JPS60144343A - Stable liquid antimony organic sulfur-containing compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Antimony mercaptide has been proposed as a stabilizer for halogenated vinyl resins to inhibit thermal decomposition during molding and processing of the halogenated vinyl resins into useful articles. Prior art patents disclosing such antimony organosulfur-containing compounds and their use as stabilizers include U.S. Pat. .220, No. 3,
No. 466.261 and No. 31530.158 are included. In past commercial implementations, such as Shijinabe,
Antimony mercaptide has various disadvantages, such as its tendency to leach from molded or processed pVC plastic materials and its cost, and there are no other advantages of use that outweigh such disadvantages. Due to its shortcomings, it was not widely used as a stabilizer. No. 3,887,508 to the present applicant is directed to improvements in the use of antimony organosulfur-containing compounds in combination with carboxylic acid metal salts. U.S. Patent No. &887
, 508, the use and effectiveness of such antimony compounds improves the thermal stability of vinyl halide resins to an unexpected degree. However, there are several such antimony compounds vl! I tend to deteriorate or become unstable on storage.

+f Gusho 51-6300, which is the earlier application filed by the present applicant.
1 aims to record 9 in the history of antimony organic compound S-1 compound halogenated vinyl chloride and shaving ice.

The invention, in one aspect, provided a synergistic thermal stabilizer composition of an antimony compound and an ortho-dihydric phenol as stabilizers. Another advantageous feature is the provision of antimony organosulfur-containing compounds that are liquid at ambient temperatures and storage stable. Such stable liquid compositions are easily incorporated into halogenated vinyl resin systems and provide synergistically heat-stabilized resin systems with high resistance to both initial discoloration of molded articles and long-term thermal degradation. It has been found that antimony organosulfur-containing compounds can be made storage stable by certain dihydric phenols,
It was done.

This application further extends liquid antimony compositions that are made stable to storage or use at ambient temperatures by the addition of phenolic compounds. For example,
Liquid antimony organosulfur-containing compounds, including antimony mercaptoate esters, tend to deteriorate if left unattended. Such deterioration is observed due to the formation and/or precipitation of solids in this liquid compound. The exact reason for this deterioration phenomenon is not known. Nevertheless, the resulting heterogeneous liquid not only increases fiber opening, but also, in line with the practical requirements of metering and mixing antimony compounds into halogenated vinyl resins for cheapening purposes. Inhomogeneity causes variations in appearance, which reduces the marketability of antimony stabilizers. Therefore, according to the present invention, the liquid antimono compound is made storage stable at the same temperature by incorporating a phenolic component such as ortho-dihydric phenol.

There is a reasonably preferred weight ratio of antimony organosulfur-containing compound to specific phenol to achieve stability. This will become clear from a detailed example. However, we would like to emphasize that the most desirable weight ratios of each of the essential components of the compositions of the invention for a particular application can be determined according to the methods of the invention. Therefore, in its broader aspects, the invention is not limited to the weight ratios of the components. The concentration of a particular phenol in a particular antimony-organosulfur-containing compound to achieve optimal stability under conditions will vary as exemplified herein. Generally, however, the phenol is from about 0.1 to about 20% by weight of the antimony compound, as set forth in the aforementioned application, Antimony Organosulfur-Containing Compounds.
IF with antimony, preferably in an amount of about 1-10% by weight.
fA is combined with a sulfur-containing compound.

Antimony organosulfur-containing compounds that are storage stabilized according to the present invention are generally characterized by having 5b-s groups or bonds. Such antimony compounds can be liquid at ambient or room temperature and atmospheric conditions. On the other hand, such antimony compounds can be solid at normal temperatures and can be softened or melted at elevated temperatures. Therefore, liquid stability at ambient conditions means that an antimony compound is normal liquid at room temperature or at ambient temperatures and pressures where such compounds are prone to decomposition due to ambient conditions.
, in either a hot melt or solvent-containing state. In the most preferred form, it is achieved in a liquid composition that is storage stable at room or ambient temperatures. Such liquid compositions can be easily metered and mixed with other compositions and are thus easily formulated, marketed, and used.

Generally, most antimony organic compounds suitable for use in the present invention are derived from trivalent azithimones and include mercaptides that can be characterized by the formula:

Formula 1, Sb (SR)3 In the above formula R represents a hydrocarbon or substituted hydrocarbon group such as a group selected from the group consisting of alkyl, aryl or aralkyl. Examples of darkening groups are alkyls such as ethyl, propyl, glutyl, octyl, nonyl, lauryl and octadecyl; aryls and aralkyls such as phenyl, benzyl, naphthyl, xylyl or phenylethyl. The group SR of formula 10 can be, for example, the residue of a mercaptan or a mercaptoalcohol.

As shown, aliphatic and aromatic mercaptans can be used to form asR*.

In the case of aliphatic mercaptans, those having 8 to 18 carbon atoms, such as decyl or dodecyl mercaptans, are usually preferred. This is because lower mercaptans are unsuitable for the preparation and use of stabilizers due to their unpleasant odor. Suitable aromatic mercaptans are, for example, thionaphthol, thiobenzyl alcohol, phenoxyethyl mercaptan and others. Suitable mercaptals: Examples of J-R and 17 may include monothioethylene glycol, monothioethylene glycol, thioglycerol, thiodiethylene glycol, and others. Specific examples of such antimony mercaptides are anticentrilauryl mercaptide, anticentriphenyl mernonoptide and antimony tribenzyl mercaptide. This formula 5b(SR)3 or similar formulas and compounds represented by them are exemplified by Mizuta Patent No. 2.684.956, among others.
No. 3,466,261.

Antimony B products other than the antimony mercaptide of Formula I above are considered suitable for use in the present invention. Such adducts are generally called antimony mercapto esters, and J'I- has the following formulas: u, Sb (S
RCOUR'1g In the above formula, R is selected from the group consisting of alkylene, arylene and aralkylene groups, and R' is a substituted or unsubstituted alkyl, aryl or mixed aryl-alkyl group. Thus, R can be derived from mercaptoacetic acid, β-mercaptopropionic acid, thiomalic acid, thiosalicylic acid, and the like.

Similarly, R' can be derived from decanol, glycerol, glycols, monoesters, dihydroabiethyl alcohol, phenoxyethanol, pentaerythritol, and the like. Particularly preferred are esters of mercapto alcohols, such as thioglycols, whose hydroxyl groups are esterified with aliphatic, aromatic or cycloaliphatic saturated or unsaturated hydronic acids. Readily available mercapto acid esters include esters of thioglycolic acid, such as ethyl thiodalicolate, isooctyl thioglycolate, and generally monobasic and dibasic aliphatic and aromatic mercapto acids, such as beta-thioglobionic acid, thio It is an ester of lactic acid, thiobutyric acid and mercaptolauric acid.

Specific examples of antimony mercapto esters include antimony tris (isooctyl thioglycolate), antimony tris (glycolsomercamethacetate), antimony tris (dodecyl thioglycolate), and dodecyl mercapto antimony bis (isooctyl thioglycolate). 1. and antimontris (inoctyl-β
-mercaptopropionate). Patents illustrating the use of formula n or similar formulas and compounds represented thereby include, among others, US Pat. No. 4,680,726 and US Pat. No. 3,530,158.

The antimony M-sulfur compounds with SbS groups represented by 21 and Otori fall within the broader specification shown by the following formula: Stratified, R55bX, -.

In the above formula, R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, 7-chloroalkenyl and hybrid aryl-alkyl and substituted groups thereof, and X consists of sulfide or mercaptide. Selected from the group, 9'L is a crab number from 0 to 20. Of course, other X groups are defined by 2 and l and fr
In the above formula, R of the group SR is selected from alkyl, aryl, hybrid aryl-alkyl and substituted groups thereof, and R of the group 5RCOOR' is selected from alkylene, aryle/, aralkylene, and the like. R' of the group 5RCOOR'
is selected from alkyl, aryl, hybrid aryl-aralkyl and substituted groups thereof. This is also clearly l
't'', and with respect to the above US patent, when X is divalent, e.g. sulfide, the compound has n- R56 as exemplified by butyl antimony sulfide
You can get X. It will therefore be appreciated that the above formula is a single representative representation of the class of antimony compounds consistent with the teachings of the present invention. In the compounds R, SbX, which can be used in the practice of the present invention, R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl or aryl or inert <=ertst)*
These groups can be substituted. For those where R is alkyl, it includes methyl, ethyl, n-propyl, i-propyl, butyl, i-butyl, n-amyl, n-octyl, 2-ethylhexyl, as well as phenylethyl, benzyl, etc. Substituted alkyls can be included. Representative alkenyl groups that may be used include vinyl, 2-propenyl (i.e., thialyl), 1-
Inertly substituted alkenyl groups such as propenyl, 1-butenyl, 2-butenyl, etc., and 4-phenyl, buten-1-yl, etc. can be included. Typical cycloalkyl groups are cyclohexyl, cycloheptyl, cyclooctyl, and 2-methylcycloheptyl,
3-2 f k V can include inertly substituted cycloalkyl groups including clohexfur, 3-methylcyclohexyl, and the like. Typical alkynyl groups that may be used include propylen-1-yl, propylene-2-yl, butyn-1-yl, phenylethynyl, ethynyl, and the like. A typical aryl group that can be used is phenyl.

May include tolyl, xylyl, chlorophenyl, trimethylaminophenyl, and the like. When more than one R or X is present in formula (1), such groups can be the same or different. Includes dimercaptans including typical family, cycloaliphatic, or aromatic dimercaptans and the like. Specific compounds when n is 1 or 2 are n-notylantemon dilauryl mercagutide, n-butylantanti.

Monsulfide, di-n-butylantimony lauryl mercaptide, sophenylantimony lauryl mercaptide, ditolyl antimony n-amyl mercaptide, sobennodi, v7 ntimonylic mercaptide, diallyl antimony cyclohexyl mercaptide, diphenylantimony alkyl mercaptide peptide, socyclohexyl antimony n-hexyl mercaptide, ditolylantimony phenyl mercaptide, di-isopropylantimony 2
-ethylhexyl mercaptide, di-p-chlorophenylantimony n-butyl mercaptide, diphenylantimony ethyl mercaptoacetate. A patent illustrating such an antimony compound is U.S. Patent No. 3.53.
No. 0.158 and No. 399°220. When the R group is aryloxy, alkyloxy, alkaryloxy, acyloxy, etc., the specific ftl from which this group is derived is 2-ethylhexyl, phenol, nonylphenol, xylenol, 2-ethylhexane. acids, including oleic acid, lauric acid, benzoic acid, and the like. Of course, antimony mercaptide, antimony mercapto acid, antimony mercapto acid ester, etc. do not themselves form part of this invention, and the above patents and their specific disclosures do not assist cancer practitioners in carrying out this invention. It is clear that these compounds and methods of their preparation are taught in such a way as to enable their use.

Phenol The terms "phenol" and "phenols" as used herein are intended to include mononuclear or polynuclear phenols exemplified by benzene or naphthalene nuclei and substituted forms of such nuclei.

As reported in the applicant's above-referenced pending application, such mononuclear or polynuclear phenolic ortho-dihydric phenols can be used in the present invention to provide liquid, storage-stable compositions of antimony compounds at ambient temperatures. Specific examples of such ortho-dihydric phenols that have been discovered by those skilled in the art include catechol, tertiary-butylcatechol, and 2,3 dihydroxynaphthalene. The present inventor has determined that the stability of such an antimony compound is determined by the following formula: R', R'', R3, R4, or R11 are hydrogen, alkyl, aryl, hydroxyl, alkoxy, aryloxy, alkaryl, aralkyl, and the aryl or alkyl other substituted groups, etc., provided that they are not all hydrogen, or they can be substituted with one of the aromatic or alkylated aromatic nuclei, as in the case where the phenolic nucleus is naphthalene. It has been found that the alkyl substituents of mononuclear or polynuclear phenols of this formula can be methyl, ethyl, Includes straight or branched groups of Cl-42 such as propyl, pentyl, hexyl, hegetyl, dodecyl or tert-butyl, isopropyl, etc. Form δ.The phenols of the present invention are characterized by their performance and commercial utility. Therefore, catechol derivatives are presently preferred.Other dihydric or trihydric phenols, or monovalent -
Mono- or polyhydric phenols can be used. Included in such phenols are seven no, g,
triisobutyl or inoctylphenol i2,
4.5-) Lihydroquiptylophenone; butylated hydroxyanisole, which is a mixture of ortho- and metabutyl iZrahydroxyaniso,-;
cqwinol) H resorcinol; 216-sort
-butyl-p-cresol; resorcinol monobenzoate and Up-octylphenyl salicylate.

It is understood that stabilization can be achieved using certain phenols, along with other advantages as demonstrated experimentally in numerous embodiments of the present invention, and a further understanding thereof will be apparent from the detailed description therein. It will be.

The prototype of the invention and its method of practice will be further understood with reference to the following detailed examples illustrating the types of specific materials and their amounts used to stabilize antimony compounds according to the invention. □ These examples are intended to be illustrative of the invention and should not be considered limiting, particularly since Applicants have provided extensive disclosure regarding the nature of the invention.

In the examples in Tables I and II below, various combinations of antimony organosulfur-containing compounds and phenols are blended to form liquid compositions on a parts by weight basis. All amounts of components are based on coulometric percentages or simply as indicated. Phenol is incorporated into liquid antimony tris-isooctylthioglycole (ATG) on the basis of about 0.1 to about 20 weight percent of antimony compounds as shown in the table. ATG and t-butylcatechol (TBC)
or ATG and butylated hydroxyanisole (BHA)
The stability of the resulting blend at room temperature and atmospheric pressure (
(20-25[deg.]C and atmospheric pressure) in open bottles, respectively, as reported in Tables 1 and 2.

Table 1 % TBC Time In the above table, "clear" means a homogeneous, clear liquid; "very slightly cloudy" means the appearance of very little non-solvent particles; 1 and 1 cloudy 7
respectively mean increasing non-solvent appearance; and "opaque" means loss of transparency. Thus,
As can be seen by the two tables above, at room temperature and normal pressure, unmodified liquid antimony compounds develop haze and become opaque after being left for several weeks. No degradation is shown in the presence of small amounts of t-butylcatechol (see Table 1). T
The stabilization reaction of BC appears to be linear with increasing amount. However, Table 3 shows that the stabilization response of butylated hydroxyanisole (BHA) is not completely linear. Rather, improvements are observed with varying amounts between 0.1 and 5.0 inches, with full transparency being maintained over a period of 8 weeks with approximately 0.3 inches to 2 inches of BHA.

Accelerated storage stability testing was also performed. In these tests, an apparatus is constructed to supply air to liquid antimony samples containing varying amounts of phenol.

Connect the air supply to the flow meter and then to the hose! l
) Connect to a 1000 ml vacuum flask containing 750 btl of water. After bubbling this water,
Air bubbles through the liquid through the glass tube, so
A 400m beaker containing 150v of antimony tris-isooctylthioglycolate heated to 260°F was introduced.

Subsequently, the antimony liquid was placed in a beaker and the desired percentage of phenol was added to the liquid sample.

The liquid was then stirred with t*5 cFH of air supplied at a temperature maintained at 260°F. As the minutes progressed, the moment of opacity was recorded as the time when the centrally located glass tube in the beaker generating air became no longer visible when looking through the side of the beaker. Using the accelerated test described above, opacification occurred for the various percentages of TBC shown on the surface layer! :
, lρtc (sub-control), the cells became opaque in 22 minutes.

Table m 0 22 0.5 44 1.25 61 2.0 68 2.5 81 3.5 . 112 5, 0 1 3 8 TBC thus achieves increased volume and primary stabilization of liquid antimony over a period of time. The accelerated surface kernel data separates the TBC peripheral test results in the sense that stability increases with increasing phenol content.

Accelerated testing was also conducted on EHA under the same conditions described above. Report the results in Table ■.

Table ■ Chi EHA Opacification (min) 0 22 0.5 31 1, 25 28 2.038 25 43 ao 36 a・523 4, 2 5 2 5 5.0 26 Thus, the accelerated data in Table ■ is above Paralleling the data in Table 1 and similarly demonstrating its reliability in predicting long-term storage stability for liquid antimony compositions.゛Using an accelerated test, at 25 thiphenol components in ATG, butylated hydroxyanisole; p-dihydroxybenzene; regular dihydroxybenzene; 2,6-sheet
#det-f-tyl-/zo-secresol resorcinol monoinzoate; p-octylphenyl salicylate)
; mM of di- and tri-alkylphenols in which the alkyl groups substituted in the 2, 3 and 5 positions are isobutyl or isooctyl, o-no and drooxybenzene and 2,4.5-)! An improvement in stability of at least about 20 minutes was observed for J hydroxybutophenone. Butylated hydroxyanisole, 2,2'-bis(
4-hydroxyphenyl)gulonogun, 4,4'-butylidenebis(6-t-det-butyl-cresol)
, 4,4'-thiobis-(6-tart-butyl-starvation)
In the case of phenols such as 2-8 dihydroxynaphthalene (cresol), and 2-8 dihydroxynaphthalene, improvements have been observed at concentrations between 0.5 and 5.0 h, but the optimum value varies depending on the phenol and the particular antimony compound.

In addition to the above examples, various O-dihydric phenols and liquid antimonytris (inoctyl-β-mer kadetoglobionate), hereafter referred to as "ATp". Each of the five phenol-containing combinations was a storage stable liquid at ambient temperature. The O-dihydric phenols were ij 4-tert, butylcatechol, catechol and 2,3-so and droxynaphthalene. .

As mentioned above, antimony compounds can be liquids in their normal state, ie, at room temperature and atmospheric pressure. The antimony compound can also be made into a liquid by adding a medium. In this connection, antimontris (
lauryl mercaptide) is a pasty solid at ambient temperature. A composition of 50% hydrocarbon solvent and 50% antimontris (lauryl mercaptide) was formulated and was a clear liquid at room temperature and ambient pressure.

When a sample of such composition was tested for stability under the accelerated method described above, the control without phenolic stabilizer became opaque after about 35 minutes. When 4-5% by weight of tertiary-butylcatechol was added and the accelerated test was run under the same conditions as the control above, the phenolic compound-containing composition did not become opaque until 70 minutes had elapsed. Therefore, normal state M or mediated ( 5olvαted'
Liquid antimony stabilizers in the J state can be stabilized according to the principles of the present invention.

It will also be appreciated that other ingredients may be used to achieve the benefits of the present invention. Accordingly, it will be apparent from the teachings herein that other modifications may be made without departing from the spirit and scope of the invention.

Claims (1)

[Claims] Formula % (wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, hybrid aryl-alkyl, and substituted groups thereof) and X is sulfur, SR and 5RCO
The group consisting of OR' is chosen, where the base 5
R (DR is selected from the group consisting of alkyl, aryl, hybrid aryl-alkyl and substituted groups thereof;
R in the group 5RCOOR' is selected from alkylene, arylene 1 aralkylene, and substituted groups thereof;
By of RCOOR/ is selected from alkyl, aryl, hybrid aryl-alkyl and substituted groups thereof, and 5ti
A liquid containing an antimony organic sulfur-containing compound having an integer of from (II) meta- and para-dihydric phenols and substituted meta- and para-dihydric phenols; (ii) trihydric phenols and substituted An antimony-based composition stable under ambient conditions, characterized in that it consists essentially of a phenol selected from trihydric phenols. 2. The composition of claim 1, wherein the phenol is butylated hydroxy-anisole. A composition according to claim 1, which is liquid at room temperature and storage stable for at least several weeks. 4 The antimony compounds include antimony tris (isooctyl thioglycolate), antimony tris (isooctermercabutoglobionate), dodecylmercaptoantimony bis(isooctyl thioglycolate),
4. The composition of claim 3, wherein the composition is selected from the group consisting of antimontris (glycol dimercaptoacetate), and mixtures thereof. 5. The composition according to claim 4, wherein the phenol is glylated hydroxy-anisole. & The phenol is contained in an amount of about 0.1% to about 2% by weight of the heptase compound.
A composition according to claim 1 containing in an amount of 0% by weight. 7.Formula%Formula% (In the above formula, R is alkyl, alkenyl, alkynyl,
selected from the group consisting of aryl, cycloalkyl, cycloalkenyl, hybrid aryl-alkyl, and substituted groups thereof, and X is sulfur, SR and BRC
OOR', where R of the group SR is selected from the group consisting of alkyl, aryl, hybrid aryl-alkyl and substituted groups thereof, and R of the group 5RCOOR' is selected from alkylene, arylene, aralkylene, and substituted groups thereof, and the group 5R
R/ in COOR/ is selected from alkyl, aryl, hybrid aryl-alkyl and substituted groups thereof, and n is θ~
an antimony organic sulfur-containing compound which is liquid in its standard state and has an integer of 2), and as a stabilizer therefor, a small amount of
Gtylated hydroxyanisole, p-dihydroxybenzene, m-dihydroxybenzene, 2,6-di-t-f
Tyrnosolacresol, resorcinol monopenzoate, p-octylphenyl salicylate, mono-isobutylphenol, di-isobutylphenol, triisobutylphenol, mono-isooctylphenol, di-isooctylphenol, triisooctylphenol, 2,4 .5-) Lihydroxyptylophenone, 2
．． 2-bis(4-hydrotriphenyl)propane, 4.
A room temperature liquid consisting essentially of a phenol selected from the group consisting of 4-butylidene-bis(@-tart-butyl-m-cresol) and 4,4'thiobis-(6-tert-butyl-m-cresol). and a storage-stable antimony-paced composition. 8. The composition of claim 7, wherein the relative amount of phenol present is from about 1 to about 20 times the antimony compound. 9. The antimony compound is antimony tris (isooctyl thioglycolate), antimony tris (isooctyl mercaptoglobionate to dodecyl mercapto antimony bis(isooctyl thioglycolate)), antimony tris (glycol dimercaptoacetate),
and mixtures thereof. 1α The composition of claim 8, wherein the phenol is butylated hydroxy-anisole.