JP2002275365A - Improved stabilizer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new stabilizer composition, as a heat stabilizer for uses for a transparent or translucent hard PVC, for which a 1-3C alkyl organotin compound can be employed without causing plate-out and/or rheology problems. SOLUTION: The stabilizer composition comprises at least a blend of liquids below: (a) at least one 1-3C alkyl organotin compound, and (b) at least one complex ester derived from at least one dehydration condensation reaction product between at least one polyol (A) and at least one unsaturated fatty acid compound (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to improved organotin heat stabilizers for halogen-containing organic polymers. The present invention
The present invention also relates to a method for stabilizing a halogen-containing organic polymer with the improved organotin heat stabilizer of the present invention. The present invention also relates to halogen-containing organic polymers and products containing the improved organotin heat stabilizers of the present invention.

[0002] Many halogen-containing organic polymers, such as polyvinyl chloride ("PVC"), are used, for example, in building siding, shutters, window and door frame profiles, rainwater transport systems (eg, gutters, downspouts), enclosures. It has a useful combination of properties as a structural material that can be extruded, calendered or shaped into a wide variety of products for packaging applications.

[0003] Unfortunately, PVC polymers are known in the plastics industry to be unstable, decompose and fade when heated to the molten state. This is especially a problem in transparent or translucent packaging applications where small amounts of degradation can cause unacceptable yellowing of the resulting plastic product.

[0004] Therefore, when making transparent or translucent plastic products and the like from PVC, it is known to stabilize the polymer against thermal decay so that they are easily processed. Typical stabilizers used for this purpose include those known as tin stabilizers, especially alkyl organotin stabilizers. Various alkyl organotin stabilizers include:
It is readily available from market sources.

One of the most common alkyl organotin stabilizers used industrially in rigid PVC applications is a "C ₈ octyl organotin" stabilizer, such as dioctyltin di (isooctylthioglycolate). Is raised. Despite its widespread use, there is a continuing need to improve such alkyl organotin stabilizers.
One way in which such stabilizers may be more useful to the plastics industry is to make them more active at lower usage levels and / or to reduce the haze effects in transparent or translucent PVC products. There will be.

[0006] One attempt to improve the performance of alkyl organotin stabilizers involves lower alkyl organotin materials (ie, C ₈
Having a lower alkyl group). However, it has been observed that doing so poses more problems than it solves. For example, in some PVC formulations, C ₄ an alkyl organotin stabilizer from C _1, it has been observed that can cause plate-out problems in processing equipment. this is,
It can also cause undesirable rheological problems.

[0007] Plate-out problems are believed to occur because lower alkyl organotin stabilizers have a similar solubility in PVC as some internal lubricants. Therefore,
This results in PVC saturation and subsequent migration of internal lubricant from the PVC to the machine surface.

The rheological problem originates on the one hand from the plate-out problem. Specifically, P
The removal of some internal lubricant from the VC polymer changes the rheological properties of the polymer composition. This will significantly change the processing parameters of the composition. Those skilled in the processing industry is for large changes in processing conditions rigid PVC from when the C ₈ octyl organotin stabilizer conventional is employed, it is often hesitate. Thus, if alternative heat stabilizers are developed, the plastics processing industry will find that the use of
It would require that the _8- octyl organotin stabilizer maintain essentially the same rheological properties as those used when used.

[0009] Despite the above-mentioned adverse effects associated with the use of lower alkyl organotin stabilizers, theoretically, lower alkyl organotin stabilizers have significant benefits in transparency, translucency and / or thermal stability. I will provide a.

One example in which this theory is tried is described in Neynaber Chemie GMBH, British Patent No. 1,292,548. There, while processing the PVC, C ₄ butyl organotin stabilizer is used. On the other hand this literature, while indicating that the PVC polymer can be processed with C ₄ butyl organotin stabilizer, does not disclose whether the encounter with the plate-out and / or inconvenient rheology problems. Also, not disclosed that may be employed even at lower alkyl organotin stabilizer than C _4.

No. 4,202,806 to Yoshida et al.
Discloses heat stabilizers for chlorine-containing resins derived from the dehydration condensation product of pentaerythritol and / or polypentaerythritol. These heat stabilizers are partially esterified with mono- or polybasic acids and higher fatty acids. Yoshida et al. Report that the hydroxyl content of the esterified product is in the range of 10% to 40% by weight, since almost completely or fully esterified polyols have little effect on the thermal stability of the chlorine-containing resin. Is essential. Yoshida et al. Disclose that these stabilizers can be employed in combination with tin stabilizers, but such combinations may result in the plate-out and / or unfavorable rheology associated with the use of lower alkyl organotin stabilizers. It does not disclose solving processing problems or reaching the stability of a single organotin stabilizer.

[0012] In view of the above, plastic processing industry, transparent or a C ₁ as a heat stabilizer for translucent rigid PVC applications C ₃ greatly welcome the alkyl organic tin compounds may be used, provided that such use, the plate Out and / or without rheological problems.

[0013] Accordingly, one object of the present invention, to solve the above problems, a transparent or semi-transparent hard PVC, etc., as a heat stabilizer for halogen-containing organic polymer compositions, C ₃ alkyl organotin from C ₁ It is to provide a means that allows the use of the composition.

Another object of the present invention does not cause the problem described above from C ₁ while include C ₃ organotin compositions, transparent or semi-transparent rigid, halogen-containing organic polymer compositions heat stabilizer composition such as PVC It is to provide.

These and other objects, which will be readily apparent to those of ordinary skill in the art after reading this specification, are those of C ₁ to C ₃
This has been achieved by inventing an organotin-containing heat stabilizer composition for a halogen-containing organic polymer composition comprising an alkyl organotin compound and a complex ester. While these are the two essential components of the novel organotin-containing heat stabilizer compositions disclosed herein, they can be simultaneously or sequentially as a blend, before or during processing of the polymer composition. In either case, it can be added to the halogen-containing organic polymer composition.

In a first embodiment of the present invention, at least a) at least one C ₁ -C ₃ alkyl organotin compound; and b) (A) at least one polyol and (B) at least one unsaturated fatty acid compound. With 1
At least one complex ester derived from the above dehydration-condensation reaction product
er), comprising an organotin-containing heat stabilizer composition comprising a liquid blend.

In a second aspect of the present invention, there is provided a halogen-containing organic polymer composition comprising a halogen-containing organic polymer and an organotin-containing heat stabilizer composition, wherein the heat stabilizer composition comprises at least a ) at least one _C 1 -C ₃ alkyl organotin compound; and b)
It comprises a liquid blend of (A) at least one polyol and (B) at least one complex ester derived from one or more dehydration condensation reaction products with at least one unsaturated fatty acid compound.

In a third aspect of the present invention, there is provided a method of preparing a halogen-containing organic polymer composition comprising blending a halogen-containing organic polymer with an organotin-containing heat stabilizer composition, wherein the heat stabilizer comprises composition, at least, a) at least one C ₁ -C ₃ alkyl organotin compound; and b) (a) at least one polyol and (B) at least one of the one or more dehydration condensation reaction of an unsaturated fatty acid compound A liquid blend of at least one complex ester derived from the product.

In a fourth embodiment of the present invention, the halogen-containing organic polymer is simultaneously or sequentially added with at least:
derived from and b) (A) at least one polyol and (B) at least one of the one or more dehydration condensation reaction product of an unsaturated fatty acid compound; a) at least one C ₁ -C ₃ alkyl organotin compound Provided is a method of preparing a halogen-containing organic polymer composition, comprising adding at least one complex ester.

The term "parts" as used herein is intended to mean "parts by weight". Unless otherwise noted, “total parts by weight” do not necessarily add up to 100 in total. As used herein, the term "phr" refers to "resin 100
It is intended to mean "parts per part" and is on a weight basis. The term "weight percent" used here
Is intended to mean "parts per hundred". The term “alkyl,” as used herein, refers to a linear,
Branched and cyclic saturated hydrocarbon chemical groups are meant. The term "C
_In " _N- alkyl", N is a number, meaning a saturated alkyl group consisting of N carbon atoms. As used herein, the term "hydroxyl content" refers to the weight percent of -OH hydroxyl functionality based on the total weight of the complex ester component. As used herein, the term "molecular weight"
Mean weight average molecular weight. All ranges disclosed herein are inclusive and combinable.

[0021] The invention disclosed herein is, in part, includes a C ₃ alkyl organotin compound and at least one complex esters from at least one of C _1, on the development of novel organotin-containing heat stabilizer composition. The novel organotin-containing heat stabilizer composition not only provides improved heat stability for the transparent hard chlorinated resin composition, but also provides it without the disadvantageous processing conditions described above. .

In the present invention, the complex ester is derived from one or more dehydration condensation products of at least one polyol and at least one unsaturated fatty acid compound.

In one embodiment of the present invention, the stabilizer composition is a homogeneous liquid. As used herein, "uniform"
The organotin compounds and complex esters mean that they are completely miscible so that they maintain a single liquid phase for an extended period of time according to thermodynamic principles. As used herein, "liquid" means at a temperature of less than 75C, typically less than 50C, more typically less than 25C, and even more typically less than 0C. It means that the fluid takes the shape of the container.

[0024] In these aspects of the invention the stabilizer composition is a homogeneous liquid, each C ₁ to C ₃ alkyl organotin compounds and complexes esters are liquid, as defined herein. However, any one or both of these components may be in the solid state as long as the resulting stabilizer composition blend is liquid. If the composition solidifies, the alkyl organotin compound tends to phase separate from the complex ester within the stabilizer composition.

Because of their homogenous liquidity, the stabilizer compositions of these aspects of the invention are readily added and dispersed to rigid polyvinyl halide resins at relatively low processing and mixing temperatures. These lower mixing temperatures greatly improve the internal flow of the resulting resin composition and reduce the tendency of the composition to adhere to the processing machine. Furthermore, it is possible to obtain a shaped, calendered or extruded end product with improved surface smoothness, clarity and reduced yellowness.

The heat stability characteristics of the stabilizer composition of the present invention are as follows:
_It increases as the amount of ₁ to C ₃ alkyl organotin compound increases relative to the amount of complex ester.
However, increasing the relative amount of the organotin compound usually involves an increased tendency for the organotin compound to plate out during the chlorinated resin processing. Similarly, too low an amount of complex ester will cause the chlorinated resin to melt too quickly, while excess complex ester will result in too slow melting of the chlorinated resin requiring significant changes in processing parameters. Will cause.

Any amount of at least one of C ₁ to C ₃
An alkyl organic compound component may be used in the stabilizer composition in practicing the present invention. However, the amount used will generally be at least 50 weight percent. Typically, the amount of C ₃ alkyl organotin compounds from C ₁ to be used is at least 70 weight percent, at least 80 weight percent and more typically, even more typically at least 85 weight percent. The weight percentages are based on the combined total weight of the alkyl organotin component of the stabilizer and its complex ester component.

On the other hand, C ₃ alkyl organotin compounds from C ₁ used in the stabilizer compositions of the present invention is generally 99.
Less than 9 weight percent. Typically used C
The amount of from ₁ C ₃ alkyl organotin compound is less than 98 weight percent, more typically less than 95 weight percent, 92 weight percent and even more typically. The weight percentages are based on the combined total weight of the alkyl organotin component of the stabilizer and its complex ester component.

Similarly, any amount of at least one complex ester component may be used in the stabilizer composition in practicing the present invention. However, the amount used will generally be less than 50 weight percent. Typically, the amount of complex ester used is 3
It is less than 0 weight percent, more typically less than 20 weight percent, and even more typically less than 15 weight percent. The weight percentages are based on the combined total weight of the alkyl organotin component of the stabilizer and its complex ester component.

On the other hand, the amount of complex ester component used in the stabilizer composition of the present invention is generally greater than 0.1 weight percent. Typically, the amount of complex ester component used is greater than 2 weight percent, more typically greater than 5 weight percent, and even more typically greater than 8 weight percent. The weight percentages are based on the combined total weight of the alkyl organotin component of the stabilizer and its complex ester component.

Although any C ₁ to C ₃ alkyl organotin compounds can be employed in the present invention, typically, such organotin compounds have a liquid state. Here "from C ₁ C ₃ alkyl organotin" as used refers to one, means any organic tin compound in which two or three organic groups are bonded to one or more tin atoms. Any suitable C ₁ -C ₃ alkyl organotin compounds can be employed,
Leistne issued on June 26, 1953
r) et al., U.S. Pat. No. 2,753,325; Reisner et al., 2,641,596, issued June 9, 1953.
No .; Weinberg published on August 11, 1953 (Wei
No. 2,648,650; and 197.
7 December 13 _{C 3 C 1 to} as disclosed in No. 4,002,881 issued to Kugel (Kugele)
Alkyl organotin mercaptocarboxylates and C
It is particularly useful to employ a C ₃ alkyl organic stannous acid mercapto alcohol ester _1. Many suitable alkyl organotin compounds are also disclosed in 1992
Year, Van North Tran Rd Hold, J.M. Edenbaum Publications, pp. 309-326; D. Also described in Dworkin's Handbook of Plastic Additives and Modifiers, Chapter 19, Polyvinyl Chloride Processing Stabilizers; Tin and Derivatives, which include a number of organotin-sulfides, -oxides, -carboxylates. Trate, -anhydride, -mercaptide, -mercapto alcohol ester and mercaptocarboxylate. Particularly useful as liquid organotin compounds are the following C ₁ alkyl organotin compounds: dimethyltin bis (isooctylthioglycolate), mono- and di-methyltin bis (2 mercaptoethyl oleate), mono- and di- Methyl tin bis (2-mercaptoethyl laurate), dimethyl tin bis (2-ethylhexyl thioglycolate), and methyl tin tris (2-ethylhexyl thioglycolate). The following C ₂ and C ₃ organotin compounds are also expected to be suitable: di - Echirusuzubisu (2-ethylhexyl thioglycolate), ethyl tin tris (2-ethylhexyl thioglycolate),
Di-propyltin bis (2-ethylhexylthioglycolate), propyltin tris (2-ethylhexylthioglycolate), di-isopropyltin bis (2-ethylhexylthioglycolate), isopropyltin tris (2-ethylhexylthioglycolate) ). Mixtures of one or more organic tin compounds having a large alkyl group than C ₃ can also comprise one or more mixture components may be employed as long as C ₃ alkyl organotin compounds from C _1.

The complex ester employed is derived from one or more dehydration condensation products of at least one polyol and at least one unsaturated fatty acid compound. In a preferred embodiment of the present invention, the complex ester is derived from a dehydration condensation product with at least one polyol, at least one polybasic acid, and at least one unsaturated fatty acid compound. Various methods for preparing complex esters are described in German Patent No. 1,292,548 to Niinabelhemie GMBH and US Pat. No. 3,637,5 to Malec et al.
No. 01, No. 4,202,806 to Yoshida et al. And No. 4,338,2 to Worshech et al.
No. 26.

Whereas the above references disclose many complex esters having a hydroxyl content of 10% or more, the hydroxyl content of the complex ester used in the present invention generally has a hydroxyl content of less than 10%. In certain embodiments, the hydroxyl content of the complex ester employed in practicing the present invention is typically less than 10%, more typically less than 7%, and even more typically less than 5%. %.

[0034] Typically, as the hydroxyl content of the complex ester component decreases, the complex ester becomes more incompatible with chlorinated resins such as PVC and behaves more like an external lubricant. Thus, the plateout of the lower alkyl organotin compound is reduced as the hydroxyl content of the complex ester is reduced. Unlike partial esters, complex esters having a hydroxyl content of less than 10% are considered to be completely or almost completely esterified.

[0035] Any suitable polyol component may be used in making the complex esters employed in practicing the present invention. Examples of such suitable polyols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,
Examples include 6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, mannitol and sorbitol. In certain embodiments of the invention, particularly useful polyol components have 3 to 6 hydroxyl groups, and typically have 3 to 4 hydroxyl groups. In one particular embodiment of the present invention, the polyol employed comprises pentaerythritol.

[0036] Any suitable unsaturated fatty acid compound may be used in making the complex esters employed in practicing the present invention. Examples of such suitable fatty acid compounds include mono-, having a single carboxylic acid group,
Di- and poly-unsaturated alkyl carboxylic compounds are mentioned.

[0037] Generally, the unsaturated fatty acid compound employed is selected from alkenoic, alkadienoic and alkatrienoic acids. Typically, these alkenoic, alkadienoic and alkatrienoic acids have 8 to 32 carbon atoms in their aliphatic groups, and in mixtures thereof.
More typically it has from 12 to 28 carbon atoms and even more typically has from 14 to 24 carbon atoms. In certain preferred embodiments of the present invention, the unsaturated fatty acid compounds employed include oleic acid, elaidic acid, erucic acid, linoleic acid, linolenic acid and mixtures thereof. These unsaturated fatty acids, when the complex ester is blended with the lower alkyl organotin compound,
Ensure that a liquid is formed.

It is also envisioned that saturated alkyl carboxylic compounds may be further employed in the complex ester. Although such saturated compounds tend to increase the melting point of the complex ester, the amount of the saturated compound can be any amount as long as the complex ester forms a liquid blend with the lower alkyl organotin compound. Examples of such saturated alkyl carboxylic acid compounds that may be included include fatty acids such as caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and mixtures thereof.
For practical reasons, mixtures of fatty acids from natural fats and oils are generally used.

Complex esters can be prepared according to various art-known procedures. For example, a polyol and any polybasic acid, in the presence or absence of a solvent,
And at an elevated temperature in the absence or presence of an acid catalyst such as a mineral acid such as phosphoric acid and sulfuric acid, an organic acid such as alkylbenzenesulfonic acid, and a Lewis acid such as tin chloride and magnesium chloride, or a base catalyst. It can be subjected to a dehydration condensation reaction. 1992, Van North Tran Drainhold, J.M. Edenbaum, publications, pages 773-774,
R. A. The various preparation methods described in Lindner's "Plastic Additives and Modifiers Handbook, Chapter 55, Acid-Ester Lubricants" are also applicable, wherein the aliphatic alcohols described herein are also used herein. It contains the polyols and polyol-polybasic acid intermediates used.

One example of a method for obtaining a dehydration-condensation reaction product with at least one polyol, at least one fatty acid compound and an optional polybasic acid to provide a complex ester used in the stabilizer composition of the present invention. ,
The dehydration condensation reaction is performed such that the resulting condensation product has a hydroxyl content of less than 10% by weight. These low hydroxyl levels are such that the fatty acid reacts with substantially all of the hydroxyl groups of the polyol or polyol-polybasic acid condensation product with the stoichiometric ratio of the polyol, any polybasic acid and unsaturated fatty acid. Can be provided by controlling

Any of the polybasic acids that may be employed in practicing certain embodiments of the present invention may be either aliphatic or aromatic. For the purpose of providing a liquid complex ester, a soft aliphatic polybasic acid such as adipic acid may be employed.

When used, the aliphatic polybasic acids typically have at least 4 carbon atoms. Examples of such aliphatic polybasic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, tricarballylic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacine Acids, malic acid, tartaric acid, citric acid, 5-norbornene-2,3-dicarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and mixtures thereof. When used, such aliphatic polybasic acids may be in the form of esters, acid halides and / or acid anhydrides.

[0043] Any aromatic mono- and polybasic acids can be employed as polybasic acids. However, in certain embodiments, it is desirable to minimize their use as they tend to make the complex ester excessively soluble in halogen-containing organic polymer compositions such as PVC. Examples of aromatic acids that may be employed in practicing certain aspects of the invention include benzoic acid, o-, m-
And p-toluic acid, o-, m- and p-hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxylnaphthoic acid, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid and mixtures thereof. If employed, these aromatic carboxylic acids can be in the form of esters, acid halides and / or acid anhydrides.

The hydroxyl content of the complex ester can be achieved by adjusting the molar ratio of the polyol, polybasic acid and unsaturated fatty acid. For example,
The molar ratio of polyol: polybasic acid: unsaturated fatty acid is x:
y: z.

Typically, x is a number between 1 and 15, more typically a number between 2 and 12, and even more typically a number between 3 and 10. And most typically a number between 5 and 8. Since the polybasic acid is optional, y can be zero, but typically y is less than 14, more typically between 1 and 11, and even more typically between 2 and 9 And most typically between 4 and 7
Between. In certain preferred embodiments, y is
Same as or smaller than x.

The value z is such that the number of moles of unsaturated fatty acid is unreacted hydroxyl between the polyol and the polybasic acid such that a complete dehydrocondensation reaction results in a minimum number of residual hydroxyl groups, typically zero. It is selected to be equal to the number of moles of the group. For example, when the polyol has m hydroxyl groups and the polybasic acid has n acid groups, z is at most equal to mx + ny when there is no condensation reaction between the polyol and the polybasic acid. Should. However, typically, the polyol and the polybasic acid react such that each of the acid groups of the polybasic acid reacts with one hydroxyl group of the polyol. In this case, the number of residual hydroxyls is mx-ny, which value is typically equal to z.
Thus, from another perspective, the value mx-ny is greater than zero. As an example, if the polyol is pentaerythritol (m
= 4), the polybasic acid is adipic acid (n = 2) and the molar ratio of pentaerythritol to adipic acid is 7: 6 (x = 7, y
= 6), z is typically 14.

In addition to providing a hydroxyl content of less than 10%, the conversion (ie, the degree of dehydration) can also control the molecular weight of the complex ester. For the purpose of adjusting plateout and process rheology, the molecular weight of the complex ester used in the present invention is typically at least 1,000 g / mol, more typically at least 2,000 g / mol, and even more typical. Typically, it is at least 5,000 g / mol. Correspondingly, the molecular weight of the complex ester employed in the present invention is typically up to 50,000 g /
Moles, more typically up to 25,000 g / mol, even more typically up to 10,000 g / mol. The higher the molecular weight, the higher the viscosity of the complex ester.
In one preferred embodiment of the present invention, a complex ester having a molecular weight of at least 1,000 g / mol is provided, typically by esterifying a polyol-polyacid intermediate condensate with an unsaturated fatty acid. .

Thus, an almost completely or fully esterified reaction product having a hydroxy content of less than 10% is a complex ester which, when employed in the liquid stabilizers of the present invention, reduces plate out and rheological problems. Is particularly desirable in providing

The C ₁ -C ₃ alkyl organotin compounds and complex esters can be blended to prepare the liquid stabilizer compositions of the present invention. In preparing these blends, the components can be individually liquid or solid.

[0050] In certain preferred embodiments of the present invention, both essential components are liquid. Thus, in such preferred embodiments, C ₃ alkyl organotin stabilizers and liquid complex esters from the liquid C ₁ is blended together. The order of addition of the components in this process is not critical, but at least 2
It is common to add the complex ester slowly while maintaining the temperature of the blend at 5 ° C, typically at least 50 ° C.

An advantage was observed when the blend was homogeneous. If such a system is desired, the components are:
At an appropriate time and temperature, the stabilizer composition is mixed until the appearance is uniform.

In addition, these blends are prepared when either or both the organotin compound and the complex ester component are dissolved or dispersed in a liquid, for example, during the synthesis of either or both of these components. Can be done. In one preferred embodiment, the complex ester component is added to the aqueous mixture C ₁ methyl organotin compound is synthesized. For example, during the synthesis of a methyltin mercaptide compound by the reaction of methyltin chloride with an ester and a base in an aqueous phase, the methyltin mercaptide product forms an organic phase that is insoluble in water, and To separate. The aqueous phase is removed and an aqueous washing step with any water can be performed to purify the organic phase. The complex ester solution is then added to the organic phase and stirred until a homogeneous blend is obtained.

Under the above process, the temperature is adjusted to maintain a liquid state. Typically, such a temperature is 15
It is in the range from 100C to 1000C. Often the temperature is 70
It is kept below ℃.

In a further aspect of the present invention, it is desirable to purify the liquid stabilizer composition. In these cases, purification may be provided by distilling off impurities such as unreacted reactants and reaction by-products (eg, water) from the stabilizer composition. Distillation methods are, of course, known in the art, such as vacuum distillation. Additional impurities, such as insoluble salts, can be further removed by filtration.

The halogen-containing organic polymers which can be stabilized according to the invention comprise from 14 to 75%, for example 27% by weight
Chlorinated polyethylene, chlorinated natural and synthetic rubber, chlorinated rubber, chlorinated polystyrene, chlorinated polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, vinyl chloride with 1 to 90% of chlorine, typically 1 to 30% % Of copolymerizable ethylenically unsaturated substances such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarate and maleate, vinyl propionate, methyl acrylate, 2- Ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other alkyl methacrylates, methyl alpha-chloroacrylate, styrene, trichloroethylene, vinyl ethyl ether Copolymers with vinyl ethers such as vinyl chloride, vinyl chloroethyl ether and vinyl phenyl ether, vinyl ketones such as vinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-2-chloroethylene, acrylonitrile, chloroacrylonitrile, arylidene diacetate and chloroallylidene diacetate Is included. Examples of typical copolymers include vinyl chloride-vinyl acetate (96: 4, commercially available as VYNW), vinyl chloride-vinyl acetate (87:13), vinyl chloride-vinyl acetate-maleic anhydride (86: 13:
1), vinyl chloride-vinylidene chloride (95: 5); vinyl chloride-diethyl fumarate (95: 5) and vinyl-2-ethylhexyl acrylate (80:20).

[0056] In certain preferred embodiments, the halogen-containing organic polymer comprises a vinyl halide polymer, more particularly a vinyl chloride polymer. It is usually made from a monomer comprising vinyl chloride alone or a mixture of monomers comprising at least 70% by weight of vinyl chloride polymer, based on the total weight of vinyl chloride.

In preparing the transparent or translucent hard halogen-containing organic polymer composition of the present invention, the halogen-containing organic polymer and the liquid stabilizer composition of the present invention may be prepared by adding a liquid heat stabilizer to a plastic resin formulation. Can be blended in various amounts.

[0058] The stabilizer composition may be added as a preblend to the halogen-containing organic polymer. However,
It is within the scope of the present invention to add the organotin and complex ester compounds to the halogen-containing organic polymer either simultaneously or sequentially.

Further, when added as a preblend, before the halogen-containing organic polymer composition is processed,
And / or in the process, a halogen-containing organic polymer composition could be added. This also means that when the components of the stabilizer composition of the invention are added simultaneously or sequentially,
Is true. Specifically, under this latter condition, both components may be added to the halogen-containing organic polymer before and / or during the processing step. However, since the components are added separately, one can be added before the start of the processing step, while the other is added during the processing step.

From the above disclosure, one of ordinary skill in the art is expected to envision many different dosing scenarios. All such variations are intended to be protected by the present invention. Although different addition scenarios will likely produce different results, the preferred scenarios will depend in part on the end user's processing parameters and / or the desired properties of the end product.

[0061] The concentration of the stabilizer composition in the resulting halogen-containing organic polymer will depend, in part, on the processing parameters of the end user and / or the desired properties of the final product. However, in certain preferred embodiments, the stabilizer composition of the present invention comprises at least 0.05 ph
r has a useful lower limit of typically at least 0.10 phr, more typically at least 0.20 phr, and even more typically at least 0.5 phr. Similarly,
In certain preferred embodiments, the stabilizer compositions of the present invention have a useful upper limit of up to 10 phr, typically up to 5 phr, and even more typically up to 3 phr. 3
Use in total amounts greater than phr is often fundamentally governed by economics. Below 0.5 part total, the effectiveness of the composition will decrease.

EXAMPLES In the following examples, the thermal stability of PVC formulations prepared with the stabilizer of the present invention (Example 1) was measured using a commercially available methyl organotin stabilizer containing no complex ester (Example 2). ) Was compared with the thermal stability of the PVC formulation prepared using The results of Example 2 show a surprising synergy in the stability performance resulting from the combination of the methyl organotin stabilizer and the complex ester.

The thermal stability of the PVC formulation prepared with the stabilizer of the present invention (Example 3) was also determined using a commercial octyl-, methyl-organotin stabilizer (Example 4). The thermal stability of the two PVC formulations was compared. The stabilizer of Example 3 not only provides the same processing characteristics as the octyl organotin stabilizer, but also has better transparency and better than such films prepared with the octyl organotin stabilizer. Hard transparent P with less yellowing
A VC film is also provided.

[0064] Example 1 stirrer, 90 parts by weight of the two C ₁ methyl organotin compound mixture into reactor equipped with a heater and a thermocouple is added, continue complex ester 10 parts by weight was added. The mixture of the two C ₁ methyl organotin compounds is a 3: 1 (by weight) mixture of dimethyltin bis (2-ethylhexylthioglycolate): methyltin tris (2-ethylhexylthioglycolate). The complex ester was a dark amber odorless liquid obtained from the 7: 6: 14 dehydration condensation product of pentaerythritol: adipic acid: oleic acid. This complex ester has a hydroxy content of less than 3% and about 5,300
It had a molecular weight of g / mol. The liquid blend was stirred at above 50 ° C. for about 10 minutes until a uniform color was obtained.

The performance of this stabilizer was measured using the commercially available methylorganotin stabilizer: ADVAST (ADVAST).
AB) Compared to that of TM-181FS stabilizer (Rohm and Haas Company, Philadelphia, PA, USA).

Example 2 A PVC dry blend formulation ("masterbatch") useful for preparing extruded clear films was prepared with the following components (parts by weight). PVC-SPVC57 100 MBS Impact modifier 4.5 Cetyl stearyl phthalate 1.0 Advalbe 0.4 -E-2107 (Rohm and Haas) PE oxide wax 0.2 Stabilizer containing methyl organotin 0.9

The dynamic thermal stability of the PVC composition prepared with the stabilizer of Example 1 was determined according to the following test using AdvaStab ™.
181 FS: two PVC dry blend masterbatch compositions comprising each component of the formulation,
Each was effectively prepared with 0.9 phr of a methylorganotin stabilizer (Example 1 with 90 weight percent methylorganotin compound was formulated at 1.0 phr). PVC dry blend masterbatch 2
20 g is 25 rolls per minute on a laboratory two roll mill.
Melted counterclockwise and sheared at 195 ° C. for 45 minutes with an automatic arm. Thawed film samples were taken every 3 minutes and allowed to cool to prepare one square inch of rigid PVC film. The color of the PVC film was measured with a HunterLab spectrophotometer.

Color reference scale (L,
As part of a, b), the b value was measured to monitor the decomposition of PVC, as it is the result of yellowing in the early stages of decomposition. The higher the b-value, the more yellow the film. The results recorded in Table 1 show that the stabilizer of Example 1 substantially reduces the yellowing of the PVC film, especially at processing times longer than 15 minutes, with a yellowing of about 3
It was reduced by 0%.

[0069]

[Table 1]

The static thermal stability of these compositions was measured to compare the stability performance independent of the processing history. Dry blends (prepared as described above) were formed into films using a two roll mill. The mill time was kept short to minimize variations in the processing history of the composition. Pieces were cut from each of the films and placed on a support in a 195 ° C. oven. The pieces were slowly removed from the oven to provide an oven residence time gradient for the pieces from 1 minute to 90 minutes. Delta E, which indicates the overall fade in the stabilized PVC composition, was measured along the length of the strip to show the fade as a function of oven residence time. Delta E value 1
00 indicates a non-fading, highly transparent film (non-degraded), while a value of 0 indicates a dark, faded film (substantially degraded)
showed that. The results reported in Table 2 show that after 25 minutes, TM-18 for the composition prepared with the stabilizer of Example 1
It shows that fading occurs more slowly than that of 1FS.

[0071]

[Table 2]

Example 3 A stabilizer composition of the present invention similar to that described in Example 1 was prepared as follows: First, a methyltin mercaptide stabilizer was prepared by adding methyltin chloride and 2-tin. Prepared by aqueous reaction of an ester of ethylhexyl thioglycolate with a base. The stabilizer product forms an organic phase,
It was insoluble in water and phase separated. The aqueous phase was removed and the methyltin mercaptide product was subsequently washed with water to purify the organic phase. The aqueous phase is then removed,
The complex ester of Example 1 was added and stirred at above 50 ° C. for about 10 minutes until a homogeneous phase was obtained. The homogenous stabilizer blend product was purified by vacuum distillation at a pressure of less than 0.1 pounds per square inch in a jacketed steam-heated vessel, followed by filtration to remove salts generated by water removal. .

The performance of the stabilizer composition was compared to that of some commercially available alkyl organotin stabilizers in Example 4: Advastab TM-404 methyl organotin stabilizer (Rohm and Haas, USA , Philadelphia, PA), Ilgastab (IRG)
(ASTAB) 17 MOK octyl organotin stabilizer (Witco Corp, Greenwich, CT, USA).

Example 4 The dynamic thermal stability of a transparent rigid PVC composition prepared with the stabilizer composition of Example 3 (1.35 phr) was measured using Advastab TM-404 (1.35 phr) and Irgastab 17MOK. (1.50 phr) compared to two similar compositions stabilized. These compositions are described in Example 2
The two-roll mill was tested according to the Dynamic Thermal Stability Test.
The amounts of commercially available stabilizers were chosen such that the metal tin content in the formulation was approximately the same. The tin content of the stabilizer composition of Example 3 was about 10% less than that of either of the two commercial stabilizers. Except for the stabilizer content indicated in this example, the PVC formulation was prepared as described in Example 2.

The dynamic stability results show that the PVC masterbatch film prepared with the commercial octyl organotin stabilizer has the greatest yellowing and the film prepared with the commercial methyl organotin stabilizer has the least. Films prepared with the stabilizer composition of Example 3, indicating having yellowing,
It showed intermediate yellowing between the two commercial stabilizers.

The processing characteristics of these three PVC masterbatch film compositions were compared by measuring the time: torque curves for each composition at 165 ° C. by using the Brabender technique. The PVC melting time was determined as the time from peak torque to maximum torque. The results are recorded in Table 3.

[0077]

[Table 3]

The results listed in Table 3 show that the stabilizer composition of Example 3 provides essentially the same processing characteristics as that of the commercially available octyl organotin stabilizer. Commercial methyl organotin stabilizers result in faster PVC
Produces melting time.

The clarity of the 3 mm plates prepared with each of these three PVC masterbatch film compositions was also compared. Hunterlab spectrophotometer
Used to determine the percent haze of each plate. Recorded in Table 4. The results show that in comparison to the commercial octyl organotin stabilizer, the stabilizer composition of Example 3 had a percent haze of about 50% in the clear rigid PVC formulation.
% Decrease.

[0080]

[Table 4]

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Claims (10)

[Claims] [Claim 1] At least the following stabilizer composition comprising a liquid blend: a) at least one C ₁ C ₃ alkyl organotin compound from; and b) (A) at least one polyol and (B) at least one unsaturated At least one complex ester derived from one or more dehydration condensation products with a saturated fatty acid compound; 2. The dehydration condensation product of at least one complex ester of (A) at least one polyol; (B) at least one unsaturated fatty acid compound; and (C) at least one polybasic acid. The stabilizer composition according to claim 1, which is derived from 3. The stabilizer composition of claim 2, wherein at least one polyol comprises pentaerythritol, at least one unsaturated fatty acid compound comprises oleic acid, and at least one polybasic acid comprises adipic acid. object. 4. The stabilizer composition according to claim 1, wherein the hydroxyl content of the at least one complex ester is less than 10 percent by weight, based on the total weight of the at least one complex ester. 5. The stabilizer composition according to claim 1, wherein the molecular weight of the at least one complex ester ranges from 1,000 to 50,000 g / mol. 6. based on the total weight of the sum of alkyl organotin compound and complex esters is the amount of at least 50 weight percent of at least one C ₁ C ₃ alkyl organotin compounds, and at least one complex ester The stabilizer composition according to claim 1, wherein the amount of the stabilizer is up to 50 weight percent. 7. based on the total weight of the sum of alkyl organotin compound and complex esters is the amount of at least 85 weight percent of at least one C ₁ C ₃ alkyl organotin compounds, and at least one complex ester The stabilizer composition according to claim 6, wherein the amount is up to 15 weight percent. 8. C ₃ alkyl organotin compound from at least one C ₁ is methyl organotin - sulfide, methyl organotin - oxide, methyl organotin - carboxylate, methyl organotin - anhydride, methyl organic tin mercaptide, The stabilizer composition according to claim 1, comprising at least one compound selected from the group consisting of methylorganotin-mercaptoalcohol ester and methylorganotin-mercaptocarboxylate. 9. At least one C ₃ alkyl organotin compounds from C ₁ of, dimethyltin bis (isooctyl thioglycolate), mono - and di - Mechirusuzubisu (2-mercaptoethyl oleate), mono - and di - Mechirusuzubisu 2. The composition of claim 1, comprising at least one compound selected from the group consisting of (2 mercaptoethyl laurate), di-methyltin bis (2-ethylhexylthioglycolate), and methyltin tris (2-ethylhexylthioglycolate). A stabilizer compound as described above. 10. A include halogen-containing organic polymer and an organic tin-containing heat stabilizer composition, the heat stabilizer composition contains at least a) at least from one of C ₁ C ₃ alkyl organotin compound; and b) (A) A halogen-containing organic polymer composition comprising a liquid blend of at least one polyol and at least one complex ester derived from one or more dehydration condensation products of (B) at least one unsaturated fatty acid compound.