."`
7 Yellow with black edges . ;. `.
0/ \0 ' ~
/ --r ~ ~ :
(HO)r"--A~p O
in which Ar is a mono or bicyclic aromatic nucleus and m is an integer of from 0 to about 5. Z is one or a plurality of : .
organic radicals as defined above for Rl to R6, taken singly ~ ~ .
or together in sufficient number to satisfy the valences of the ~;
two phosphite oxygen atoms. Z can also be hydrogen, and can include additional bicyclic aromatic groups of the type ~HO)~"-Ar, The term "organic phosphite" as used herein is inclusive of the above-described mono-, di- and triphosphites. ~i`
Usually, the phosphite will not have more than about sixty carbon atomsO
Exemplary are monophenyl di-2-ethylhexyl phosphite, diphenyl mono-2-ethylhexyl phosphite, di-isooctyl monotolyl phosphite, tri-2-ethylhexyl phosphite, phenyl dicyclohexyl phosphite, phenyl diethyl phosphite, triphenyl phosphite, ~ -tricresyl phosphite, tri(dimethylphenyl) phosphite, trioctadecyl phosphite, triisooctyl phosphite, tridodecyl phosphite, isooctyl diphenyl phosphite, diisooctyl phenyl ~ ;:
~ ,''.
` :
phosphite, tri(t-octylphenyl) phosphite, tri(t-nonylphenyl) phosphite, benzyl methyl isopropy:L phosphite, butyl dicresyl phosphite, isooctyl di(octylphenyl) phosphite, di(2-ethylhexyl) (isooctylphenyl) phosphite, tri(2-c~yclohexylphenyl) phosphite, tri-a-naphthyl phosphite, tri(phenylphenyl) phosphite, tri(2-phenyl ethyl) phosphite, monododecyl phosphite, di(p-tert-butyl phenyl) phosphite, decyl phenyl phosphite, tert-butyl~
phenyl 2-ethylhexyl phosphite, ethylene phenyl phosphite, ethylene t-butyl phosphite, ethylene isohexyl phosphite, ethylene isooctyl phosphite, ethylene cyclohexyl phosphite, 2-phenoxy- 1, 3, 2-dioxaphosphorinane, 2-butoxy- 1, 3, 2-dioxaphos-phorinane, 2-octoxy-5, 5-dimethyl~dioxaphosphorinane, 2-cyclohexyloxy-5, 5-diethyl dioxaphosphorinane, monophenyl phosphite, 2-ethylhexyl phosphite, isooctyl phosphite, cresyl phosphite, t-octylphenyl phosphite, t-butyl phosphite, diphenyl phosphite, diisooctyl phosphite, dicresyl phosphite, dioctylphenyl `:
phosphite, didodecyl phosphite, di-a-naphthyl phosphite, ethylene phosphite, butyl cresyl phosphite, phenyl-mono-2-ethylhexyl ~;
phosphite, isooctyl monotolyl phosphite and phenyl cyclohexyl phosphite~
Exemplary pentaerythrityl phosphites are 3, 9-diphenoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane (diphenyl- ~:
pentaerythritol-diphosphite), 3, 9 di(decyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(isodecyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5) -undecane, 3, 9- -: .
26 :
~ ~ x ~
di(octadecyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3-phenoxy-9-isodecyloxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(methoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(lauryloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di-p-tolyoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3-methoxyethyloxy-9- ~:~
isodecyloxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(ethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(butoxyethoxy)-2, 4, 8, 10 tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3-methoxyethoxy- .
9-butoxyethoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxyethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(butoxyethoxyethoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9 di(methoxyethoxyethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxy(polyethoxy) ethyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane :
(where the (polyethoxy)ethoxy group has an average molecular weight of 350), 3, 9-di(methoxy(polyethoxy)ethoxy)-2, 4, 8, 10- .
tetraoxa-3, 9-cliphosphaspiro-(5, 5)-undecane (where the (polyethoxy)-ethoxy group has an average molecular weight of 550).
~. - -., ~2~
Exemplary of the bis aryl phosphites are: bis(4, 4'- :
thio-bis(2-tertiary-butyl- 5-methyl-phenol)) isooctyl phosphite, mono(4, 4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)) di-phenyl phosphite, tri-(4, 4'-n-butlidene-bis(2-tertiary-butyl- :; ;
5 5-methyl-phenol)) phosphite, (4, 4'-benzylidene-bis(2-tertiary-butyl-5-methyl-phenol)) diphenyl phosphite, isooctyl 2,2'-bis(parahydroxyphenyl) propane phosphite, tridecyl 4,4'-n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol) phosphite, ` .
4, 4'-thiobis(2-tertiary-butyl-5-methylphenol) phosphite, 2- ~:
ethylhexyl-2, 2'-methylene-bis(4-methyl-6-1'-methylcyclohexyl) ~
phenol phosphite, tri(2, 2 ' -bis- (para-hydroxyphenyl) propane) ::
phosphite, tri(4, 4'-thio-bis(2-tertiary-butyl-5-methyl-phenol) ;~
phosphite, isooctyl-(2, 6-bis(2'-hydroxy-3, 5-dinonylbenzyl)-4- : ;
nonyl phenyl)) phosphite, tetratridecyl 4, 4'-n-butylidene- -~
15 bis(2-tertiary-butyl-5-methyl phenyl) diphosphite, tetra-isooctyl 4, 4'-thiobis(2-tertiary-butyl-5-methyl phenyl) diphosphite, 2, 2'~
methylene-bis(4-methyl-6-1'-methyl cyclohexyl phenyl) ~-polyphosphite, isooctyl-4, 4'-isopropylidene-bis-phenyl- - .
polyphosphite, 2-ethylhexyl-2, 2'-methylene-bis(4-methyl-6, 1'- :
20 methyl-cyclohexyl) phenyl triphosphite, tetratridecyl-4,4'-oxydiphenyl diphosphite, tetra-n-dodecyl-4, 4'-n-butylidenebis -(2-tertiary-butyl-5-methylphenyl) diphosphite, tetra-tridecyl-4, 4'-iso-propylidene bisphenyl diphosphite, hexatridecyl butane- .
1, 1, 3-tris(2'-rnethyl-5'-tertiary-butylphenyl-4') triphosphite. ~ ~
'':.
~.
::;`
2 ~
Preferred classes of additional stabilizers that can be used include the phenols, aliphatic polyhydroxy compounds;
esters, amides, and hydrazides of thioalkylenedicarboxylic acids and nitrilotrialkylenetricarboxylic acids; ketoacetic acid compounds; and organic nitrogen compounds such as the esters of betaaminocrotonic acid, diphenylthiourea, and 2-phenylindole. Phenol stabilizers can be included in amounts corresponding to 0. 01 to about 0. 2 parts per 100 parts of polymer being stabilized~ Typical phenol stabilizers are butylated hydroxy-toluene (BHT), 4, 4'-isopropylidenebisphenol, -~
and 1, 1, 3 -tris(2 ' -methyl-4 ' -hydroxy- 5' -t-butylphenyl) butaneO
The phenol stabilizers contain one or more phenolic hydro~yl groups, and one or more phenolic nuclei and can contain from about eight to about three hundred carbon atoms In addition, the phenolic nucleus can contain any oxy or thio ether group.
The a~cyl-substituted phenols and polynuclear phenols, ~ "
because of their molecular weight, have a higher boiling point, and therefore are preferred because of their lower volatility.
There can be one or a plurality of alkyl groups of one or more carbon atoms. The alkyl group or groups including any alkylene groups between phenol nuclei preferably aggregate at least four carbon atomsO The longer the alkyl or aLkylene chain, the better the compatibility with polypropylene, inasmuch as the phenolic compound then acquires more of an aliphatic ~ ~
-,'' . '' 29 ~
'`'~
hydrocarbon character, and therefore there is no upper limit on the number of aLkyl carbon atoms. Usually, from the standpoint of availability, the compound will not have more than about eighteen carbon atoms in an alkyl, alicyclidene ;
and alkylene group, and a total of not over about fifty carbon atoms. The compounds may have from one to four alkyl radicals per phenol nucleus The phenol contains at least one and preferably at least two phenolic hydroxyls, the two or more hydroxyls being in the same ring, if there is only one. In the case of bicyclic phenols, the rings can be linked by thio or oxyether groups, ~
or by alkylene, alicyclidene or arylidene groups. -The monocyclic phenols which can be employed have the structure: ;
(R),~l~(O~)x2 ;
::
R is selected from the group consisting of hydrogen;
halogen; and organic radicals containing from one to about ;~
thirty carbon atoms, such as alkyl, aryl, alkenyl, a~aryl, araLkyl, cycloalkenyl, cycloalkyl, aLkoxy, and acyl ~
R'IC-- ~ -O :'. .
where R' is aryl, alkyl or cycloa~yl. ~ -, .~. . .
x, and x2 are integers from one to four, and the sum of ~
xl and x2 does not exceed six. -,' ~''.', : :-'', The polycyclic phenol employed in the stabilizer combination is one having at least two aromatic nuclei linked ~ -by a polyvalent linking radical, as clefined by the formula:
( I r)~ Y-( I r)~l2 (OH)"~l (H)n~a wherein Y is a polyvalent linking group selected from the group consisting of oxygen; carbonyl; sulfur; sulfinyl;
aromatic, aliphatic and cycloaliphatic hydrocarbon groups;
and oxyhydrocarbon, thiohydrocarbon and heterocyclic groups.
The linking group can have from one up to twenty carbon atoms Ar is a phenolic nucleus which can be a phenyl or a polycar~oxylic group having condensed or separate phenyl rings: each Ar group contains at least one free phenolic hydroxyl group up to a total of fiveO The Ar rings can also include additional rings connected by additional linking nuclei of the type Y, for example, Ar-Y--A~Y-Ar.
ml and m2 are numbers from one to five, and n1 and -n2 are numbers of one or greater, and preferably from one ,.-....
to four.
The aromatic nucleus Ar can, in addition to phenolic hydroxyl groups, include one or more inert substituents. -Examples of such inert substituents include hydrogen, halogen atoms~ e. g. chlorine, bromine and fluorine; organic radicals containing from one to about thirty carbon atoms,~ `
25 such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl, alkoxy, aryloxy and acyloxy " ~
31 ~
~ ~ 2 r t c~ ~3 ~
R ' C-O ~ ~
O . ~
where R' is aryl, alkyl or cycloalkyl, or thiohydrocarbon ~;
groups having from one to about thirty carbon atoms, and ~ .
5 carboxyl -C~ :'' O ;~
groups. Usually, however, each aromatic nucleus will not have more than about eighteen carbon atoms in any hydrocarbon substituent groupO The Ar group can have from -:
one to four substituent groups per nucleus.
Typical aromatic nuclei include phenyl, naphthyl, phenanthryl, triphenylenyl, anthracenyl, pyrenyl, chrysenyl, ~
and fluorenyl groupsO ~ -;
When Ar is a benzene nuc leus, the polyhydric .
polycyclic phenol has the structure: -;~. ~ . : .. .~ .
~~ OH~ ~0~ :' ~ '``'' E~ YT~
~ y~ R~
wherein Rl, R2 and R3 are inert substituent groups as . ~
de~cribed in the previous paragraph, ml and m3 are integers~- .
from one to a maximum of five, m2 is an integer from one . -to a maximum of four, xl and X3 are integers from zero to ~ -four, and x2 is an integer from zero to three; Yl is an integer - .
from zero to about six and Y2 is an integer from one to five, ~:
preferably one or two 2 ?~ 2 2 ~
Preferably, the hydroxyl groups are located ortho and/
or para to Y.
Exemplary Y groups are alkylene, alkylidene, and alkenylene arylene, aLkyl arylene, arylalkylene, cycloalkylene, 5 cycloalkylidene, and oxa- and thia-substituted such groups;
carbonyl groups, tetrahydrofuranes, esters and triazino groups~
The Y groups are usually bi, tri, or tetravalent, connecting two, .:
three or four Ar groupsO However, higher valence Y groups, ``
connecting more than four Ar groups, can also be used. ` `
10 According to their constitution, the Y groups can be assigned to subgenera as follows~
. ~:
(1) Y groups where at least one carbon in a chain or cyclic arrangement connect the aromatic groups, such as --CEt~CE3r-;--(CHI~;~CH~;
~ ~ , 15 -O~OEr, ~O;-C~
~ J ~
X ' .',~' CH, C~
CH_;_C~ b~ C~_; ....
7 b~, C2~ C~3 cHr b--C~ CH~}C~
33 `~
, 1 . ' ' ' ' ' '" ' ' ' ; ~ ' ~22~5 `
,,``.
-C~C}; o_; ~ C.
o~,)~: {~C~<~
~, o~c~l :`.````.'`'`
--CH~--~ J--C}~
Y ' ,- ., 10--CH~ ~ H~ I2C~ /CEI~, --~r,c C~3-- - .
' H b c~
15-EC/I~ C~; b~
CE~ ~OH;
H3~\l/C~ /~H-- ~Ht (2) Y groups where only atoms other than carbon link . ~
the aromatic rings, such as ~ .
-O~ ~, --S- and-(S)x--O O
where x is a number from one to ten;
(3) Y groups made up of more than a single atom :
including both carbon and other atoms linking the aromatic nuclei, such as 2 ~
--C ~3:~0--i~ C H--C ~I~ O--C ~I~C
H~
~0~ ~ '.. -':` '.' --O--CH~C~I~O--;--C~Irt 8 tC}~
--C~.~ S~C~;--S--CH~ S--;--C ~ CH~
--C~C~ ~--CH~;--c--o--~c~ o--c--;
10C1--C~I~OOCC}~iC~
O O
c~ cH~a O c~c~o a C~I2C~
15N~ \N ;--C~S--; ~;
~o N
20--CH~S--CH~; a~d ¦ S ~
Although the relation of effectiveness of chemical structure `
is insufficiently understood, any of the most effective phenols have Y groups of subgenus (1), and accordingly this is preferredO Some of these phenois can be prepared by the 25 aLkylation of phenols or alkyl phenols with polyunsaturated hydrocarbons such as dicyclopentadiene or butadiene, ~.~
-` 2 ~ 2 2 ~
:: ,.. ..
. -. :`, Representative phenols include guaiacol, resorcinol ``.
monoacetate, vanillin, butyl salicylate, 2, 6-ditert-butyl-4- ` ` `
methyl phenol, 2-tert-butyl-4-methoxy phenol, 2, 4-dinonyl phenol, 2, 3, 4, 5-tetradecyl phenol, tetrahydro~ naphthol, ~ ~ ;
o-, m- and p-cresol, o-, m- and p-phenylphenol, o-, m-and p-xylenols, the carvenols, symmetrical xylenol, thymol, o-, m- and p-nonylphenol, o-, m- and p-dodecylphenol, and o-, m- and p-octyl-phenol, o- and m-tertbutyl-p-hydroxy- ~ ~ `
anisole, p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n- `. .
decyloxy-cresol, eugenol, isoeugenol, glyceryl monosalicylate, methyl-p-hydroxy-cinnamate, 4-benzyloxy-phenol, p-acetyl-am inophenol, p-stearyl-am inophenol methyl-p-hydroxybenzoate, p-di-chlorobenzoyl-aminophenol and p-hydroxysalicyl anilideO .
E~emplary polyhydric phenols are orcinol, propyl gallate, ` ~
cetechol, resorcinol, 4-octyl-resorcinol, 4-dodecyl-resorcinol, .
4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol, :
hexahydroxybenzene, 4-isohexylcatechol, 2, 6-ditertiary-butyl- ~ -resorcinol, 2, 6-diisopropyl-phloro~lucinol.
Exemplary polyhydric polycyclic phenols methylene-bis-(2, 6-ditertiarybutyl-phenol), 2, 2-bis-(4-hydroxyphenyl)-propane, methylene-bis(p-cresol), 4, 4'-benzylidenebis-(2-tertiary butyl-5-methylphenol), 4, 4'-cyclohexylidenebis-(2-tertiary butylphenol), 2, 2'-methylene-bis(4-methyl-6-(1'-methyl-cyclohexyl)-phenol), 2, 6-bis(2'-hydroxy-3'-tertiary-butyl-5'-methylbenzyl)-4-methylphenol, (2-tertiary-butyl-5-methyl-36 :
: .
~22~3~
phenol)! 2, 2'-bis(4-hydroxy-phenyl) butane, ethylenebis- i (p-cresol), 4, 4'-oxobis-phenol, 4, 4'-oxobis(3-methyl-5-isopropyl-phenol), 4, 4'-oxobis-(3-methyl-phenol), 2, 2'-oxobis-(4-dodecyl-phenol), 2, 2'-oxobis-(4-methyl-5-tertiary-butyl-phenol), 4, 4'-thio-bis-phenol; 4, 41-thio-bis-(3-methyl-6- ; ~`.tertiary-butyl-phenol), 2, 2'-thio-bis-(4-methyl-6-tertiary- ~:
butyl-phenol), 4, 4' -n-butylidene- (2- t-butyl- 5-methyl-phenol), 2, 2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-phenol), 4, 4'-cyclohexylenebis-(2-tertiary-butyl-phenol), 2, 6-bis-(2'-hydroxy-3'-t'-butyl-5'-methyl-benzyl)-4-methyl-phenol, 4, 4'-oxobis(naphthalene-1, 5-diol), 1, 3'-bis(naphthalene-2, 5-diol)propane, and 2, 2'-butylenebis-(naphthalene-2,7-diol), (3-rnethyl- 5-tert-butyl-4-hydroxyphenyl)-4'-hydroxyphenyl) ;
propane, 2, 2'-methylenebis-(4-methyl-5-isopropylphenol), 2, 2'-methyl~nebis-(5-tert-butyl-4-chlorophenol), (3, 5-di-tert- -:
butyl-4-hydroxyphenyl)-(4'-hydroxyphenyl) ethane, (2-hydroxy~
phenyl)-(3', 5'-di-tert-butyl-4', 4-hydroxyphenyl)ethane, 2, 2'-methylenebis-(4-octylphenol), 4, 4'-propylenebis-(2-tert-butyl-phenol), 2, 2'-isobutylenebis-(4-nonylphenol), 2, 4-bis-(4-hydroxy-3-t-butylphenoxy)-6-(n-octylthio)-1, 3, 5-triazine, 2, 4, 6-tris(4-hydroxy-3-t-butylphenoxy)-1, 3, 5-triazine, 2, 2'-bis-(3-t-butyl-4-hydroxyphenyl) thiazolo-(5,4-d) thiazole, 2, 2'-bis(3-methyl-5-t-butyl-4-hydroxyphenyl) thiazolo-(5, 4-d)-thiazole, 4, 4'-bis(4-hydroxy-phenyl) pentanoic acid octadecyl ester, cyclopentylene-4, 4'-bisphenol, 2-ethylbutylene-4, 4'- ~ -~
'; ~ '' 37 ~
, ~, 2~.2~
bisphenol, 4, 4'-cyclooctylenebis(2-cyclohexylphenol), B, .B-thiodiethanol-bis(3 -tert-butyl-4 -hydroxyphenoxy ac etate), 1, 4-butane-diobis(3-tert-butyl-4-hydroxyphenoxy acetate), .
pentaerythritoltetra(4-hydroxyphenol propionate), 2, 4, 4'-tri- :~
hydroxy benzophenone, bis(2-tert-butyl-3-hydroxy-5- ~ ~.
methylphenyl sulfide, bis(2-tert-butyl-4-hydroxy-5-methyl-phenyl) sulfide, bis(2-tert-butyl-4-hydroxy-5-methyl-phenyl sulfoxide), bis-(3-ethyl-5-tert-butyl-4-hydroxy benzyl) sulfide, bis(2-hydroxy-4-methyl-6-tert-butyl-phenyl) sulfide, 4, 4'-bis(4-hydroxyphenyl) pentanoic acid octadecyl thiopropionate ester, 1,1, 3-tris(2'-methyl-4'-hydroxy-5'-tert-butylphenyl) butane, 1, 1, 3-tris-(1-methyl-3-hydroxy-4-tert-butylphenyl) butane, 1, 8-bis(2-hydroxy-5- ` ~ ~:
methylbenzoyl-n-octane, 2, 2'-ethylene-bis-[4'-(3-tert-butyl-4-hydroxyphenyl)-thiazole], 1-methyl-3-(3-methyl-5-tert-butyl-4-hydroxybenzyl)-naphthalene, 2, 2'-(2-butene) `~
bis-(4-methoxy-6-tert-butyl phenol) and pentaerythritol -hydroxyphenyl propionate~
A particularly desirable class of polyhydric polycyclic phenols are the dicyclopentadiene polyphenols, which are of the type:
R~
Rl . n .
~ ~ ~ ,7 ~
in which Rl and R2 are lower a~{yl, and can be the same or different, and n is the number of the groups enclosed by the brackets, and is usually from 1 to about 5, These are described in U. S, patent NoO 3, 567, 683, dated March 2, 1971 5 to Spacht. A commercially available member of this class is Wingstay L, exemplified by the dicyclopentadiene tri(2-tert-butyl-4-methyl-phenol) of the formula:
0~: ,0~ " 0~';~ :
c(}~
H~ Er~ ~r~ ;
The polyhydric polycyclic phenols used in the invention can also be condensation products of phenol or a~yl-phenols with hydrocarbons having a bicyclic ring structure and a double bond or two or more double bonds, such as cY-pinene, B-pinene, 15 dipentene, limonene, vinylcyclohexene, dicyclopentadiene, allo-ocimene, isopreneandbutadiene. Thesecondensatlon ~ d products are usually obtained under acidic conditions in the ~ --form of more or less complex mixtures of monomeric and polymeric compounds. However, it is usually not necessary ~ -20 to isolate the individual constituentsO The entire reaction product merely freed from the acidic condensation catalyst and unchanged starting material, can be used with excellent resultsO
While the exact structure of these phenolic condensation products is uncertain, the Y groups linking the phenolic nuclei all fall into the preferred subgenus 1. For method of preparation, see, e.g., U S. patent No. 3, 124, 555, U,S. patent No.
3, 242,135, British patent No~ 961, 5040 Aliphatic polyhydroxy compounds can be included in amounts corresponding to 0.1 to about 1 part per 100 parts of polymer being stabilized. Typical aliphatic polyhydroxy compounds are glycerol, polyglycerol, monodi-, and tri-pentaerythritol, mannitol, sorbitol, and partial esters of these with saturated and unsaturated fatty acids having 6 to 22 carbon atoms.
The esters, amides, and hydrazides of thiodialkylene dicarboxylic acids and nitrilotri-aL"ylenetricarboxylic acids can be included in amounts corresponding to 0.1 to about 1 part per 100 parts of polymerO Typical of these are dimethyl thiodipropionate, dilauryl and distearyl thiodipropionates, -~
2, 2 '-thiobis(acetyl ethanolamine), 3, 3 '-thiobis(propionyl-diisopropanolamine, nitrilotriacetic acid (NTA) propylene glycol ester, NIA tris(ethylamide), NTA bis (hydroxyethyl) N-butylamide, 3, 3~-thiodipropionyldihydrazide and 6, ~
thiodihexanoyldihydrazide. ~ ;
The thiodipropionic acid ester has the following formula:
Ft lOOCCH2CH2--~CH2CH2COOY
-,'''.' in which Rl is an organic radical selected from the group ~;
consisting of hydrocarbon radicals such as aLkyl, alkenyl, aryl, cycloalkyl, mixed a~yl aryl, and mixed alkyl cycloalkyl ~`
radicals; and esters thereof with aliphatic carboxylic acids;
5 and Y is selected from the group consisting of (a) hydrogen, (b) a second R radical R2, which can be the same or different from the R, radical, (c) a polymeric chain of n thiodipropionic ~;
acid ester units:
R 1O[OCCH2CH2SCH2CH2COOXO]nOCCH2CH2-~CH2CH2COOZ ~ :
10 wherein Z is hydrogen, R2 or M; n is the number of thiodipropionic acid ester units in the chain; and X is a bivalent hydrocarbon group of the type of Rl; the value of n can range upwards from 1, but there is no upper limit on n .
except as is governed by the ratio of carbon atoms to sulfur :: .
. . .
atoms as stated below; and (d) a polyvalent metal M of .
. . .
Group II of the Periodic Table such as zinc, calcium, cadmium, barium, magnesium and strontium. ~
The molecular weights of the R and Y radicals are taken - .
such that with the remainder of the molecule, the thiodipropionic : `
20 ester has a total of from about ten to about sixty carbon atoms per sulfur atom. . `
Accordingl~, the various thiodipropionic ac id ester .: ~
species coming within the above-mentioned categories within ;.
the general formula can be defined as follows: ~
~., 41 ~`
2 ~
(a) R lOOCCH2CH2SCH2CH2COOH
(b) RlOOCCH2CH2SCH2CH2COOR2 (c) R~O[()CCH2CH2SCHzCH2COOX-O]nOCCH2CH2SCH2CH2COOZ ~ ~;
(d) [RlOOCCH2~H2ScH2cH2c0o]2M
5 In the above formulae, Rl and R2, M, X and Z are the same as before. In the polymer (c), as in the other forms of thiodipropionic acid esters, the total number of carbon atoms per sulfur atom is within the range from about ten to about sixty.
The R radical of these esters is important in furnishing compatibility with the polypropylene. The Y radical is ;
desirably a different radical, R2 or M or a polymer, where `
R is rather low in molecular weight, so as to compensate for this in obtaining the optimum compatibility and nonvolatilityO
Where Y is a metal, the thiodipropionic acid ester furnishes `
the beneficial properties of the polyvalent metal salt which is ;
described belowO
The aryl, alkyl, aL'senyl and cycloalkyl groups may, if -desired, contain inert~ nonreactive substituents such as 2û halogen and other carbocyclic and heterocyclic ring structures condensed therewithO ~-Typical R radicals are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, -~
n-octyl, isooctyl, 2-ethyl hexyl, t-octyl, decyl, dodecyl, 25 octadecyl, allyl, hexenyl, linoleyl, ricinoleyl, oleyl, phenyl, '-''''.' ' .
'.
2 ~ 2 2 ~
xylyl, tolyl, ethylphenyl, naphthyl, cyclohexyl, benzyl, cyclopentyl, methylcyclohexyl, ethylcyclohexyl, and ;
naphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl, pentaerythrityl, and polyoxyalkylene radicals such as those 5 derived from diethylene glycol, triethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, and .
polyoxypropyleneoxyethylene glycol, and esters thereof with any of the organic acids named below in the discussion of the ~.
polyvalent metal salts, including in addition those organic acids ` `
having from two to five carbon atoms, such as acetic, propionic, . `
butyric and valeric acids~ `
Typical X radicals are alkylene radicals such as ethylene, tetramethylene, he~amethylene, decamethylene, ~ ~.
alkyl- and aryl-substituted a~cylene radicals such as 1, 2- ~: .
15 propylene, CH~ ICHI CH~ snd --C:~CE--,_CH~C--CH~,~ nd--CH--;
1H1 b~
arytene radicals such as phenyIene {}' ' .`' 20 methylenephe~ylene -C~
dimethyIene phellylene, _CH~CH~
2 ~ ~ 2 ~
and alieyclene radicals such as cyclohe~ylc~e <3~
a~d cyclopentylene -~ .. ~, .
1-~ r ~
\/ .. .;
As exemplary of the thiodipropionic acid esters ~: `
which can be used, there can be mentioned the following:
monolauryl thiodipropionic acid, dilauryl thiodipropionate, ~ .
butyl stearyl thiodipropionate, di(2- ethylhexyl)- thiodipropionate, diisodecylthiodipropionate, isodecyl phenyl thiodipropionate, .: :.,:
benzyl lauryl thiodipropionate, benzyl phenyl thiodipropionate, ; :~
the diester of mixed coconut fatty alcohols and thiodipropionic . `
acid, the diester of mixed tallow fatty alcohols and thiodipropionic acid, the acid ester of mixed cottonseed oil .
fatty alcohols and thiodipropionic acid, the acid ester of mixed ~ ~`
soybean oil fatty alcohols and thiodipropionic acid, cyclohexyl ;
. .
nonyl thiodipropionate, monooleyl thiodipropionic acid, hydroxyethyl lauryl thiodipropionate, monoglyceryl thiodipropionic ~ ~`
acid, glyceryl monostearate monothiodipropionate, sorbityl isodecyl thiodipropionate, the polyester of diethylene glycol ~ ~.
and thiodipropionic acid, the polyester of triethylene glycol - ~ .
and thiodipropionic acid, the polyester of hexamethylene glycol :~
and thiodipropionic acid, the polyester of pentaerythritol and thiodipropionic acid, the polyester of octamethylene glycol and -",~
2 ~ 3 ~
~'``''~
thiodipropionic acid, the polyester of p-clibenzyl alcohol and ; -thiodipropionic acid, ethylbenzyl lauryl thiodipropionate, ~ -strontium stearyl thiodipropionate, magnesium oleyl thiodipropionate, calcium dodecylbenzyl thiodipropionate, and mono(dodecylbenzyl) 5 thiodipropionic acid.
These esters are for the most part known compounds, ~`
but where they are not available, they are readily prepared by esterification of thiodipropionic acid and the corresponding "
alcohol, Ketoacetic acid compounds that can be used with the stabilizer compositions of this invention in amounts of about 0O 05 to about 0~ 5 parts per 100 parts of polymer being stabilized include 2-ethylhexyl acetoacetate, glyceryl tris(acetoacetate) and dehydroacetic acid.
The keto acetic acid compound should be nonvolatile and stable at processing temperatures. It should also be nitrogen-free. In general, compounds having at least eight carbon atoms in the molecule fulfill these requirements. The free keto acetic acids, for some reason that is unknown, do 20 not possess the stabilizing effectiveness of the esters or of the anhydride dimers. However, metal salts of these keto acids can be used as the metal salt component of the stabilizer combination oE the invention, and in combination with the ester and/or anhydride dimer have excellent stabilizing effectiveness.
:~
~2~
The keto acetic acid esters of this invention have the following general formula:
(R-CI--CH2--Cl--O),~R ' .`.. ., o O '~
5 wherein R is an inert organic group having from one to about thirty carbon atoms, R' is an inert organic radical having from one to about thirty carbon atoms, and x is a number from on0 to ten. The ester molecule has a total of at least eight carbon atoms R and R' can be hydrocarbon groups, and can b~ allcyl, allcenyl, aryl, aLkylaryl, aryl allcyl, cycloallcyl, cycloallcenyl, and heterocyclicO The open chain groups can be straight or branched, and the cyclic and alicyclic groups can be saturated or unsaturated. The R and R' groups can also be substituted by -~
15 inert groups such as halogen (fluorine, chlorine, bromine and iodine) alkoxy or epoxy -C--C'- hydroxy OH and ether O ' `
- C~C- groups. There will not usually be more than ten of such substituents, depending of course upon the number of 20 available substituent positions in the R and R' groups.
Thus, the R' radical for example can include free hydroxyl OH groups, up to a practical maximum of ten, but generally not more than one hydroxyl group per carbon atom, and the R' raclical can carry a plurality of R-CI-CH2-C~
- -46 ~-~2~
::`..;
ester groups, up to a total of about ten, the value of x. It will `
be understood that where R' has more than one OH group, the value of x represents only an average value of the number of i;
possible ester species that may exist, dependent on the total number 5 of H groups on R'. For instance, in the case of a di-ester (x=~), where R' has three free OH groups, there can also be ~.;
pentaester, tetraester, triester and monoester species presentO .
Indeed, in such cases, x can be a decimal number, for instance, 2, 5, indicating the presence of a mixture of monoester, diester, .
triester and higher ester species in proportions to give this average value for xO Those skilled in the art will perceive the increased possibilities as x increases to ten or more.
Exemplary R and R' hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, tert-amyl, hexyl, heptyl, tert-octyl, 20ethyl hexyl, isononyl, decyl, undecyl, dodecyl, ~ ~:
palmityl, stearyl, oleyl, ricinoleyl,linoleyl, linolenyl, behenyl, tridecyl, phenyl, xylyl, tolyl, naphthyl, cyclohexyl, methyl-cyclohexyl, cyclopentyl, tetrahydrofurfuryl, cycloheptyl, isononylphenyl, iEuryl, and pyranylO :
Exemplary hydroxy-substituted R' groups include . :~
hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyamyl, 2-hydroxyamyl, 2, 2-dimethylol propyl, 2, 2-dihydroxyamyl, 1,1-methylol hydroxybutyl, 2-(di-hydroxyethyl)-butyl, ;
~ ~ 2 ~
1-(dihydroxy ethyl) propyl, 3-4 dihydroxyheptyl, 4-5 dihydroxyoctyl, `
7, 8-dihydroxyhepta-decyl, 6, 7-dihydroxytetradecyl, 1, 2, 3- ;
trimethylol octadecyl, 1, 2, 3, 4, 5, 6-hexahydroxy heptyl, 10-hydroxyeicosyl, 2, 3-dihydroxypropyl, 4-hydroxybutyl, 3, 4-dihydroxybutyl, 2, 3, 4-trihydroxybutyl, 1, 3, 4-trihydroxybutylO ~ .:
These esters are readily prepared according to known ~ ~ `
procedures by transesterification of a simple ester of the corresponding keto acetic acid, such as ethyl acetoacetate, :
with the corresponding alcohol. If the corresponding keto acetic acid is stable, direct esterification is possible If a ~ -polyhydric alcohol is used, mixed esters of the acid and : `.
alcohol are obtained, according to the molar proportions of :
each, and mixtures of the various possible esters will also be .:
present in most case. .:~
Typical esters are:
(2)Is~C,E[~ C E[2~ 5 .(3~~8 c~ o ~P~ r~
2 5 a~"GE~ p~ ;
2~2~
' ::
Q ; ;`:
5~ QE~9O~ "O'~
. O `:`
,a~--~a~ ,C~I,aO~
O ~`~`.'~'`.
~)lCH~ sC~H~ . ; ;
(~0)C~8Ht7C CE?C--O--C3H7-iso :-O ~ ~ " ~ ~ r~
. , o 11 ., ~. ., ,;, . 1 ~. , : ' , ~13) a~ r~ -, ~E~-~B~a~E
(14) ~ O~t~
CEt--I a~ o--CH, ~--QH~OE
Q3~
~i~t` [ClI~--OE~--O--GHs--37 tl6) ;- OHsll-a~ O~
pHt.--Q--CH~--O--,~ H~
tl~t ~o3~H~ ~?~
. - :
49 .::
(18) [a~7~5~ H~ 0~ ]?G~[O~
. ~ g.a~ .Q..~H,~
. ~20) [t~rt-O~H9--C--C~It~--Q 4.H~ Q~
'21`
. ~ll~a~ o~ 3-~ ~HaO~
0 (~ IQ~a~C.. eE~ a~ (CHa~H)~
s~ ~ ~ 7 : ~
.' . . O~[r~C~ Q~ -Q-~;
(2~ QH~--~Cl~ ¢.--.Q}~C--Q ¢aH~
(25) C~Ha~H--~ O~ ¢--O:EIi~--O ~35~III lso (2û) OH~C)H?--O~CHrCH~ O~C--O--OH~O:~aOE~
(~ ¢~
~a~ O~--pH~--O--OHI¢H~Q--C,HaCH~Q~
~28) OH~O:EI~[O OHa--OH~I?--0--~3HaC--OlI~11 OOH~
(2,~ [Ç~ --Q--JQ:~p~I~[QQH~q~ a ~ -~ G H O
` ~ '' ~ -\
- 2~22~
The keto acid anhydride dimers have the ormula: ~
S ~ r II. R
R~OO0~ :
~ Lo "", O ',` ` "
R is again as above and Rl is hydrogen or R'. ~;
Exemplary are dehydroacetic acid, isodehydroacetic acid, dehydropropionyl acetic acid, dehydrobenzoyl acetic acid, isodehydro-3,4-dichlorobenzoylacetic acid, and esters of isodehydroacetic acid such as the methyl, ethyl, n-butyl ;~:
2~ethyl hexyl and glyceryl esters.
Organic nitrogen compounds that can be used with the stabilizer compositions of this invention in amounts of about 0, 05 to about 0. 5 parts per 100 parts of polymer being l`
stabilized include 2-ethylhexyl 3-aminocrotonate, 1,4-butanediol bis(3-aminocrotonate) and 2, 2'-thiodiethyl 3-aminocrotonate;
thiocarbanilide and 2-phenylindole, 1, 3-dibutylthiourea, :
phenylurea, and p-ethoxyphenylureaO ~.
The stabilizer compositions of this invention are effective with any vinyl chloride polymer. The term "vinyl -.
chloride polymer" as used herein is inclusive of any polymer ~-formed at least in part of the recurring group, 2~22~
` , X .
-CH C-~1 X '","' and having a chlorine content in excess of 4û% In this group, the X groups can each be either hydrogen or chlorineO ;~
In polyvinyl chloride homopolymers, each of the ~ groups is ~ ~
hydrogen. Thus, the term includes not only polyvinyl chloride ~;
homopolymers but also after chlorinated polyvinyl chlorides as ~-a class, for example, those disclosed in British patent No. 893, 288 and also copolymers of vinyl chloride in a major proportion and other copolymerizable monomers in a minor proportion, such as copolymers of vinyl chloride and vinyl `;
acetate, copolymers of vinyl chloridewith maleic or fumaric acids or esters, and copolymers of vinyl chloride with styrene, ~5 propylene, ethylene, 1-hexene, or vinyl n-dodecyl ether. The invention also is applicable to mixtures of polyvinyl chloride in ;
a major proportion with a minor proportion of other synthetic `
resins such as chlorinated polyethylene or copolymers of acrylonitrile with butadiene and styrene.
The invention is of application to the stabilization of rigid polyvinyl chloride resin compositions, that is, resin compositions which are formulated to withstand high processing temperatures, of the order of 190C and higher, and of plasticized polyvinyl chloride resin compositions of conventional formulation where resistance to heat distortion is not a requisiteO
The respective definitions of rigid and plasticized resins are as follows. The rigid resins are those resins to which plastici~ers ~ ~ ~ 2 ~
are not added, and which are generally worked at about 190C.
The ASTM definition (1961 D-883, Part 9, page 804) is as follows: :
"a plastic which has a stiffness or apparent modulus 5 of elasticity greater than 7000 grams per square centimeter (100, 000 psi) at 23Co "
The plasticized resin would therefore have a modulus of elasticity of less than 7000 grams per square centimeter, `~
and would have added to it the plasticizer compound, i' Conventional plasticizers well known to those skilled in the art can be employed such as, for example, dioctyl phthalate, octyl diph0nyl phosphate and epoxidized soybean oil.
The preparation of the stabilized polymer composition is easily accomplished by conventional procedures. The selected stabilizer combination along with such compounding ingredients as plasticizers, colors, lubricants, antistatic agents etc. as may be needed, is blended with the polymer being stabilized, using, for instance, plastic mixing rollers, at a temperature at which the mix is fluid and thorough blending facilitated, typically at from 120 to 180C for a time sufficient to form a homogeneous sheet, five minutes, usually~ After the ~:
mass is formed, it is sheeted off in the usual way, :~
. ~ ,...-., 53 :.~
~'2~3~ :
A sufficient amount of the heat stabilizer or combination is used to improve the resistance of the synthetic polymer to deterioration in physical properties during heat processing, including, for example, discoloration, reduction in melt viscosity and embrittlementO Very small amounts are usually ~ ~
adequate, Amounts within the range from about 0O 001 to about ~`;
5% total heat stabilizers by weight of the polymer are satisfactory. Preferably, from 0.01 to 3% is employed, for optimum stabilization~
The ~-diketone is used in an amount to impart resistance to ~; -deterioration when exposed to moderate temperatures within the range from about 150 to about 215F after heat processing, including, for example, discoloration and embrittlement.
Very small amounts are usually adequate. Amounts within the ~;
range from about 0. 001 to about 5% B-diketone by weight of the polymer are satisfactoryO Preferably, from 0. 01 to 3% is ~ ~
employed, for optimum effect~ -When all components are solid$, the stabilizer systems of the invention are readily rendered in solid particulate form, comprising a blend of: `
(a) B-diketone in an amount of from about 10 to about ;~
35 parts by weight; `
(b) heat stabilizer in an amount of from about 10 to about 35 parts by weight, including, for example, (1) a polyvalent met al organic acid salt in an amount of from about 10 to about 35 parts by weight; ; -`
~`
54 ~
''`' ~2~3~
(2) a phenolic antioxidant in an amount from about ~ ... ..
lû to about 35 parts by weight;
(3) other heat or light stabilizers.
When the stabilizer is a liquid, the B-diketone can be dissolved therein, with gentle warming and agitation if necessary. Particularly preferred ~-diketones found soluble in liquid stabilizers include dibenzoylmethane and stearoylbenzoylmethaneO
The stabilizer compositions OI the invention can include any conventional polyvinyl chloride resin additives, including in addition lubricants such as stearic acid, paraffin wax, polyethylene wax, stearamide, petrolatum, and natural waxes, as well as emulsifiers, antistatic agents, flame- `
proofing agents, pigments and fillers.
The stabilizer compositions of the invention can be compounded with polyvinyl chloride resins, properly formulated, and shaped by standard plastics processing techniques (including calendering, extrusion, injection and compression ~` ;;
molding, blow molding, rotational molding, slush and dip molding, solution casting, electrostatic spray and fluidized bed coating), to form a wide variety of motor vehicle components for both interior and exterior use, such as dashboards, seat coverings, floor mats, door panels~ arm and head rests, receptacles, compartments, body side moldings, window trim ~ -moldings, seat corners and head liners, door and window knobs, `
and crash dashboards~ j . .,-~,.
,- ' ~'' , . ..
~
~22~3~
Compounding components such as plasticizers, : -stabilizers, lubricants, impact modifiers, processing aids, ~: `
fillers, colorants, antistatic agent's, tackifiers, flame retardants, fungicides, antiblocking agents, etc. can be ~ `~
5 incorporated to facilitate processing of such motor vehicle components The following Examples in the opinion of the inventors represent preferred embodiments of their invention.
2 ~ 3 ~3 Examples 1 to 5 Polyvinyl chloride resin compositions were made up having the following formulation:
Ingredient Parts by Weight ~:
:
Polyvinyl chloride homopolymer 100 ;
(Diamond 450) Dioctyl phthalate 50 : ~
Drapex 6. 8 (epoxidized soybean oil) 8 ~:
Calcium carbonate (Atomite) 20 ~.
Stearic acid 0.3 . :;~
~
Stabilizer 2. 5 ~ `
Composed of ~
~arlum non~l phenate (120 5% Ba, 21,2 approx, 5UU/o solution) .:
Zinc 2-ethyl hexoate (8. 5% Zn, 21. 2 .
50% solution) -. `
,-, ., ~:
Phenyl diisodecyl phosphite 42.6 Stearoyl benzoyl methane 0 to 5 as noted in Table I
Mineral spirits 10 to 15 to make ~:
up difference in ~::
w~ight of stearoyl .
benzoyl methane . ~ -. .
The stabilizer system, dioctyl phthalate, epoxidized .
. ~
soybean oil, calcium carbonate and stearic acid were blended ~ ~:
with the polyvinyl chloride resin on a two-roll mill, and then `
sheeted offO To determine heat processing stability, samples ..
25 were cut off from the sheets and heated in a Geer oven at 350F
and at 375F, for up to two hours. Samples were withdrawn at ' :,,.
57 .~
~ ~ ~ 2 c~ ~ ~3 fifteen minute intervals to follow the progress of any .
deterioration, as evidenced by discoloration and/or embrittlementO
Deterioration was rated according to the following scale~
Ratin~ Color 0 Unchanged ~ ;~
First perceptible discoloration ~yellow or buff) :
2 Very pale discoloration (yellow or buff) 3 Pale yellow or buff .
4 Light yellow or buff Yellow ~ ~
6 Deep yellow ."`
7 Yellow with black edges . ;. `.
8 Dark yellow brown : -g Dark brown Black The results are shown in Tables I and II:
~ ~ 2 s~
Table I
Color Rating at 350C
Control Examplés - -2 3 4 5 ..
Amount of B-diketone none ~ ~ ~ ~Y ~7c Time (minutes) O O O O O O O .,.'.
0 0 0 0 0 0 `-0 0 0 0 0 o 0 0 0 0 0 0 ``.:
0 0 0 0 0 0 ~ `
1 1 1 1 1 1 .~
105 2 2 2 2 2 2 `
... .
:
59 ~:
r Table II " ~
-Color Rating at 375F ` ~
ControlExamples ; ~ .;
5Amount of ~-diketone none1~ ~ ~ ~FYo 5~0 Time (minutes) `.
O O O O O O O '`" ' 0 0 0 0 0 0 ``~.
0 0 0 0 0 0 ~``
3 3 3 3 3 3 ~:
7 7 7 7 7 7 ``` `:
8 8 8 8 8 8 ``
~ ~ 2 s~
Table I
Color Rating at 350C
Control Examplés - -2 3 4 5 ..
Amount of B-diketone none ~ ~ ~ ~Y ~7c Time (minutes) O O O O O O O .,.'.
0 0 0 0 0 0 `-0 0 0 0 0 o 0 0 0 0 0 0 ``.:
0 0 0 0 0 0 ~ `
1 1 1 1 1 1 .~
105 2 2 2 2 2 2 `
... .
:
59 ~:
r Table II " ~
-Color Rating at 375F ` ~
ControlExamples ; ~ .;
5Amount of ~-diketone none1~ ~ ~ ~FYo 5~0 Time (minutes) `.
O O O O O O O '`" ' 0 0 0 0 0 0 ``~.
0 0 0 0 0 0 ~``
3 3 3 3 3 3 ~:
7 7 7 7 7 7 ``` `:
8 8 8 8 8 8 ``
9 9 9 9 9 9 :
105 10 10 10 10 10 10 `:
The results in Tables I and II show that the ~-diketone, stearoyl benzoyl methane, has no noticeable effect on heat `
stability at 350 and 375F, since the Control is equivalent to any of Examples 1 to 5.
Samples also were placed in a Geer oven and held at 20 215F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in a -motor vehicle, such as automobile, with the following results: `~
Table III .
Color Rating at 215F ; . .
Control Examples _ _ 2 3 4 5 :
Amount of B-diketone none ~ ~Y. ~ ~o 5 Tirne (days) O O O O O O O ',', o O O O O O -."`,"
2 0 0 0 0 0 0 .`.
: - .
4 1 0 0 0 0 0 `
1 0 0 0 0 0 `.
6 2 0 0 0 0 0 .-7 2 0 0 0 0 0 :.
The ~-diketone, stearoyl benzoyl methane, clearly :
overcomes the instability evidenced by the Control, even in an amount as low as 1%, ~;
2 ,~
. ,~
Examples 6 to 9 Polyvirlyl chloride resin compositions were made up . .~.
having the following formulation: - :
Ingredient Parts by Wei~ht .. -.~ , Polyvinyl chloride 100 :
homopolymer ~
Dioctyl phthalate 50 Drapex 6. 8 5 ~
(epoxidized soybean oil) ~.
Calcium carbonate 20 `;
(Atom ite) ` ~
Stearic ac id 0. 3 `~:
Stabilizer 3. 0 . ` .
Controls Exam~les Composed of: 1 2 _ 7 8 9 Barium nonyl phenate 21. 2 21.2 21.221.2 21. 2 210 2 solution 120 5% Ba Zinc 2-ethyl hexoate 21,2 - 21.221.2 21.2 - ~ .
(8D 5% Zn) (50% solution) Phenyl diisodecyl 42. 6 42. 6 42. 642. 6 42. 6 42. 6 ;
phosphite ZnCl2 ~ phenyl diisodecyl - 15 - _ _ 15 :
phosphite (PDDP) ~:
Stearoyl benzoyl - - 1. 00. 25 0. 5 lo O
m ethane Mineral spirits 15.0 1500 14. 0 14. 75 14. 5 15. 0 ~
:~:
,/ .
~ ~ 7J ~ i ~
The stabilizer system and other ingredients (dioctyl phthalate, epoxidized soybean oil, calcium carbonate and stearic acid) were blended with the ~olyvinyl chloride resin -` `
on a two-roll mill, and then sheeted off. Samples were cut . ~
off from the sheet and heated in a Geer oven at 350F and . .
375F for up to two hours~ Samples were withdrawn at fifteen ;;.
minute intervals to follow the progress of any deterioration as evidenced by discoloration and/or embrittlement. Deterioration was rated according to the scale of Examples 1 to 5. The .
results are shown in Tables IV to VI: `
Table IV
Color Rating at 350F
Controls Examples Time (minutes) 1 2 6 7 8 . ~ .
o o o 0 o o 0 0 o 0 0 o 0 0 1 0 0 0 1 `~
`', ~'~
'~ ': ' ~
63 ~ .
: ~ "
Table V
Color Rating at 375F ~":
Controls Exar~ple~
Time (minutes) 1 2 6 7 8 9 - `
0 0 0 0 0 0 0 .
~ 0 0 0 `-`
0 0 0 0 0 0 ~ -7 5 7 7 7 5 :
105 10 10 10 10 10 10 `:
The results in Tables I and II show that the ~-diketone, stearoyl benzoyl methane, has no noticeable effect on heat `
stability at 350 and 375F, since the Control is equivalent to any of Examples 1 to 5.
Samples also were placed in a Geer oven and held at 20 215F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in a -motor vehicle, such as automobile, with the following results: `~
Table III .
Color Rating at 215F ; . .
Control Examples _ _ 2 3 4 5 :
Amount of B-diketone none ~ ~Y. ~ ~o 5 Tirne (days) O O O O O O O ',', o O O O O O -."`,"
2 0 0 0 0 0 0 .`.
: - .
4 1 0 0 0 0 0 `
1 0 0 0 0 0 `.
6 2 0 0 0 0 0 .-7 2 0 0 0 0 0 :.
The ~-diketone, stearoyl benzoyl methane, clearly :
overcomes the instability evidenced by the Control, even in an amount as low as 1%, ~;
2 ,~
. ,~
Examples 6 to 9 Polyvirlyl chloride resin compositions were made up . .~.
having the following formulation: - :
Ingredient Parts by Wei~ht .. -.~ , Polyvinyl chloride 100 :
homopolymer ~
Dioctyl phthalate 50 Drapex 6. 8 5 ~
(epoxidized soybean oil) ~.
Calcium carbonate 20 `;
(Atom ite) ` ~
Stearic ac id 0. 3 `~:
Stabilizer 3. 0 . ` .
Controls Exam~les Composed of: 1 2 _ 7 8 9 Barium nonyl phenate 21. 2 21.2 21.221.2 21. 2 210 2 solution 120 5% Ba Zinc 2-ethyl hexoate 21,2 - 21.221.2 21.2 - ~ .
(8D 5% Zn) (50% solution) Phenyl diisodecyl 42. 6 42. 6 42. 642. 6 42. 6 42. 6 ;
phosphite ZnCl2 ~ phenyl diisodecyl - 15 - _ _ 15 :
phosphite (PDDP) ~:
Stearoyl benzoyl - - 1. 00. 25 0. 5 lo O
m ethane Mineral spirits 15.0 1500 14. 0 14. 75 14. 5 15. 0 ~
:~:
,/ .
~ ~ 7J ~ i ~
The stabilizer system and other ingredients (dioctyl phthalate, epoxidized soybean oil, calcium carbonate and stearic acid) were blended with the ~olyvinyl chloride resin -` `
on a two-roll mill, and then sheeted off. Samples were cut . ~
off from the sheet and heated in a Geer oven at 350F and . .
375F for up to two hours~ Samples were withdrawn at fifteen ;;.
minute intervals to follow the progress of any deterioration as evidenced by discoloration and/or embrittlement. Deterioration was rated according to the scale of Examples 1 to 5. The .
results are shown in Tables IV to VI: `
Table IV
Color Rating at 350F
Controls Examples Time (minutes) 1 2 6 7 8 . ~ .
o o o 0 o o 0 0 o 0 0 o 0 0 1 0 0 0 1 `~
`', ~'~
'~ ': ' ~
63 ~ .
: ~ "
Table V
Color Rating at 375F ~":
Controls Exar~ple~
Time (minutes) 1 2 6 7 8 9 - `
0 0 0 0 0 0 0 .
~ 0 0 0 `-`
0 0 0 0 0 0 ~ -7 5 7 7 7 5 :
10 10 10 10 .
The results in Tables IV and V show that the B-diketone, stearoyl benzoyl methane, contributes no noticeable improvement ~ .:
to heat stability at 350 and 375F.
Samples also were placed in a Geer oven and held at 15 215F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in a motor vehicle such as an automobile, with the following results:
~ .
J' ~
Table VI ~. .
Color Rating at 215F
Control~Exam~les Time (d_ys) 1 2 6 7 8 9 O O OOOOO -`':'.'.
2 1 1 0 0 0 0 ~-3 1 1 0 0 0 0 ~ -4 2 2 0 0 0 0 ~;"`
7 3 3 0 1 1 1 ~`
The ~-diketone, stearoyl benzoyl methane, clearly improves stability at 215F after heat processing, as ` ~:
evidenced by comparison of Controls 1 and 2 with Examples 6 to 9.
'',`'' ~ ~ 2 r~
Example 10 Polyvinyl chloride resin compositions wsre made up `
~ .~
having the following formulation: ~ .
Ingredient Parts by Weight ` .
5Polyvinyl chloride homopolymer 100 :
Dioctyl phthalate 50 - ::
Drapex 6, 8 .
(epoxidized soybean oil) 5 Calcium carbonate 20 `
Stearic ac id 0, 3 Stabilizer 3,`0 Stabilizer composed of: ControlExample 10 Diphenyl isodecyl phosphite 40 40 . ~ ~:
Isooctyl thioglycolate trithio-10 10 :
phosphite Diphenyl phosphite 4 4 Antioxidant 4 4 Barium nonyl phenate-barium 28 28 -~:
carbonate Zinc chloride phenyl diisodecyl 18 18 :~:
phosphite Stearoyl benzoyl methane - 1. 0 -~
:
2~22~-.g'3 ~;
',.,'..~, The stabilizer system and other ingredients (dioctyl~ ~;
phthalate, epoxidized soybean oil, calcium carbonate and - ~;
stearic acid) were blended with the polyvinyl chloride resin -~
on a two-roll mill, and then sheeted off. Samples were cut` ~:
off from the sheet and heated in a Geer oven at 350F and 375F for up to two hours. Samples were withdrawn at fifteen.:
minute intervals to follow the progress of any deterioration as ` ~
evidenced by discoloration and/or embrittlement. Deterioration :~ `
was rated accordin~ to the scale of Examples 1 to 5. The results are shown in Tables VII to IX.
Table VII ~ :
;.
Color Rating at 350F
Time (minutes) C~ntrol Example 10 `
O O O ~:
0 0 `
0 o ~
0 0 ~;
2 2 ` ~;
105 4 4 --:
~;-67 :~
~ ?.~ r3`-~ ~.'.. ''.
Table VIII
:. :
Color Rating at 375F ::
Time (minutes) Control Example 10 O O o , `.:
0 o ;~
2 2 .`
3 3 :.
10 90 4 4 `~ `
120 7 7 :
The results in Tables VII and VIII show that the B- ~
diketone, stearoyl benzoyl methane, contributes no noticeable : :-improvement to heat stability at 350 and 375F.
Samples also were placed in a Geer oven and held at ~ -215F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in a motor vehicle` ~.
such as an automobile, with the following results~
'''~' 2 ~ 2 ~
Table ~
, ......
Color Rating at 215F
Time (days) Example 10 Control ~
O O O ' .' 0 o 4 0 2 `-o 3 ~:
6 1 4 `
The ~-diketone, stearoyl benzoyl methane, clearly improves stability at 215F after heat processing, as evidenced by comparison of the Control with Example lOo ~ `
69 `~
~22~
Examples 11 to 14 .. ~
:
Polyvinyl chloride resin compositions were made up ~
ha~ing the following formulation: :
Ingredient Parts by Weight .
Polyvinyl chloride homopolymer (Oxy 9400) 100 Santicizer 711 (mixed C7-C11 alk~l phthalate) 30 Drapex 6. 8 (epoxidized soybean oil) 5O 0 .::
Omyalite 90T (calcium carbonate) 15 ;~
Loxol GT-71 (fatty ester lubricant) 0~25 .~.
Mic rocheck l lD ~fungic ide) 3 . 0 ; .~ .
TiO2 (R101) 0.25 Dibenzoyl methane 0. 3 ; .
Stabilizer 2, 5 Examples _ 1_ 12 13 14 Stabilizer composed of: ;
Barium nonyl phenate solution 50% (12. 5% Ba) 14.7 17. 6 ~ _ Ba nonyl phenate-Ba 2-ethyl hexoate (12% Ba) 14.7 17. 6 - -Ba nonyl phenate-BaCO3 (27% Ba) - - 24, 9 28 ~:
Zinc 2-ethyl he~oate (22% Zn) 1.3 1.6 207 Cd benzoate tallate solution (14% Cd) 33, 3 20,0 Cd 2 ethyl he~oate benzoate tallate solutio.n (14% Cd) 14. 7 17. 6 ~2,~3~
. ';:':
Examples . .~ .
li 12 13 14 ~ -.: ;, Cd 2-ethyl hexoate (10% Cd) in PDDP - - 41. 2 Diphenyl isodecyl phosphite 140 5 17.4 - 40 ~. .;
Phenyl diisodecyl phosphite (PDDP) 21. 2 Triphenyl phosphite 3O 2 3, 8 Diphenyl phosphite 0. 31 1. 6 3 4 ~ .
ZnCl2~ phenyl diisodecyl : :
phosphite - - - 18 Isooctyl thioglycolate trithiophosphite - - - 10 Oleic acid - 0. 8 0. 6 -Mineral spirits 1. 4 0, 85 5 Cinnamic acid - 0, 75 0, 35 Antioxidant 1. 0 0. 4 1 4 Dibenzoyl methane 1200 12,0 1200 12. 5 In addition, four Controls were made up exactly like Examples 11, 12, 13 and 14, but without the dibenzoyl methaneO ~ ::
The stabilizer system and other ingredients were -blended with the polyvinyl chloride resin on a two-roll mill and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two hours. Samples were withdrawn at fifteen minute intervals ~;
and their appearance observed according to the color rating ~;
chart of Examples 1 to 5O The results are shown in Tables ~ . ;
X and XIo ~ 2 ~
Table X ~;
Color Rating at 350F
Controls Examples Time (minutes) 1 2 3 411l ~2 13 114 0 0 0 0 0 0 0 0 0 `-0 0 1 1 0 0 0 0 ;
120 1 1 2 2 1 1 1 2 ;~
Table :XI
Color P~ating at 375F
Controls Examl~les Time ~minutes) 1 2 3 411 12` 13 14 :
o O O O O O O O O '~
0 0 0 1 0 0 :
1 1 1 2 1 1 0 1 :;~
3 3 3 3 2 2 1 2 ;~
105 7 7 7 5 5 5 5 5 :~
120 8 8 8 7 7 7 7 7 :
,':~
72 .
The dibenzoyl methane clearly contributes no noticeable effect on heat stabilitsT at 350 and 375F.
Samples also were placed in a Geer oven and held at 215F for up to seven days to simulate the moderate .:
temperatures experienced by a motor vehicle component in ~ .
a motor vehicle, such as an automobile, with the following results:
Table. XII
Color Rating at 215F
C trols Examples Time (days) 1 2 3 4 fl 0 0 0 0 0 0 0 0 0 `';`~`~
0 0 0 0 ~;
4 3 3 4 4 0 0 0 0 ;
4 4 5 5 0 0 1 1 `~
q 6 6 7 6 2 2 3 3 ~:~
The ~-diketone, dibenzoyl methane, markedly improves stability at moderate temperatures after heat processing.
On the other hand, the B-diketone has no noticeable effect :
on stability at low temperatures of the order of 120F (50C)o ` -This is shown by exposure to fluorescent light in a QUV
fluorescent bulb weathering device, operating at 120F (50C) in a 4 hour cycle, with the lights on 4 hours and then off 4 hours, ~
for up to 16 days. The samples so exposed gave the following ~ ~;
results~
73 ~
2~22~
Table XlII
QUV Exposure at 120~F ` ~.
Controls Examples Time ~hours) 1 2 3 4 11 12 13- 14 :
_ o 0 0 0 0 0 0 0 0 ~`
118 1 1 1 1 1 1 1 1 ~`
283 2 2 2 2 2 2 2 2 :
. ..
2 ~ ~.' 2 h ~3 5 Examples 15 to 17 : -.
Polyvinyl chloride resin compositions were made up having the following formulation: ~ ~
Ingredient Parts by Weight ~ .
Polyvinyl chloride homopolymer . .
(Tenneco 22 5) 100 Santiciz~r 711 (mixed C7-C11 alkyl phthalate plasticizer) 30 Drapex 6. 8 epoxldized soybean oil 4. 5 : .
2-hydroxy-4-n-octoxy benzophenone 1. 0 ~: .
Stearic acid 0,25 " -Stabilizer 3. ;
Examples ~::
Control 15 16 17 Stabilizer composed of:
Barium nonyl phenate BaCO3 (27% Ba) 3, 92 16 16 16 ~
Barium nonyl phenate ~ .
(12. 5% Ba) 24.81 - - - ; -Cd 2-ethyl-hexoate (20% Cd) 3, 92 - - ~
Cd benzoate-2-ethyl hexoate tallate (14% Cd) 43,1 50 50 50 Zn~2-ethyl hexoate 1. 3 1. 5 1. 5 lo 5 Diphenyl phosphite 4 4 4 4 -~
Diphenyl isodecyl phosphite 17 17 17 17 ~`;
Oleic acid 0. 67 - - .
Cinnamic acid 0.4 0. 5 0. 5 oO 5 Antioxidant 1.0 Dibenzoyl methane - 2. 5 5.0 7. 5 ~ .
Hydrocarbon diluent - 8. 5 600 3O 5 ''.'''''' ' f)-The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two .5:
hours. Samples were withdrawn at fifteen minute intervals, and the discoloration rated according to the scale in Examples 1 to 5~ The results are shown in Tables XIV and XV
Table XIV
Color Rating at 350F
Examples ~.
Time ~minutes)Control 1516 1~
.
O O O O O
- ~:
76 ~:
2~
Table XV ~
, .
Color Rating~ at 375~F
Examples Time (minutes)Control 15 16 17 0 0 0 0 ~
120 7 7 7 8 ~;
The ~-diketone, dibenzoyl methane, clearly does not contribute to heat stability at 350 or 375F.
A plate-out test was run on all four resin compositions.
Red pigment was added to the composition and the mix milled `~
on the two-roll mill for five minutes at 325F, and sheeted off The clean-up sheet run thereafter was exactly the same in all -four cases, showing the ~-diketone had no effect. ~ -Thick press-polished panels were prepared from each composition, and were indistinguishable, one from the other, again showing the B-diketone had no effect.
Samples also were placed in a Geer oven and held at 25 215F for up to fourteen days, to simulate the moderate temperatures experienced by motor vehicle components in a motor vehicle such as an automobile, with the following results:
Table XVI
Color Rating at 215F ~ ~
Examples _ ~ .
~) Control 15 16 17 . .
O O O O O
2 0 0 0 ~
1~ 3 1 0 0 0 ;
6 2 0 0 0 ~ .
8 3 1 1 1 ~:
9 3 1 1 1 ..
3 1 1 1 `` .
The results in Tables IV and V show that the B-diketone, stearoyl benzoyl methane, contributes no noticeable improvement ~ .:
to heat stability at 350 and 375F.
Samples also were placed in a Geer oven and held at 15 215F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in a motor vehicle such as an automobile, with the following results:
~ .
J' ~
Table VI ~. .
Color Rating at 215F
Control~Exam~les Time (d_ys) 1 2 6 7 8 9 O O OOOOO -`':'.'.
2 1 1 0 0 0 0 ~-3 1 1 0 0 0 0 ~ -4 2 2 0 0 0 0 ~;"`
7 3 3 0 1 1 1 ~`
The ~-diketone, stearoyl benzoyl methane, clearly improves stability at 215F after heat processing, as ` ~:
evidenced by comparison of Controls 1 and 2 with Examples 6 to 9.
'',`'' ~ ~ 2 r~
Example 10 Polyvinyl chloride resin compositions wsre made up `
~ .~
having the following formulation: ~ .
Ingredient Parts by Weight ` .
5Polyvinyl chloride homopolymer 100 :
Dioctyl phthalate 50 - ::
Drapex 6, 8 .
(epoxidized soybean oil) 5 Calcium carbonate 20 `
Stearic ac id 0, 3 Stabilizer 3,`0 Stabilizer composed of: ControlExample 10 Diphenyl isodecyl phosphite 40 40 . ~ ~:
Isooctyl thioglycolate trithio-10 10 :
phosphite Diphenyl phosphite 4 4 Antioxidant 4 4 Barium nonyl phenate-barium 28 28 -~:
carbonate Zinc chloride phenyl diisodecyl 18 18 :~:
phosphite Stearoyl benzoyl methane - 1. 0 -~
:
2~22~-.g'3 ~;
',.,'..~, The stabilizer system and other ingredients (dioctyl~ ~;
phthalate, epoxidized soybean oil, calcium carbonate and - ~;
stearic acid) were blended with the polyvinyl chloride resin -~
on a two-roll mill, and then sheeted off. Samples were cut` ~:
off from the sheet and heated in a Geer oven at 350F and 375F for up to two hours. Samples were withdrawn at fifteen.:
minute intervals to follow the progress of any deterioration as ` ~
evidenced by discoloration and/or embrittlement. Deterioration :~ `
was rated accordin~ to the scale of Examples 1 to 5. The results are shown in Tables VII to IX.
Table VII ~ :
;.
Color Rating at 350F
Time (minutes) C~ntrol Example 10 `
O O O ~:
0 0 `
0 o ~
0 0 ~;
2 2 ` ~;
105 4 4 --:
~;-67 :~
~ ?.~ r3`-~ ~.'.. ''.
Table VIII
:. :
Color Rating at 375F ::
Time (minutes) Control Example 10 O O o , `.:
0 o ;~
2 2 .`
3 3 :.
10 90 4 4 `~ `
120 7 7 :
The results in Tables VII and VIII show that the B- ~
diketone, stearoyl benzoyl methane, contributes no noticeable : :-improvement to heat stability at 350 and 375F.
Samples also were placed in a Geer oven and held at ~ -215F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in a motor vehicle` ~.
such as an automobile, with the following results~
'''~' 2 ~ 2 ~
Table ~
, ......
Color Rating at 215F
Time (days) Example 10 Control ~
O O O ' .' 0 o 4 0 2 `-o 3 ~:
6 1 4 `
The ~-diketone, stearoyl benzoyl methane, clearly improves stability at 215F after heat processing, as evidenced by comparison of the Control with Example lOo ~ `
69 `~
~22~
Examples 11 to 14 .. ~
:
Polyvinyl chloride resin compositions were made up ~
ha~ing the following formulation: :
Ingredient Parts by Weight .
Polyvinyl chloride homopolymer (Oxy 9400) 100 Santicizer 711 (mixed C7-C11 alk~l phthalate) 30 Drapex 6. 8 (epoxidized soybean oil) 5O 0 .::
Omyalite 90T (calcium carbonate) 15 ;~
Loxol GT-71 (fatty ester lubricant) 0~25 .~.
Mic rocheck l lD ~fungic ide) 3 . 0 ; .~ .
TiO2 (R101) 0.25 Dibenzoyl methane 0. 3 ; .
Stabilizer 2, 5 Examples _ 1_ 12 13 14 Stabilizer composed of: ;
Barium nonyl phenate solution 50% (12. 5% Ba) 14.7 17. 6 ~ _ Ba nonyl phenate-Ba 2-ethyl hexoate (12% Ba) 14.7 17. 6 - -Ba nonyl phenate-BaCO3 (27% Ba) - - 24, 9 28 ~:
Zinc 2-ethyl he~oate (22% Zn) 1.3 1.6 207 Cd benzoate tallate solution (14% Cd) 33, 3 20,0 Cd 2 ethyl he~oate benzoate tallate solutio.n (14% Cd) 14. 7 17. 6 ~2,~3~
. ';:':
Examples . .~ .
li 12 13 14 ~ -.: ;, Cd 2-ethyl hexoate (10% Cd) in PDDP - - 41. 2 Diphenyl isodecyl phosphite 140 5 17.4 - 40 ~. .;
Phenyl diisodecyl phosphite (PDDP) 21. 2 Triphenyl phosphite 3O 2 3, 8 Diphenyl phosphite 0. 31 1. 6 3 4 ~ .
ZnCl2~ phenyl diisodecyl : :
phosphite - - - 18 Isooctyl thioglycolate trithiophosphite - - - 10 Oleic acid - 0. 8 0. 6 -Mineral spirits 1. 4 0, 85 5 Cinnamic acid - 0, 75 0, 35 Antioxidant 1. 0 0. 4 1 4 Dibenzoyl methane 1200 12,0 1200 12. 5 In addition, four Controls were made up exactly like Examples 11, 12, 13 and 14, but without the dibenzoyl methaneO ~ ::
The stabilizer system and other ingredients were -blended with the polyvinyl chloride resin on a two-roll mill and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two hours. Samples were withdrawn at fifteen minute intervals ~;
and their appearance observed according to the color rating ~;
chart of Examples 1 to 5O The results are shown in Tables ~ . ;
X and XIo ~ 2 ~
Table X ~;
Color Rating at 350F
Controls Examples Time (minutes) 1 2 3 411l ~2 13 114 0 0 0 0 0 0 0 0 0 `-0 0 1 1 0 0 0 0 ;
120 1 1 2 2 1 1 1 2 ;~
Table :XI
Color P~ating at 375F
Controls Examl~les Time ~minutes) 1 2 3 411 12` 13 14 :
o O O O O O O O O '~
0 0 0 1 0 0 :
1 1 1 2 1 1 0 1 :;~
3 3 3 3 2 2 1 2 ;~
105 7 7 7 5 5 5 5 5 :~
120 8 8 8 7 7 7 7 7 :
,':~
72 .
The dibenzoyl methane clearly contributes no noticeable effect on heat stabilitsT at 350 and 375F.
Samples also were placed in a Geer oven and held at 215F for up to seven days to simulate the moderate .:
temperatures experienced by a motor vehicle component in ~ .
a motor vehicle, such as an automobile, with the following results:
Table. XII
Color Rating at 215F
C trols Examples Time (days) 1 2 3 4 fl 0 0 0 0 0 0 0 0 0 `';`~`~
0 0 0 0 ~;
4 3 3 4 4 0 0 0 0 ;
4 4 5 5 0 0 1 1 `~
q 6 6 7 6 2 2 3 3 ~:~
The ~-diketone, dibenzoyl methane, markedly improves stability at moderate temperatures after heat processing.
On the other hand, the B-diketone has no noticeable effect :
on stability at low temperatures of the order of 120F (50C)o ` -This is shown by exposure to fluorescent light in a QUV
fluorescent bulb weathering device, operating at 120F (50C) in a 4 hour cycle, with the lights on 4 hours and then off 4 hours, ~
for up to 16 days. The samples so exposed gave the following ~ ~;
results~
73 ~
2~22~
Table XlII
QUV Exposure at 120~F ` ~.
Controls Examples Time ~hours) 1 2 3 4 11 12 13- 14 :
_ o 0 0 0 0 0 0 0 0 ~`
118 1 1 1 1 1 1 1 1 ~`
283 2 2 2 2 2 2 2 2 :
. ..
2 ~ ~.' 2 h ~3 5 Examples 15 to 17 : -.
Polyvinyl chloride resin compositions were made up having the following formulation: ~ ~
Ingredient Parts by Weight ~ .
Polyvinyl chloride homopolymer . .
(Tenneco 22 5) 100 Santiciz~r 711 (mixed C7-C11 alkyl phthalate plasticizer) 30 Drapex 6. 8 epoxldized soybean oil 4. 5 : .
2-hydroxy-4-n-octoxy benzophenone 1. 0 ~: .
Stearic acid 0,25 " -Stabilizer 3. ;
Examples ~::
Control 15 16 17 Stabilizer composed of:
Barium nonyl phenate BaCO3 (27% Ba) 3, 92 16 16 16 ~
Barium nonyl phenate ~ .
(12. 5% Ba) 24.81 - - - ; -Cd 2-ethyl-hexoate (20% Cd) 3, 92 - - ~
Cd benzoate-2-ethyl hexoate tallate (14% Cd) 43,1 50 50 50 Zn~2-ethyl hexoate 1. 3 1. 5 1. 5 lo 5 Diphenyl phosphite 4 4 4 4 -~
Diphenyl isodecyl phosphite 17 17 17 17 ~`;
Oleic acid 0. 67 - - .
Cinnamic acid 0.4 0. 5 0. 5 oO 5 Antioxidant 1.0 Dibenzoyl methane - 2. 5 5.0 7. 5 ~ .
Hydrocarbon diluent - 8. 5 600 3O 5 ''.'''''' ' f)-The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two .5:
hours. Samples were withdrawn at fifteen minute intervals, and the discoloration rated according to the scale in Examples 1 to 5~ The results are shown in Tables XIV and XV
Table XIV
Color Rating at 350F
Examples ~.
Time ~minutes)Control 1516 1~
.
O O O O O
- ~:
76 ~:
2~
Table XV ~
, .
Color Rating~ at 375~F
Examples Time (minutes)Control 15 16 17 0 0 0 0 ~
120 7 7 7 8 ~;
The ~-diketone, dibenzoyl methane, clearly does not contribute to heat stability at 350 or 375F.
A plate-out test was run on all four resin compositions.
Red pigment was added to the composition and the mix milled `~
on the two-roll mill for five minutes at 325F, and sheeted off The clean-up sheet run thereafter was exactly the same in all -four cases, showing the ~-diketone had no effect. ~ -Thick press-polished panels were prepared from each composition, and were indistinguishable, one from the other, again showing the B-diketone had no effect.
Samples also were placed in a Geer oven and held at 25 215F for up to fourteen days, to simulate the moderate temperatures experienced by motor vehicle components in a motor vehicle such as an automobile, with the following results:
Table XVI
Color Rating at 215F ~ ~
Examples _ ~ .
~) Control 15 16 17 . .
O O O O O
2 0 0 0 ~
1~ 3 1 0 0 0 ;
6 2 0 0 0 ~ .
8 3 1 1 1 ~:
9 3 1 1 1 ..
3 1 1 1 `` .
12 4 2 2 2 :
13 5 2 2 2 .
The B-diketone clearly improves resistance to discoloration at 215F after heat-processing.
.. ..
.
~ ~ ~ 2 ~
Example 18 Polyvinyl chloride resin connpositions were made up . ~ `
having the following formulation~
Ingredient Parts by Weight ~ -P olyvinyl chloride homopolym er ~ .
(Tenneco 225) 100 Santicizer 711 (mixed C7-C11 :.
a~yl phthalate plasticizer) 30 -Drapex 6. 8 epoxidized soybean oil 4 Blue dye 0.01 "~``
Stearic acid 0.25 Stabilizer 3. 0 ~ .
Control Exam~le 18 `~
Stabilizer composed of~
Barium nonyl phenate BaCO3 ;
(27~o Ba) 32.5 16 ~ ~ :
Cd 2-ethyl-hexoate (20% Cd) - 50 Cd benzoate-2-ethyl hexoate tallate (14% Cd) 27.4 -. . ~ -Zn~ 2-ethyl hexoate (22% Zn) 3~1 1. 5 ~ .` `.~ ~
Diphenyl phosphite 1. 6 4 Diphenyl isodecyl phosphite - 1~
Diphenyl 2-ethyl hexyl - `.
phosphite 35.
Cinnam ic acid - . 5 Mineral Spirits - 8. 5 ~ , Dibenzoyl methane 2, 5 2 ~J ~ .3 ~
The stabilizer system and other ingredients were ~ .
blended with the polyvinyl chloride resin on a two-roll mill, -and then sheeted offO
Blue-tinted convertible rear window press-polished panels were prepared from each composition, and clippings ~`
taken from each were placed in a Geer oven and held at 215F
for up to fourteen days, to simulate the moderate temperatures experienced by such rear windows when installed in an :;
automobile, with the following results: -:
: :.
`';
', ',..' ~
2 ~ 2 2 ~
`..',;;
Table XVII
Color at 215F
Time (days) Control Example 18 ` :~
0 Blue Blue ::
1 Unchanged Unchanged `
2 . Faded Blue Unchanged `
Barely Perceptible Unchanged 3 Blue Tint " ~` `
4 Light Gray Unchanged .`~
Gray Tan Faded Blue ;.
6 Light Tan Faded Blue 7 Light Tan Faded Blue : `
8 Light Tan Faded Blue : ~
9 Light Tan Barely Perceptible : ~`
Blue Tint Medium Tan Barely Perceptible Blue Tint .::
11 Medium Tan Light Gray ` .~`
12 Dark Tan Light Gray 13 Dark Tan Gray Tan 14 Dark Tan Gray Tan The ~ diketone clearly improves resistance to discoloration at 215F after heat-processing. ~
81 ., ~ '':
2 ~ 2 ,~
Example 19 Polyvinyl chloride resin compositions were made up having the following formulation~
Ingredient Parts by Weight Polyvinyl chloride homopolymer ~ -(Tenneco 225) 100 Santicizer 711 (mixed C7-C11 aL~yl phthalate plasticizer) 35 Drapex 6. 8 epoxidized soybean oil 5 `
Atomite (CaCO3) 20 Stearic acid 0. 25 .
Stabilizer 2. 5 Control E:xample 19 .:
...: .
Stabilizer composed of ~
Barium nonyl phenate BaCO3 ~::
(27~o Ba) 32. 5 16 Cd 2-ethyl-hexoate (20% Cd) 27.4 50 ~
Cd benzoate-2-ethyl hexoate ~ `. .`
Tallate (14% C'd) Zn. 2-ethyl hexoate 3.1 lo 5 `
Diphenyl phosphite 1.6 4 -Diphenyl isodecyl phosphite - 17 Diphenyl 2-ethyl hexyl phosphite 3 5 Cinnamic acid - 0. 5 ~-Mineral Spirits - 8. 5 Dibenzoyl methane - 2. 5 ' ' '' 82 ~
The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off~ Samples were cut off from the sheets -~:
and heated in a Geer oven at 350F and 375F for up to two hours, Samples were withdrawn at fifteen minute intervals, :~
and the discoloration rated according to the scale in ;;
Examples 1 ,to 5. The results are shown in Tables XVIII and XIXo ~ ~' Table XVIII
Color Rating at 350~F
.:
10~Time (minutes) Control Example 19 , O '`.'.' .~.' 0 0 ~-:
0 0 ',~:
0 0 '`~
105 1 1 - :''`''-~.~..' ;.
83 `:
~ ~ 2 ~ ~3 c3 l3 :
Table X~
Color Rating at 3753F
Time (minutes) ~~ohtrolExample 19 O `'`;
~.
0 0 -:
1 1 . :. .
1 1 :`
2 2 .
3 3 . ~ i 105 5 5 ` ````
120 7 7 ::
The ~-diketone, dibenzoyl methane, clearly does not contribute to heat stability at 350 or 375F.
Glove compartment boxes were prepared from each ..
composition, The boxes were placed in a Geer oven and held at 215F for up to fourteen days, to simulate the moderate -;
temperatures experienced by such components in an . .~`
automobile, with the following results:
~ J~ f~ 3 Table XX _ ~:
Color at 215 F
~) Control : Example 19 ;~
0 White White ~.
1 Unchanged Unchanged 2 Unchanged Unchanged 3 Dirty White Unchanged 4 Dirty White Unchanged :
Light Tan Unchanged ~-6 Light Tan Unchanged 7 Light Tan Dirty White 8 Medium Tan Dirty White 9 Medium Tan Dirty White :;
Medium Tan Dirty White 11 Dark Tan Dirty White ; :
12 Dark Tan Dirty White 13 Dark Tan Light Tan :
14 Dark Tan Light Tan The ~-diketone clearly improves resistance to 20 discoloration at 215F after heat-processing.
?~
Examples 20 to 24 `
- , .
Polyvinyl chloride resin compositions were made up having the following formulation: ~
Ingredient Parts by Weight -Polyvinyl chloride homopolymer (Oxy 9400) 100 ~antici~r 711 (mixed C7-C11 -` `
allcyl phthalate) 30 Drapex 6.8 (epoxidized soybean oil) 5.0 Omyalite 90T (CaC03) 15 -:
L~xiol GT-71 (fat~y ester lubricant~ O. 25 Microcheck 1 lD (fungic ide) 3.0 ` `
T iO2 (R 101) ' 0.25 `
Heat ~tabilizer 2. 5 ~ ':
Controls Examples 2 20 21 22 23 24 `
Heat stabilizer composed of: -. . .
Ba nonyl phenate-BaCO3 (27% Ba) 2409 24.~ 24.9 24.9 24,9 24.9 24,9 Zinc 2-ethyl hexoate `
(22% Zn) 2.7 2.7 2.7 2.7 2.7 2.7 207 Cd 2-ethyl hexoate ~-(10% Cd) 41.2 41.2 41.2 41.2 41.2 41.2 41.2 Phenyl diisodecyl pho~phite 21.2 21.2 21.2 21.2 2102 21.2 2102 Diphenyl phosphite 3 3 3 3 3 3 3 Oleic acid 006 0.6 0.6 006 0,6 006 006 Mineral spirits 5 5 5 5 5 5 5 Cinnamic acid 0.35 0.35 0.35 0.35 0.35 0.35 0O35 30 Antioxidant 86 -~
2 ~ 3 : ~
Parts by Weight per 100 Parts of Polymer Other Stabilizers Controls Examples added sepa ately 1 _2 _ 21 22 23 24 2-Hydroxy-4-octyl~
oxybenzophenone 0~ 5 2, 5 0. 5 0O 5 1.0 0O 5 0~ 5 -"
Stearoyl benzoyl :
methane - 0, 2 0. 5 - - 0. 5 0O 5 Dibenzoyl methane - - - 0.2 0, 5 The stabilizer system and other ingredients were . ~"
blended with the polyvinyl chloride resin on a two-roll mill and then sheeted off~ Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two : .
hours~ Samples were withdrawn at fifteen minute intervals ~
and their appearance observed according to the color rating ` .
chart of Examples 1 to 5~ The results are shown in Tables X~ and XX, 87 :
2 ~ 2 2 ~ 3 r3 ~'-,','''~
.",, Table X~ : .
Color Rating at 350F . :
Controls Examples Time (minutes) 1 2 ~) 21 22 23 24 : :
0 0 0 0 0 0 0 0 ..
4 5 0 0 0 0 0 0 0 `
0 0 0 0 `
0 0 o 0 0 0 0 -:.
105 1 ~ 1 1 1 1 1 `
Table ~II
t5 Color Rating at 375F
Controls E:xamples ` ~ `
Time (minutes) 1 Z ~ Z ~ 24 O O O O O O O O ''~' 0 0 0 0 0 0 0 ~
~0 30 0 0 0 0 0 0 0 ` .
0 0 0 0 0 o 0 0 0 0 0 o 0 0 ``~
105 1 1 1 1 1 1 1 .
~'''.' 88 ~ ~
2 2 ~
. ................................................................... ~ -, . .
:``' The dibenzoyl methane clearly contributes no noticeable `- `
effect on heat stability at 350 and 375F. . .
Samples also were placed in a Geer oven and held at 250F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in -- ~
a motor vehicle, such as an automobile, with the following `
results: ;
., Table XXIII
Color at 250F ::
Controls Examples Time (days) 1 2 20 21 22 23 24 0 White Wllite White White White Wllite White Pink Off White White White White White White 2 Tan Tan Pink Off Off Off Off White White White White 3 Tan Tan Pink Off Off Off Pink :`.
White White White .
4 Tan Tan Pink Pink Pink Off Pink White Dark Tan Pink Pink Pink Pink Pink Tan 6 Dark Tan Pink Pink Pink Pink Pink ~:~
Tan 7 Dark Tan Tan ~'ink Pink Pink Pink Tan The B-diketones dibenzoyl methane and stearoyl dibenzoyl methane markedly improve stability at moderate temperatures after heat processing.
~ .
-~` 2~22~.5 ~ ~
,.,, :.'.:.'...
xample 25 . .
Polyvinyl chloride resin compositions were made up; `;
having the following formulation: "
In~redient Parts by Wei~
Polyvinyl chloride homop~lymer (Oxy 9400) 100 Santici~er 711 (mixed C7-C11 ~`
alkyl phthalate) 30 Drapex 6. 8 (epoxidize,d soybean oil) 5. 0 Omyalite 90T (CaCO3) 15 Lorol GT-71 (fatty ester lubricant) 0, 25 .
TiO2 (R101) 0.25 Stabilizer 2, 5 Control Example 25 Stabilizer composed of:
, :
Ba nonyl phenate-BaCO3 (27% Ba) 21 21 Zinc 2-ethyl hexoate (22% Zn) 4.6 4.6 Cd 2-ethyl hexoate benzoate tallate solution (14% Cd) 17 17 ~;
Dlphenyl isodecyl phosphite 3 5 3 5 Diphenyl phosphite 1, 5 1. 5 Aromatic hydrocarbon -diluent 15.9 10. 9 Tall oil fatty acid 3 3 Antioxidant 2 2 ~
Dibenzoyl rnethane - 5 ~ --, .."~
`~ 202~5 :: ~
The stabilizer systern and other ingredients were :
blended with the polyvinyl chloride resin on a two-roll mill `-and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two hours. Samples were withdrawn at fifteen minute intervals and their appearance observed according to the color rating chart of Examples 1 to 5. The results are shown in Tables `
~IV anc~
Table XXIV
Color Rating at 350F
.~
Time (minutes) Control Example 25 O O
0 0 :~
0 ~`
105 1 1 :~
~ ` 2 ~ 2 2 g ~
`: `
Table X~
Color Rating at 375F ` -~
Time (minutes) Control Example 25 ~ -.
O O O ~, .
` ~` ~`.`
0 `:
.
105 2 2 .
The dibenzoyl methane clearly contributes no noticeable .
effect on heat stability at 350 and 375F, Samples also were placed in a Geer oven and held at 250F for up to eight days to simulate the moderate temperatures experienced by a motor vehicle component in a motor vehicle, such as an automobile, with the following results:
92 ~ ;:
2~22~5 ~ ~:
Table X~
Color at 2 50 F
Time (days) Control Example 25 0 White White `
1 Off White White 2 Light Tan Off White 3 Light Tan Off White 4 Light Tan Off White Tan Light Tan ~: `
6 Dark Tan Dark Tan -:
7 Dark Tan Dark Tan .
8 Dark Tan Dark Tan The ~-diketone, dibenzoyl methane, markedly improves ~:
stability at moderate temperatures after heat processing.
,~" ~.
2~228~
Example 26 -Polyvinyl chloride resin compositions were made up having the following formulation~
Ingredlent Parts by Weight 5 Polyvinyl chloride homopolymer (Oxy9400) 100 Santl~izer 711 (mixed C7-C11 ah'cyl phthalate) 30 Drapex 6. 8 (epoxidized soybean oil) 5J O
Omyalite 90T (CaCO3) 15 LorolGT-71 (fatty ester lubricant) 0. 25 `;
T iO2 (R 101) 0. 2 5 -Stabilizer 2. 5 Control Example 26 15 Stabilizer composed of:
Barium nonyl phenate solvent `
(50%) (12. 5% Ba) 14.7 - ;
Ba nonyl phenate-Ba 2-ethyl hexoate (12. 5% Ba) 14. 7 14. 66 `-Ba nonyl phenate-BaCO3 `-(27% Ba) 6.79 Zinc 2-ethyl hexoate - ~
(22% Zn) 1.3 1.33 ~ `
Cd benzoate tallate solvent (14% Cd) 33. 3 33.3 Cd 2-ethyl hexoate benzoate ~
tallate (14% Cd) 14. 7 14. 67 ~`
Diphenyl isodecyl phosphite 14. 5 14. 53 ~ -Triphenyl phosphite 3. 2 3. 3 ~;
Diphenyl phosphite 0. 31 1. 33 Mineral spirits 1. 4 4~ 8 ;
Antioxidant 1. 0 0. 33 Dibenzoyl methane - 5. 0 ~ ;~
~ 4 2022~S
The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two .
hours. Samples were withdrawn at fifteen minute intervals and their appearance observed according to the color rating :
chart of Examples 1 to 5. The results are shown in Tables XXVII and xx~TmO
Table ~VII :"
Color Rating at 350F
Time (minutes) Control Example 26 .
O O O ~ ~
0 0 ;
0 0 .
0 0 :
0 o `, ~:
`` 2 0 2 2 8 ~
Table X~III
-, ~
Color Rating at 375F : .
Time (minutes) ControlExample 26 ~ :
O O ' ;~`
~5 0 0 0 `
9Q 1 1 .-`~
The dibenzoyl methane clearly contributes no noticeable ~ ~:
effect on heat stability at 350 and 375F. `
Samples also were placed in a Geer oven and held at 250F for up to eight days to simulate the moderate temperatures experienced by a motor vehicle component in -a motor vehicle, such as an automobile, with the following results~
2~228~
Table X~
Colorat250F :
_ . , Time (days) Control Example 26 0 White White . .
1 White White 2 White White - ~
3 Off White Off White ~ ::
4 Light Tan Off White Light Tan Off White ;;
6 Tan Light Tan 7 Tan Light Tan 8 Tan Light Tan The B-diketone, dibenzoyl methane, markedly improves stability at moderate temperatures after heat processing. :~
. ~. . .
97 .
.:
2~228~S
Examples 27 and 28 Polyvinyl chloride resin compositions were made up having the following formulation:
gredient Parts by Weight Polyvinyl chloride homopolymer ~ -(Tenneco 225) 100 Santicizer 711 (mixed C7-Cll aLkyl phthalate plasticizer) 35 Drapex 6. 8 epoxidized soybean oil 5 Atomite (CaCO3) 20 ~;
Stearic acid 0~,25 Stabilizer 29 5 Control Example 27 Example 28 Stabilizer connposed of ~
, 13arium nonyl phenate B aC03 (27% Ba) 3. 92 16 16 .... ~
Barium nonyl phenate -~
( 12. 5% Ba) 24, 81 - -Cd 2-ethyl-hexoate (20% Cd) 3O 92 - -Cd benzoate-2-ethyl hexoate tallate (14% Cd) 43.1 50 50 Zn~ 2-ethyl hexoate (22 Yo Zn) 1. 3 1. 5 1. 5 Diphenyl phosphite 4 4 4 Diphenyl isodecyl phosphite 17 17 17 Oleic acid 0O 67 Cinnamic acid 0.4 0. 5 0O 5 Antioxidant 1, 0 - -Dibenzoyl methane - 59 0 5O 0 ~ - -Hydrocarbon diluent - 6. 0 6. 0 Zinc chelate of dibenzoyl methane - - 60 5 ~ ',.`' 2~22~
The zinc 2-ethyl hexoate and dibenzoyl methane formed the zinc chelate of dibenzoyl methane in situ. ~ `;
The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off. Samples were cut off from the sheets and ;.
heated in a Geer oven at 350F and 375F for up to two hoursO Samples were withdrawn at fifteen minute intervals, and the discoloration rated according to the scale in Examples 1 to 5. The results are shown in Tables X~ and XX~Io Table XXX
Color Rating at 350F
Time (minutes) ControlExample~27 Example 28 O O O o :
15 15 0 `
0 o 0 o o o .
120 2 2 2 ~-'~
, ~
.
~`` 2022~
Table XXXI ~ `:
Color Rating at 375F ~:
; - .
Time (minutes) Control Example 27 Example 28 O '` '~
O O ` ;: `
0 0 ` `
O o O
1 1 1 .
2 2 2 ``
The ~inc chelate of the ~-diketone, dibenzoyl methane, : ;~
clearly does not contribute to heat stability at 350 or 375F~
A plate-out test was run on all four resin compositions . ;;;
Red pigment was added to the composition and the mix milled ;
on the two-roll mill for five minutes at 325F, and sheeted off, ;
The clean-up sheet run thereafter was exactly the same in all four cases, showing the zinc chelate of the B-diketone had no 20 effect.
Thick press-polished panels were prepared from each `
composition, and were indistinguishable, one from the other, again showing the zinc chelate of the B-diketone had no effect. :
Samples also were placed in a Geer oven and held at 25 215F for up to sixteen days, to simulate the moderate temperatures experienced by motor vehicle components in a -motor vehicle such as an automobile, with the following results; ~
100 .....
,.~ .
.'-.' : ` 2i~2~5 Table XXXII ; ~:
Color Rating at 215F
Time (days)Control Example 27 Example 28 O O O O
1 0 0 0 `~`
4 1 0 ~ ~ `
O
7 2 1 ~ `
14 5 2 2 ~ ~
2 2 ~ .
.. ..
.
~ ~ ~ 2 ~
Example 18 Polyvinyl chloride resin connpositions were made up . ~ `
having the following formulation~
Ingredient Parts by Weight ~ -P olyvinyl chloride homopolym er ~ .
(Tenneco 225) 100 Santicizer 711 (mixed C7-C11 :.
a~yl phthalate plasticizer) 30 -Drapex 6. 8 epoxidized soybean oil 4 Blue dye 0.01 "~``
Stearic acid 0.25 Stabilizer 3. 0 ~ .
Control Exam~le 18 `~
Stabilizer composed of~
Barium nonyl phenate BaCO3 ;
(27~o Ba) 32.5 16 ~ ~ :
Cd 2-ethyl-hexoate (20% Cd) - 50 Cd benzoate-2-ethyl hexoate tallate (14% Cd) 27.4 -. . ~ -Zn~ 2-ethyl hexoate (22% Zn) 3~1 1. 5 ~ .` `.~ ~
Diphenyl phosphite 1. 6 4 Diphenyl isodecyl phosphite - 1~
Diphenyl 2-ethyl hexyl - `.
phosphite 35.
Cinnam ic acid - . 5 Mineral Spirits - 8. 5 ~ , Dibenzoyl methane 2, 5 2 ~J ~ .3 ~
The stabilizer system and other ingredients were ~ .
blended with the polyvinyl chloride resin on a two-roll mill, -and then sheeted offO
Blue-tinted convertible rear window press-polished panels were prepared from each composition, and clippings ~`
taken from each were placed in a Geer oven and held at 215F
for up to fourteen days, to simulate the moderate temperatures experienced by such rear windows when installed in an :;
automobile, with the following results: -:
: :.
`';
', ',..' ~
2 ~ 2 2 ~
`..',;;
Table XVII
Color at 215F
Time (days) Control Example 18 ` :~
0 Blue Blue ::
1 Unchanged Unchanged `
2 . Faded Blue Unchanged `
Barely Perceptible Unchanged 3 Blue Tint " ~` `
4 Light Gray Unchanged .`~
Gray Tan Faded Blue ;.
6 Light Tan Faded Blue 7 Light Tan Faded Blue : `
8 Light Tan Faded Blue : ~
9 Light Tan Barely Perceptible : ~`
Blue Tint Medium Tan Barely Perceptible Blue Tint .::
11 Medium Tan Light Gray ` .~`
12 Dark Tan Light Gray 13 Dark Tan Gray Tan 14 Dark Tan Gray Tan The ~ diketone clearly improves resistance to discoloration at 215F after heat-processing. ~
81 ., ~ '':
2 ~ 2 ,~
Example 19 Polyvinyl chloride resin compositions were made up having the following formulation~
Ingredient Parts by Weight Polyvinyl chloride homopolymer ~ -(Tenneco 225) 100 Santicizer 711 (mixed C7-C11 aL~yl phthalate plasticizer) 35 Drapex 6. 8 epoxidized soybean oil 5 `
Atomite (CaCO3) 20 Stearic acid 0. 25 .
Stabilizer 2. 5 Control E:xample 19 .:
...: .
Stabilizer composed of ~
Barium nonyl phenate BaCO3 ~::
(27~o Ba) 32. 5 16 Cd 2-ethyl-hexoate (20% Cd) 27.4 50 ~
Cd benzoate-2-ethyl hexoate ~ `. .`
Tallate (14% C'd) Zn. 2-ethyl hexoate 3.1 lo 5 `
Diphenyl phosphite 1.6 4 -Diphenyl isodecyl phosphite - 17 Diphenyl 2-ethyl hexyl phosphite 3 5 Cinnamic acid - 0. 5 ~-Mineral Spirits - 8. 5 Dibenzoyl methane - 2. 5 ' ' '' 82 ~
The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off~ Samples were cut off from the sheets -~:
and heated in a Geer oven at 350F and 375F for up to two hours, Samples were withdrawn at fifteen minute intervals, :~
and the discoloration rated according to the scale in ;;
Examples 1 ,to 5. The results are shown in Tables XVIII and XIXo ~ ~' Table XVIII
Color Rating at 350~F
.:
10~Time (minutes) Control Example 19 , O '`.'.' .~.' 0 0 ~-:
0 0 ',~:
0 0 '`~
105 1 1 - :''`''-~.~..' ;.
83 `:
~ ~ 2 ~ ~3 c3 l3 :
Table X~
Color Rating at 3753F
Time (minutes) ~~ohtrolExample 19 O `'`;
~.
0 0 -:
1 1 . :. .
1 1 :`
2 2 .
3 3 . ~ i 105 5 5 ` ````
120 7 7 ::
The ~-diketone, dibenzoyl methane, clearly does not contribute to heat stability at 350 or 375F.
Glove compartment boxes were prepared from each ..
composition, The boxes were placed in a Geer oven and held at 215F for up to fourteen days, to simulate the moderate -;
temperatures experienced by such components in an . .~`
automobile, with the following results:
~ J~ f~ 3 Table XX _ ~:
Color at 215 F
~) Control : Example 19 ;~
0 White White ~.
1 Unchanged Unchanged 2 Unchanged Unchanged 3 Dirty White Unchanged 4 Dirty White Unchanged :
Light Tan Unchanged ~-6 Light Tan Unchanged 7 Light Tan Dirty White 8 Medium Tan Dirty White 9 Medium Tan Dirty White :;
Medium Tan Dirty White 11 Dark Tan Dirty White ; :
12 Dark Tan Dirty White 13 Dark Tan Light Tan :
14 Dark Tan Light Tan The ~-diketone clearly improves resistance to 20 discoloration at 215F after heat-processing.
?~
Examples 20 to 24 `
- , .
Polyvinyl chloride resin compositions were made up having the following formulation: ~
Ingredient Parts by Weight -Polyvinyl chloride homopolymer (Oxy 9400) 100 ~antici~r 711 (mixed C7-C11 -` `
allcyl phthalate) 30 Drapex 6.8 (epoxidized soybean oil) 5.0 Omyalite 90T (CaC03) 15 -:
L~xiol GT-71 (fat~y ester lubricant~ O. 25 Microcheck 1 lD (fungic ide) 3.0 ` `
T iO2 (R 101) ' 0.25 `
Heat ~tabilizer 2. 5 ~ ':
Controls Examples 2 20 21 22 23 24 `
Heat stabilizer composed of: -. . .
Ba nonyl phenate-BaCO3 (27% Ba) 2409 24.~ 24.9 24.9 24,9 24.9 24,9 Zinc 2-ethyl hexoate `
(22% Zn) 2.7 2.7 2.7 2.7 2.7 2.7 207 Cd 2-ethyl hexoate ~-(10% Cd) 41.2 41.2 41.2 41.2 41.2 41.2 41.2 Phenyl diisodecyl pho~phite 21.2 21.2 21.2 21.2 2102 21.2 2102 Diphenyl phosphite 3 3 3 3 3 3 3 Oleic acid 006 0.6 0.6 006 0,6 006 006 Mineral spirits 5 5 5 5 5 5 5 Cinnamic acid 0.35 0.35 0.35 0.35 0.35 0.35 0O35 30 Antioxidant 86 -~
2 ~ 3 : ~
Parts by Weight per 100 Parts of Polymer Other Stabilizers Controls Examples added sepa ately 1 _2 _ 21 22 23 24 2-Hydroxy-4-octyl~
oxybenzophenone 0~ 5 2, 5 0. 5 0O 5 1.0 0O 5 0~ 5 -"
Stearoyl benzoyl :
methane - 0, 2 0. 5 - - 0. 5 0O 5 Dibenzoyl methane - - - 0.2 0, 5 The stabilizer system and other ingredients were . ~"
blended with the polyvinyl chloride resin on a two-roll mill and then sheeted off~ Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two : .
hours~ Samples were withdrawn at fifteen minute intervals ~
and their appearance observed according to the color rating ` .
chart of Examples 1 to 5~ The results are shown in Tables X~ and XX, 87 :
2 ~ 2 2 ~ 3 r3 ~'-,','''~
.",, Table X~ : .
Color Rating at 350F . :
Controls Examples Time (minutes) 1 2 ~) 21 22 23 24 : :
0 0 0 0 0 0 0 0 ..
4 5 0 0 0 0 0 0 0 `
0 0 0 0 `
0 0 o 0 0 0 0 -:.
105 1 ~ 1 1 1 1 1 `
Table ~II
t5 Color Rating at 375F
Controls E:xamples ` ~ `
Time (minutes) 1 Z ~ Z ~ 24 O O O O O O O O ''~' 0 0 0 0 0 0 0 ~
~0 30 0 0 0 0 0 0 0 ` .
0 0 0 0 0 o 0 0 0 0 0 o 0 0 ``~
105 1 1 1 1 1 1 1 .
~'''.' 88 ~ ~
2 2 ~
. ................................................................... ~ -, . .
:``' The dibenzoyl methane clearly contributes no noticeable `- `
effect on heat stability at 350 and 375F. . .
Samples also were placed in a Geer oven and held at 250F for up to seven days to simulate the moderate temperatures experienced by a motor vehicle component in -- ~
a motor vehicle, such as an automobile, with the following `
results: ;
., Table XXIII
Color at 250F ::
Controls Examples Time (days) 1 2 20 21 22 23 24 0 White Wllite White White White Wllite White Pink Off White White White White White White 2 Tan Tan Pink Off Off Off Off White White White White 3 Tan Tan Pink Off Off Off Pink :`.
White White White .
4 Tan Tan Pink Pink Pink Off Pink White Dark Tan Pink Pink Pink Pink Pink Tan 6 Dark Tan Pink Pink Pink Pink Pink ~:~
Tan 7 Dark Tan Tan ~'ink Pink Pink Pink Tan The B-diketones dibenzoyl methane and stearoyl dibenzoyl methane markedly improve stability at moderate temperatures after heat processing.
~ .
-~` 2~22~.5 ~ ~
,.,, :.'.:.'...
xample 25 . .
Polyvinyl chloride resin compositions were made up; `;
having the following formulation: "
In~redient Parts by Wei~
Polyvinyl chloride homop~lymer (Oxy 9400) 100 Santici~er 711 (mixed C7-C11 ~`
alkyl phthalate) 30 Drapex 6. 8 (epoxidize,d soybean oil) 5. 0 Omyalite 90T (CaCO3) 15 Lorol GT-71 (fatty ester lubricant) 0, 25 .
TiO2 (R101) 0.25 Stabilizer 2, 5 Control Example 25 Stabilizer composed of:
, :
Ba nonyl phenate-BaCO3 (27% Ba) 21 21 Zinc 2-ethyl hexoate (22% Zn) 4.6 4.6 Cd 2-ethyl hexoate benzoate tallate solution (14% Cd) 17 17 ~;
Dlphenyl isodecyl phosphite 3 5 3 5 Diphenyl phosphite 1, 5 1. 5 Aromatic hydrocarbon -diluent 15.9 10. 9 Tall oil fatty acid 3 3 Antioxidant 2 2 ~
Dibenzoyl rnethane - 5 ~ --, .."~
`~ 202~5 :: ~
The stabilizer systern and other ingredients were :
blended with the polyvinyl chloride resin on a two-roll mill `-and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two hours. Samples were withdrawn at fifteen minute intervals and their appearance observed according to the color rating chart of Examples 1 to 5. The results are shown in Tables `
~IV anc~
Table XXIV
Color Rating at 350F
.~
Time (minutes) Control Example 25 O O
0 0 :~
0 ~`
105 1 1 :~
~ ` 2 ~ 2 2 g ~
`: `
Table X~
Color Rating at 375F ` -~
Time (minutes) Control Example 25 ~ -.
O O O ~, .
` ~` ~`.`
0 `:
.
105 2 2 .
The dibenzoyl methane clearly contributes no noticeable .
effect on heat stability at 350 and 375F, Samples also were placed in a Geer oven and held at 250F for up to eight days to simulate the moderate temperatures experienced by a motor vehicle component in a motor vehicle, such as an automobile, with the following results:
92 ~ ;:
2~22~5 ~ ~:
Table X~
Color at 2 50 F
Time (days) Control Example 25 0 White White `
1 Off White White 2 Light Tan Off White 3 Light Tan Off White 4 Light Tan Off White Tan Light Tan ~: `
6 Dark Tan Dark Tan -:
7 Dark Tan Dark Tan .
8 Dark Tan Dark Tan The ~-diketone, dibenzoyl methane, markedly improves ~:
stability at moderate temperatures after heat processing.
,~" ~.
2~228~
Example 26 -Polyvinyl chloride resin compositions were made up having the following formulation~
Ingredlent Parts by Weight 5 Polyvinyl chloride homopolymer (Oxy9400) 100 Santl~izer 711 (mixed C7-C11 ah'cyl phthalate) 30 Drapex 6. 8 (epoxidized soybean oil) 5J O
Omyalite 90T (CaCO3) 15 LorolGT-71 (fatty ester lubricant) 0. 25 `;
T iO2 (R 101) 0. 2 5 -Stabilizer 2. 5 Control Example 26 15 Stabilizer composed of:
Barium nonyl phenate solvent `
(50%) (12. 5% Ba) 14.7 - ;
Ba nonyl phenate-Ba 2-ethyl hexoate (12. 5% Ba) 14. 7 14. 66 `-Ba nonyl phenate-BaCO3 `-(27% Ba) 6.79 Zinc 2-ethyl hexoate - ~
(22% Zn) 1.3 1.33 ~ `
Cd benzoate tallate solvent (14% Cd) 33. 3 33.3 Cd 2-ethyl hexoate benzoate ~
tallate (14% Cd) 14. 7 14. 67 ~`
Diphenyl isodecyl phosphite 14. 5 14. 53 ~ -Triphenyl phosphite 3. 2 3. 3 ~;
Diphenyl phosphite 0. 31 1. 33 Mineral spirits 1. 4 4~ 8 ;
Antioxidant 1. 0 0. 33 Dibenzoyl methane - 5. 0 ~ ;~
~ 4 2022~S
The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill and then sheeted off. Samples were cut off from the sheets and heated in a Geer oven at 350F and 375F for up to two .
hours. Samples were withdrawn at fifteen minute intervals and their appearance observed according to the color rating :
chart of Examples 1 to 5. The results are shown in Tables XXVII and xx~TmO
Table ~VII :"
Color Rating at 350F
Time (minutes) Control Example 26 .
O O O ~ ~
0 0 ;
0 0 .
0 0 :
0 o `, ~:
`` 2 0 2 2 8 ~
Table X~III
-, ~
Color Rating at 375F : .
Time (minutes) ControlExample 26 ~ :
O O ' ;~`
~5 0 0 0 `
9Q 1 1 .-`~
The dibenzoyl methane clearly contributes no noticeable ~ ~:
effect on heat stability at 350 and 375F. `
Samples also were placed in a Geer oven and held at 250F for up to eight days to simulate the moderate temperatures experienced by a motor vehicle component in -a motor vehicle, such as an automobile, with the following results~
2~228~
Table X~
Colorat250F :
_ . , Time (days) Control Example 26 0 White White . .
1 White White 2 White White - ~
3 Off White Off White ~ ::
4 Light Tan Off White Light Tan Off White ;;
6 Tan Light Tan 7 Tan Light Tan 8 Tan Light Tan The B-diketone, dibenzoyl methane, markedly improves stability at moderate temperatures after heat processing. :~
. ~. . .
97 .
.:
2~228~S
Examples 27 and 28 Polyvinyl chloride resin compositions were made up having the following formulation:
gredient Parts by Weight Polyvinyl chloride homopolymer ~ -(Tenneco 225) 100 Santicizer 711 (mixed C7-Cll aLkyl phthalate plasticizer) 35 Drapex 6. 8 epoxidized soybean oil 5 Atomite (CaCO3) 20 ~;
Stearic acid 0~,25 Stabilizer 29 5 Control Example 27 Example 28 Stabilizer connposed of ~
, 13arium nonyl phenate B aC03 (27% Ba) 3. 92 16 16 .... ~
Barium nonyl phenate -~
( 12. 5% Ba) 24, 81 - -Cd 2-ethyl-hexoate (20% Cd) 3O 92 - -Cd benzoate-2-ethyl hexoate tallate (14% Cd) 43.1 50 50 Zn~ 2-ethyl hexoate (22 Yo Zn) 1. 3 1. 5 1. 5 Diphenyl phosphite 4 4 4 Diphenyl isodecyl phosphite 17 17 17 Oleic acid 0O 67 Cinnamic acid 0.4 0. 5 0O 5 Antioxidant 1, 0 - -Dibenzoyl methane - 59 0 5O 0 ~ - -Hydrocarbon diluent - 6. 0 6. 0 Zinc chelate of dibenzoyl methane - - 60 5 ~ ',.`' 2~22~
The zinc 2-ethyl hexoate and dibenzoyl methane formed the zinc chelate of dibenzoyl methane in situ. ~ `;
The stabilizer system and other ingredients were blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off. Samples were cut off from the sheets and ;.
heated in a Geer oven at 350F and 375F for up to two hoursO Samples were withdrawn at fifteen minute intervals, and the discoloration rated according to the scale in Examples 1 to 5. The results are shown in Tables X~ and XX~Io Table XXX
Color Rating at 350F
Time (minutes) ControlExample~27 Example 28 O O O o :
15 15 0 `
0 o 0 o o o .
120 2 2 2 ~-'~
, ~
.
~`` 2022~
Table XXXI ~ `:
Color Rating at 375F ~:
; - .
Time (minutes) Control Example 27 Example 28 O '` '~
O O ` ;: `
0 0 ` `
O o O
1 1 1 .
2 2 2 ``
The ~inc chelate of the ~-diketone, dibenzoyl methane, : ;~
clearly does not contribute to heat stability at 350 or 375F~
A plate-out test was run on all four resin compositions . ;;;
Red pigment was added to the composition and the mix milled ;
on the two-roll mill for five minutes at 325F, and sheeted off, ;
The clean-up sheet run thereafter was exactly the same in all four cases, showing the zinc chelate of the B-diketone had no 20 effect.
Thick press-polished panels were prepared from each `
composition, and were indistinguishable, one from the other, again showing the zinc chelate of the B-diketone had no effect. :
Samples also were placed in a Geer oven and held at 25 215F for up to sixteen days, to simulate the moderate temperatures experienced by motor vehicle components in a -motor vehicle such as an automobile, with the following results; ~
100 .....
,.~ .
.'-.' : ` 2i~2~5 Table XXXII ; ~:
Color Rating at 215F
Time (days)Control Example 27 Example 28 O O O O
1 0 0 0 `~`
4 1 0 ~ ~ `
O
7 2 1 ~ `
14 5 2 2 ~ ~
2 2 ~ .
16 5 2 2 :-The zinc chelate of dibenzoyl methane clearly improves resistancè to discoloration at 215F after heat-processing.
~... ~,.
,.'-",''','''' .. - .
''~",,' 2~2~5 ~ :
A blue dye was then added with the stabilizer system --and other ingredients of the polyvi.nyl chloride resin composition -~
described above, and blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off.
Blue-tinted press-polished convertible rear window ~ ~
panels were prepared from each composition, and clippings ;; .
taken from each were placed in a Geer oven and heated at 215F
for up to sixteen days, to simulate the moderate temperatures :.
experienced by such rear windows when installed in an .~;~
automobileO The results were the same as in Table XX~IL ~`
The Zn chelate of dibenzoyl methane clearly improved .
resistance to discoloration at 215F after heat-processing. ~ "
", -',`,"..-'~.
- 2~2~
Exam~les 29 to 32 Polyvinyl chloride resin compositions were made up having the following formulation:
Ingredient Parts by Weight ~ ;~
Polyvinyl chloride homopolymer ~ :
(~eon llOX 450) 100 D~octyl phthalate 40 :
Drapex 6, 8 epoxidized soybean oil 5 ;`
Atomite (CaC09) 20 Stearic acid 0.2 Stabilizer 2, 5 Examples Control 29 30 31 32 Stabilizer composed of: ~.
Barium nonyl phenate Ba.CO3 ~ .
(27~o Ba) 3. 92 3. 92 ~6 16 16 ;
Barium nonyl phenate (12. 5% Ba) 24. 81 24. 81 Cd 2-ethyl-hexoate (20% Cd) 3, 92 3. 92 ~ -.;
Cd benzoate-2-ethyl hexoate tallate (14% Cd) 43.1 43.1 50 50 50 .
Zn~ 2-ethyl hexoate (22% Zn) 1. 3 1. 3 1. 5 1. 5 lo 5 `~
Diphenyl phosphite 4 4 4 4 4 Diphenyl isodecyl phosphite 17 17 17 17 17 . .
2 5 Oleic acid 0. 67 0.67 _ .
. . .
Cinnamic acid 0.. 4 0.4 0. 5 0~ 5 0. 5 .. . ...
Antioxidant 1. 0 1. 0 - - -Dibenzoyl methane - - 2. 5 Hydrocarbon diluent - - 2. 5 8. 5 80 5 Cadmium chelate of ~ .
dibenzoyl methane - 0.1 - 20 5 40 0 ~
'''",' 103 ~;.
2~228~
The cadmium 2-ethyl hexoate and dibenzoyl methane formed ~ ~ ~
the cadmium chelate of di~enzoyl methane in SitU in Example 290 ~ .
The stabilizer system and other ingredients were blended ;
with the polyvinyl chloride resin on a two-roll mill, and then sheeted off. Samples were cut off from the sheets and heated in a Gëer oven at 350F and 375F.for up to two ~:
hours. Samples were withdrawn at fifteen minute intervals, and the discoloration rated accorcling to the scale in -Examples 1 to 5O The results are shown in Tables ~XIII and XXXIV
Table ~xm Color Rating at 350F
Examples ; `
Time (minutes) Control 2~ 32 O O ~O O O O ;`
~;
; ~`
0 ; ~ "
~` ~
1 1 1 1 1 ~`:
' ` .
,, ~,~
. ~',.' Table ~XIV
~. ~
Color Rating at 375F ~ ~
: .
Examples -Time (minutes)Control 29 30 31 32 -0 0 o 0 o 0 - :~
0 o 0 1 1 1 1 1 .
1 1 1 1 1 .---i 2 ~ 2 2 2 120 10 10 10 10 10 ~;
The cadmium chelate of dibenzoyl me~hane clearly does not contribute to heat stability at 350 or 375F, ;~`
A plate-out test was run on all four resin compositions. . .
Red pigment was added to the composition and the mix milled - :........
on the two-roll mill for five minutes at 325F, and sheeted offO `
The clean-up sheet run thereafter was exactly the same in all .
Iour cases, showing the cadmium chelate of the B-diketone had no effect~
Thick press-polished panels were prepared from each composition, and were indistinguishable, one from the other, : ` .
again showing the cadmium chelate of the B-diketone had no effect. --Samples also were placed in a Geer oven and held at 215F for up to fourteen days, to simulate the moderate -' ~"',' : .
105 ~ ~
2~2285~
temperatures experienced by motor vehicle components in a motor vehicle such as an automobile, with the following results:
Table XXXV ;
Color Rating at 215F
Examples ~ `.
Time (days) Control 29 30 31 32 O O O
, 0 0 O
3 ```
4 1 o o 0 1 :
1 0 0 0 1 ;
6 2 0 0 0 1 :~
7 2 1 1 1 1 `
8 3 2 1 1 ~ `.
3 1 1 1 `
11 6 4 1 1 1 :-12 6 4 1 1 1 :-The cadmium chelate of dibenzoyl methane clearly improves -resistance to discoloration at 215F after heat-processing. Example - .:
29 sh~ws that even Oo l chelate is helpful, but Examples 30 and 31 ~ `
25 show that 2. 5 and 4 of chelate are better.
106 ` .
2~22~S
A blue dye was then added with the stabilizer system and other ingredients of the polyvinyl chloride resin composition described above, and blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off, ~:
Blue-tinted press `polished convertible rear window panels were prepared from each composition, and clippings ~`
taken from each were placed in a Geer oven and heated at 215F ~
for up to sixteen days, to simulate the moderate temperatures `- `
experienced by such rear windows when installed in an ~ ~`
automobile. The results were the same as in Table XX~
The cadmium chelate of dibenzoyl methane clearly :
.,.~-. .
improved re~istance to discoloration at 215F after heat-processingO
;
:
~, .
'''`'''''~
;~
107 `
~... ~,.
,.'-",''','''' .. - .
''~",,' 2~2~5 ~ :
A blue dye was then added with the stabilizer system --and other ingredients of the polyvi.nyl chloride resin composition -~
described above, and blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off.
Blue-tinted press-polished convertible rear window ~ ~
panels were prepared from each composition, and clippings ;; .
taken from each were placed in a Geer oven and heated at 215F
for up to sixteen days, to simulate the moderate temperatures :.
experienced by such rear windows when installed in an .~;~
automobileO The results were the same as in Table XX~IL ~`
The Zn chelate of dibenzoyl methane clearly improved .
resistance to discoloration at 215F after heat-processing. ~ "
", -',`,"..-'~.
- 2~2~
Exam~les 29 to 32 Polyvinyl chloride resin compositions were made up having the following formulation:
Ingredient Parts by Weight ~ ;~
Polyvinyl chloride homopolymer ~ :
(~eon llOX 450) 100 D~octyl phthalate 40 :
Drapex 6, 8 epoxidized soybean oil 5 ;`
Atomite (CaC09) 20 Stearic acid 0.2 Stabilizer 2, 5 Examples Control 29 30 31 32 Stabilizer composed of: ~.
Barium nonyl phenate Ba.CO3 ~ .
(27~o Ba) 3. 92 3. 92 ~6 16 16 ;
Barium nonyl phenate (12. 5% Ba) 24. 81 24. 81 Cd 2-ethyl-hexoate (20% Cd) 3, 92 3. 92 ~ -.;
Cd benzoate-2-ethyl hexoate tallate (14% Cd) 43.1 43.1 50 50 50 .
Zn~ 2-ethyl hexoate (22% Zn) 1. 3 1. 3 1. 5 1. 5 lo 5 `~
Diphenyl phosphite 4 4 4 4 4 Diphenyl isodecyl phosphite 17 17 17 17 17 . .
2 5 Oleic acid 0. 67 0.67 _ .
. . .
Cinnamic acid 0.. 4 0.4 0. 5 0~ 5 0. 5 .. . ...
Antioxidant 1. 0 1. 0 - - -Dibenzoyl methane - - 2. 5 Hydrocarbon diluent - - 2. 5 8. 5 80 5 Cadmium chelate of ~ .
dibenzoyl methane - 0.1 - 20 5 40 0 ~
'''",' 103 ~;.
2~228~
The cadmium 2-ethyl hexoate and dibenzoyl methane formed ~ ~ ~
the cadmium chelate of di~enzoyl methane in SitU in Example 290 ~ .
The stabilizer system and other ingredients were blended ;
with the polyvinyl chloride resin on a two-roll mill, and then sheeted off. Samples were cut off from the sheets and heated in a Gëer oven at 350F and 375F.for up to two ~:
hours. Samples were withdrawn at fifteen minute intervals, and the discoloration rated accorcling to the scale in -Examples 1 to 5O The results are shown in Tables ~XIII and XXXIV
Table ~xm Color Rating at 350F
Examples ; `
Time (minutes) Control 2~ 32 O O ~O O O O ;`
~;
; ~`
0 ; ~ "
~` ~
1 1 1 1 1 ~`:
' ` .
,, ~,~
. ~',.' Table ~XIV
~. ~
Color Rating at 375F ~ ~
: .
Examples -Time (minutes)Control 29 30 31 32 -0 0 o 0 o 0 - :~
0 o 0 1 1 1 1 1 .
1 1 1 1 1 .---i 2 ~ 2 2 2 120 10 10 10 10 10 ~;
The cadmium chelate of dibenzoyl me~hane clearly does not contribute to heat stability at 350 or 375F, ;~`
A plate-out test was run on all four resin compositions. . .
Red pigment was added to the composition and the mix milled - :........
on the two-roll mill for five minutes at 325F, and sheeted offO `
The clean-up sheet run thereafter was exactly the same in all .
Iour cases, showing the cadmium chelate of the B-diketone had no effect~
Thick press-polished panels were prepared from each composition, and were indistinguishable, one from the other, : ` .
again showing the cadmium chelate of the B-diketone had no effect. --Samples also were placed in a Geer oven and held at 215F for up to fourteen days, to simulate the moderate -' ~"',' : .
105 ~ ~
2~2285~
temperatures experienced by motor vehicle components in a motor vehicle such as an automobile, with the following results:
Table XXXV ;
Color Rating at 215F
Examples ~ `.
Time (days) Control 29 30 31 32 O O O
, 0 0 O
3 ```
4 1 o o 0 1 :
1 0 0 0 1 ;
6 2 0 0 0 1 :~
7 2 1 1 1 1 `
8 3 2 1 1 ~ `.
3 1 1 1 `
11 6 4 1 1 1 :-12 6 4 1 1 1 :-The cadmium chelate of dibenzoyl methane clearly improves -resistance to discoloration at 215F after heat-processing. Example - .:
29 sh~ws that even Oo l chelate is helpful, but Examples 30 and 31 ~ `
25 show that 2. 5 and 4 of chelate are better.
106 ` .
2~22~S
A blue dye was then added with the stabilizer system and other ingredients of the polyvinyl chloride resin composition described above, and blended with the polyvinyl chloride resin on a two-roll mill, and then sheeted off, ~:
Blue-tinted press `polished convertible rear window panels were prepared from each composition, and clippings ~`
taken from each were placed in a Geer oven and heated at 215F ~
for up to sixteen days, to simulate the moderate temperatures `- `
experienced by such rear windows when installed in an ~ ~`
automobile. The results were the same as in Table XX~
The cadmium chelate of dibenzoyl methane clearly :
.,.~-. .
improved re~istance to discoloration at 215F after heat-processingO
;
:
~, .
'''`'''''~
;~
107 `
Claims (28)
1. A shaped motor vehicle component having an improved stability at moderate temperatures, composed of a polyvinyl chloride resin composition comprising a vinyl chloride polymer formed at least in part of the recurring group, and having a chlorine content in excess of 40%, where X is either hydrogen or chlorine, at least one heat stabilizer in a sufficient amount to impart heat processing stability during shaping, and a .beta.-diketone in a sufficient amount to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer, the .beta.-diketone having the formula:
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic.
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic.
2. A shaped motor vehicle component according to claim 1, wherein M is hydrogen and the formula is
3. A shaped motor vehicle component according to claim 2, wherein the .beta.-diketone is dibenzoylmethane.
4. A shaped motor vehicle component according to claim 2, wherein the .beta.-diketone is stearoyl benzoyl methane.
5. A shaped motor vehicle component according to claim 1, wherein M is a metal and the formula is
6. A shaped motor vehicle component according to claim 5, wherein the metal is selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al and Sb.
7. A shaped motor vehicle component according to claim 1, wherein both R and R" are aromatic and R' is hydrogen.
8. A shaped motor vehicle component according to claim 1, wherein R is aliphatic or cycloaliphatic, R" is aromatic and R' is hydrogen.
9. A shaped motor vehicle component according to claim 1, in which the heat stabilizer is in a sufficient amount to improve the resistance of the polyvinyl chloride to deterioration in physical properties during heat processing, including, for example, discoloration, change in melt viscosity and embrittlement, within the range from about 0.001 to about 5%
total heat stabilizers by weight of the polymer, and the .beta.-diketone is in an amount to impart resistance to deterioration when exposed to moderate temperatures within the range from about 150° to about 280°F after heat processing, including, for example, discoloration and embrittlement, within the range from about 0.001 to about 5% .beta.-diketone by weight of the polymer.
total heat stabilizers by weight of the polymer, and the .beta.-diketone is in an amount to impart resistance to deterioration when exposed to moderate temperatures within the range from about 150° to about 280°F after heat processing, including, for example, discoloration and embrittlement, within the range from about 0.001 to about 5% .beta.-diketone by weight of the polymer.
10. A shaped motor vehicle component according to claim 1, in which the vinyl chloride polymer is polyvinyl chloride homopolymer.
11. A shaped motor vehicle component according to claim 1, in which the vinyl chloride polymer is a copolymer of vinyl chloride and another copolymerizable monomer.
12. A stabilizer system for vinyl chloride polymer compositions to be formed into a shaped motor vehicle component having an improved stability at moderate temperatures, comprising a blend of:
(a) a .beta.-diketone having the formula:
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic;
said .beta.-diketone being in an amount of from about 10 to about 35 parts by weight to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer; and (b) a heat stabilizer in an amount of from about 10 to about 35 parts by weight to impart heat processing stability during shaping.
(a) a .beta.-diketone having the formula:
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic;
said .beta.-diketone being in an amount of from about 10 to about 35 parts by weight to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer; and (b) a heat stabilizer in an amount of from about 10 to about 35 parts by weight to impart heat processing stability during shaping.
13. A stabilizer system for vinyl chloride polymer compositions according to claim 12 in which the heat stabilizer is a polyvalent metal organic acid salt, the acid being an organic nonnitrogenous monocarboxylic acid having from six to twenty four carbon atoms, and the polyvalent metal being selected from the group consisting of barium, calcium, cadmium, magnesium, strontium, stannous tin and zinc.
14. A stabilizer system for vinyl chloride polymer compositions according to claim 12 in which the heat stabilizer is an organic phosphite.
15. A stabilizer system for vinyl chloride polymer compositions according to claim 12 in which the heat stabilizer is a polyvalent metal organic acid salt, the acid being an organic nonnitrogenous monocarboxylic acid having from six to twenty four carbon atoms, and the polyvalent metal being selected from the group consisting of barium, calcium, cadmium, magnesium, strontium, stannous tin and zinc, and an organic phosphite.
16. A stabilizer system for vinyl chloride polymer compositions according to claim 12 in which the heat stabilizer is a phenolic antioxidant in an amount from about 10 to about 35 parts by weight
17. A vinyl chloride polymer composition for forming into a motor vehicle component having an improved stability at moderate temperatures, comprising a vinyl chloride polymer formed at least in part of the recurring group, and having a chlorine content in excess of 40%, where X is either hydrogen or chlorine, at least one heat stabilizer in a sufficient amount to impart heat processing stability during shaping, and a .beta.-diketone having the formula:
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic;
said .beta.-diketone being in a sufficient amount to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer.
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic;
said .beta.-diketone being in a sufficient amount to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer.
18. A shaped motor vehicle component according to claim 17, in which the vinyl chloride polymer is polyvinyl chloride homopolymer.
19. A shaped motor vehicle component according to claim 17, in which the vinyl chloride polymer is a copolymer of vinyl chloride and another copolymerizable monomer.
20. A process for preparing a motor vehicle component having an improved stability at moderate temperatures, which comprises forming a vinyl chloride resin composition at a heat processing temperature within the range from about 300 to about 400°F in the selected shape, the composition comprising a vinyl chloride polymer formed at least in part of the recurring group, and having a chlorine content in excess of 40%, where X is either hydrogen or chlorine, at least one heat stabilizer in a sufficient amount to impart heat processing stability during shaping, and a .beta.-diketone having the formula:
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic;
said .beta.-ketone being in a sufficient amount to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer, and then, after heat processing, exposing the shaped motor vehicle component to moderate temperatures within the range from about 150° to about 215°F.
wherein M is a metal or hydrogen, n is the valence of M, R, R' and R" are selected from the group consisting of aliphatic having from eleven to eighteen carbon atoms, cycloaliphatic having from eleven to eighteen carbon atoms, and aromatic hydrocarbon, haloaromatichydrocarbon, alkoxyaromatic-hydrocarbon and alkylenedioxyaromatic hydrocarbon having from six to about eighteen carbon atoms, and from none to seven halogen atoms, and from none to two alkoxy or alkylene-dioxyhydrocarbon groups, provided, that R' can also be hydrogen, and that only one of R and R" can be aliphatic or cycloaliphatic;
said .beta.-ketone being in a sufficient amount to provide, after shaping, stability at moderate temperatures not provided by any residual heat stabilizer, and then, after heat processing, exposing the shaped motor vehicle component to moderate temperatures within the range from about 150° to about 215°F.
21. A process according to claim 20, in which M is hydrogen and the formula is
22. A process according to claim 21, in which the .beta.-diketone is dibenzoylmethane.
23. A process according to claim 21, in which the .beta.-diketone is stearoyl benzoyl methane.
24. A process according to claim 20, in which M is a metal and the formula is
25. A process according to claim 24, in which the metal is selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al and Sb.
26. A process according to claim 20, in which the heat stabilizer is in a sufficient amount to improve the resistance of the polyvinyl chloride to deterioration in physical properties during heat processing, including, for example, discoloration, reduction in melt viscosity and embrittlement, within the range from about 0.001 to about 5% total heat stabilizers by weight of the polymer, and the .beta.-diketone is in an amount to impart resistance to deterioration when exposed to moderate temperatures within the range from about 150° to about 215°F after heat processing, including, for example, discoloration and embrittlement, within the range from about 0.001 to about 5% .beta.-diketone by weight of the polymer.
27. A process according to claim 20, in which the vinyl chloride polymer is polyvinyl chloride homopolymer.
28. A process according to claim 20, in which the vinyl chloride polymer is a copolymer of vinyl chloride and another copolymerizable monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2022855 CA2022855A1 (en) | 1990-08-08 | 1990-08-08 | Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2022855 CA2022855A1 (en) | 1990-08-08 | 1990-08-08 | Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2022855A1 true CA2022855A1 (en) | 1992-02-09 |
Family
ID=4145670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2022855 Abandoned CA2022855A1 (en) | 1990-08-08 | 1990-08-08 | Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2022855A1 (en) |
-
1990
- 1990-08-08 CA CA 2022855 patent/CA2022855A1/en not_active Abandoned
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4957954A (en) | Stabilizer compositions for polyvinyl chloride resins and stabilized polyvinyl chloride resin compositions | |
| US4427816A (en) | β-Diketone and hydrotalcite stabilizer compositions for halogen-containing polymers and polymer compositions containing the same | |
| US4221687A (en) | Anti-yellowing composition | |
| US4782170A (en) | Liquid polyvinyl chloride resin stabilizer systems based on complexes of organic triphosphites with zinc chloride | |
| US4244848A (en) | Halogen containing resin composition | |
| US4371651A (en) | Stabilizer compositions and polyvinyl halide resin compositions containing 1,3-dicarbonyl compounds | |
| US4080364A (en) | Stabilization of polyolefins against degradative deterioration as a result of exposure to light and air at elevated temperatures | |
| US4282141A (en) | Ortho-substituted phenyl phosphite additive composition | |
| US4298520A (en) | Phenolic ester synthetic resin stabilizers | |
| US4348308A (en) | Ortho-substituted aryl phosphite additive composition | |
| US4217258A (en) | Stabilized halogen-containing resin composition | |
| CA1339763C (en) | Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions | |
| US5985959A (en) | Stabilized vinyl chloride polymer compositions | |
| US4105629A (en) | Synthetic resin stabilizer comprising a thioether ester and hindered phenolic carbonate | |
| US4381360A (en) | 1,3-Dicarbonyl compounds and polyvinyl halide resin compositions containing the same | |
| US4950704A (en) | Improving stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions | |
| EP1621576B1 (en) | Thermal stabilizer compositions for halogen-containing vinyl polymers | |
| US4279805A (en) | Alkylene-bis-thioalkanoic acid amide stabilizers for synthetic resins and synthetic resin compositions containing the same | |
| US3261791A (en) | Polyolefins stabilized with a glyoxime | |
| EP0073386B1 (en) | Synthetic resin compositions containing 2,2,6,6-tetramethyl piperidyl ethers | |
| CA2022855A1 (en) | Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions | |
| EP0040286A2 (en) | Polyvinyl halide resin compositions containing 1,3 Dicarbonyl compounds | |
| US4224218A (en) | Stabilized vinyl chloride polymer comprising a metal mono-organic phosphite | |
| EP0047894B1 (en) | Homogeneous storage-stable liquid barium-cadmium-triphosphite stabilizer systems for polyvinyl chloride resins | |
| US4624980A (en) | N-t-alkyl-N-sec-alkyl secondary amine compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |