JPS61140589A - Hydrolytic resistance-improved pentaerythritol-spiro-bis-phosphite composition and composition containing same - 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 [Industrial Application Field] The present invention provides pentaerythritol-spiro-bis-pentaerythritol, which has improved hydrolysis resistance and can be effectively used as a stabilizer.
The present invention relates to a phosphite composition and a resin composition containing the same.

[Conventional technology]

A number of organophosphites have been proposed as stabilizers for polyvinyl chloride resins, either alone or in combination with other stabilizers such as polyvalent metal salts of fatty acids and alkylphenols. Phosphite stabilizers of this type usually contain a sufficient number of alkyl or aryl groups to fill the three valences of the phosphite; typical phosphites include, for example, Leistner (
U.S. Patent No. 2,564 to W. Leiatner et al.
, No. 646 (August 14, 1951), 2,716
．． -092 (August 25, 1955) and 2,9
No. 97,454 (August 2, 1961) and other patent documents.

Organophosphites can also be added to high molecular weight polycarbonate plastics, such as polycarbonate of 2,2'-bis(4-hydroxyphenyl)propane, as stabilizers in an amount of 0.01 to 1%, preferably 0.05 to 0.2% (
weight) may be added.

Phosphite again. It is used in conjunction with other types of stabilizers, such as polyhydric phenols, to stabilize polypropylene and other synthetic resins against deterioration due to heat or aging in atmospheric conditions.

Polyhydric phenols are considered to act as antioxidants under such conditions.

The importance of organic phosphites as stabilizers for synthetic resins is due to their ability to improve the stabilizing effect and improve compatibility and ease of blending with resins and other commonly used stabilizers. This led to the development of a number of special phosphites.

Among these special phosphites, Friedman (L
, Friedman), U.S. Patent No. 3,047,6
No. 08 (July 31, 1962) discloses spirobiphosphite of the following formula. Here R1 and R2 are alkyl or aryl.

Illechen'b'1e
ikner) is U.S. Pat. No. 4,290,976 (19
(September 22, 1981) states that dialkyl pentaerythritol diphosphites with the structural formula (where R, !: R is an alkyl group) were already known as useful stabilizers for vinyl polymers. These types are primarily used to stabilize vinyl chloride polymers and polyolefins, but have also been found to be effective in stabilizing styrene polymers such as ABS.

[Problem to be solved by the invention]

However, these dialkylpentaerythritol diphosphites could not be said to have good stability against hydrolysis. In a humid environment, it is susceptible to hydrolysis, resulting in the loss of the stabilizing effect of the polymer. Many attempts to prevent this hydrolysis have involved the use of additives, which have provided some relief, but the problem still remains, according to Hetzchenpreichner, supra.

Hodan and chassis (8ahall)
)teeth.

U.S. Patent No. 3,553,298' (January 5, 1971)
(Japan), the hydrolytic stability of a wide range of phosphite esters is improved by their combination with nitrogen-containing additives. and the additives include heterocyclic alkyl nitrogen compounds such as piperidine, pyrrolidine, piperazine, diketopiperazine, picoline, anthraquinone, N-methylpyrrolidine, thiazole, oxazolidine, inxazolidine, and oxadiazole; aromatic heterocyclic nitrogen Compounds such as oxazoline, inxacillin, thiotriazole, pyridine, picoline, pyrrole and quinoline: dialkanolamines, such as diisopropaturamine, dialkanolamine,
selected from the group consisting of tetraethanolethylene diamine and tetraisoglopanol ethylene diamine; trialkanolamines such as triisopropanolamine and triethanolamine; ammonia; and alkylamines such as triethylamine, dimethylamine and tripropylamine.

Stabilizers are typically about 0% by weight as phosphite esters.
．． 0.1% to about 5%, preferably about 0.2% to about 1%
Added.

U.S. Patent No. 4,116,926 (September 26, 1978)
(Japan), York found that triisopropanolamine is a particularly useful stabilizer for dialkylpentaerythritol diphosphites and polyalkylbisphenol-A polyphosphites.

Dialkyl pentaerythritol diphosphite has the following structural formula: where R and R' are alkyl groups. Polyalkylbisphenol-A polyphosphite) Um structure, A and B
are H006H,0(O)I, )206H,0 or RO, respectively. R is an alkyl group, and n is 1 to 5.

Most alkyl and alkylaryl pentaerythritol-spiro-bisphosphites having 14 or more carbon atoms in the alkyl or alkylaryl group, and pentaerythritol-spiro-bisphosphites themselves are also solid materials. The melting point of those substances is 40
When the temperature is above 0.degree. C., they can be easily made into granular form and therefore easily mixed with other types of solid stabilizers and formulated with synthetic resins. However, when triisoglopanolamine is used to improve hydrolytic stability, the desirable properties of pentaerythritol-spiro-bis-phosphite as an easy-to-handle particulate solid material are lost and a sticky, rather difficult-to-handle solid material is lost. It changes to

It is not easy to crush it into a granular form, and even if it becomes a single granule, it will clump by itself, and even if it is blended into a multi-component stabilizer, it will easily form lumps with other substances to be mixed.

[Means for solving problems]

According to the method of the present invention, long-chain aliphatic amines are effective in improving the hydrolytic resistance of pentaerythritol-spiro-bis-phosphite and, moreover, can be easily combined with it to create non-stick solid compositions. ), it was found to be easy to grind into granular form, easy to mix with other types of stabilizers and synthetic resins, and avoid the sticking problems that occurred in the case of triisoglopanolamine. .

The pentaerythritol-spiro-bis-phosphite of the present invention with improved hydrolysis resistance is basically: (1) pentaerythritol-spiro-phosphite of the following structure:
bis-phosphite I (wherein R1 and R2 are selected from the group consisting of alkyl groups and alkylaryl groups having from 14 to about 36 carbon atoms); and (2) improving the hydrolysis resistance of the phosphite. A sufficient amount of long chain aliphatic amine π of the following formula: (where R, , R
, and R9 is selected from the group consisting of hydrogen; aliphatic (including alkyl and alkenyl) groups having 1 to about 36 carbon atoms; and hydroxyalkyl groups having 2 to about 6 carbon atoms; R, , R, and R1 is an aliphatic group having at least 14 carbon atoms, and the remainder of R, , R, and R9 are selected from hydrogen, alkyl groups having 1 to 4 carbon atoms; preferably is R
, R, and R2, at least one of which is a hydroxyalkyl group).

The improvement in the hydrolysis resistance of pentaerythritol-spirobis-phosphite is clearly observed even when aliphatic amines are added in very small amounts of 0.1% viscosity. The improvement is seen in proportions when the aliphatic amine is added up to about 35% by weight of the composition, but in many cases amine additions of 0.5% to about 20% are adequate for normal use. Provides hydrolysis resistance. Therefore, the amount added is preferably within this range.

Examples of R, R, and R, alkyl groups of amines include methyl, ethyl, propyl, inglovir, butyl,
Secondary butyl, tertiary butyl, isobutyl, amyl, inamyl, secondary amyl.

2.2-dimethylpropyl, tertiary amyl, hexyl,
These include isohexyl, heptyl, octyl, 2-nitylhexyl, inoctyl, nonyl, isononyl, decyl, indecyl and lauryl. The following are the phosphites R1 and R2 and the amines R, R, and R1
Examples are: myristyl, palmityl, stearyl, eicosyl, behenyl, trickle, teticosyl, ophtacosyl, nonacosyl, triacontyl, hentriacontyl, tritriacontyl, and hexatriacontyl.

The R1 and R2 alkaryl groups in the phosphite are octylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-di-t-butyl-4-meth)dP dicarbonyl, ethylphenyl, iso octylphenyl, t
-octylphenyl, nonylphenyl, 2,4-di-t
-butylphenyl, benzylphenyl and phenethylphenyl.

Examples of pentaerythritol-spiro-bis-phosphites include cimilistyl pentaerythritol diphosphite, dihexadecylbentaerythritol IJ)-rudiphosphite, distearyl pentaerythritol diphosphite, bis(2,4-sheet -7” tylphenyl) pentaerythritol diphosphite, di(2,
6-di-t-butylphenyl)pentaerythritol diphosphite, di(2-t-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,4-
Di-t-butyl-6-methylphenyloctylphenyl pentaerythritol diphosphite, 2,4-di-t
-Butyl-6-methylphenyltnylphenylpentaerythritol diphosphite, bis-(2,6-di-
t-7"thyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-7"thyl-4-ethylphenyl)pentaerythritol diphosphite, 2,6-di-t-butyl- 4-methylphenyl-2,6-di-t-butylphenylbentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylpentaerythritol diphosphite, 2.6-di-t-butyl-4-
Methylphenyl-2,4-di-t-octylpentaerythritol diphosphite, 2,6-di-t-amyl-
4-Methylphenylphenylpentaerythritol diphosbuite, bis(2,6-di-t-amyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-octyl-4-methylphenyl)
0 Pentaerythritol-spiro-bis-phosphite of the present invention with pentaerythritol diphosphite/
Long chain aliphatic amine compositions can be prepared by mixing pentaerythritol-spiro-bis-phosphite and a long chain aliphatic amine in a suitable manner. It is convenient to incorporate the group amine into the melt before solidifying the composition. Pentaerythritol has a relatively high melting point.
The spiro-bis-phosphite can be mixed with the amine in a solvent that dissolves both, such as toluene or isopropanol. In the case of particulate phosphite, there is also a method of mixing or stirring it with an aliphatic amine in molten or granular form. 1. The composition of phosphite and amine does not necessarily have to be completely homogenized. In practice, conditions are such that most of the aliphatic amines are concentrated on or near the surface of the phosphite in the form of a coating or encapsulation. When used in high concentrations, it is expected to maximize its effectiveness.

[Examples and effects of the invention]

The following example shows the pentaerythritol spiro-
It serves to explain the method for producing bis-phosphites.

In a reaction vessel connected to a vacuum device and equipped with a temperature monitoring device, 62.06 t (0.20 mo/L/)% of triphenyl phosphite and 14.98 F.
11motv) and 200.0.52F was added to the anhydrous. The mixture was heated to 150°C under 11011H vacuum;
The O2 container in which the phenol produced in the reaction was collected in a distillation receiver was cooled to 80°C, and 52.5% of the stearyl alcohol was added.
20? (0,193 mol) was added. Busy reheating 1
K to 170℃ (liquid temperature) under 0flHg reduced pressure to approximately 1.5
The phenol was collected in a receiver over a period of h. Reduce the remaining liquid to 75-80
It was cooled to 0.degree. C. and filtered.

Phenol has a total of 55.3 f, or the theoretical value of 98
%Met. The product is a grayish white flaky substance with 71f
, has a melting point of 37-58°C, and has a trivalent syn content of 7.9%,
U.S. Patent No. 5 by Henckel et al.
It was determined by the oxidative titration method described in No. 056,824 (theoretical content of trivalent silane is 8.2%).

8.1 t (o, s mol) of pentaerythritol b was suspended in 125 -tetrahydrofuran, and 144.2 t (1, os mol) of syntrichloride was added dropwise over 1 hour while stirring. During this time, the temperature of the mixture was maintained at 10-15°C by external cooling. After the addition was complete, the cooling bath was removed and the mixture was left to stand, reaching 32°C after 2.5 hours.

A white precipitate was obtained.

After introducing nitrogen gas for 1 hour, 250 d of toluene was added to obtain a transparent solution. A solution of 518.8 t (s, 1 s mol) of triethylamine in 200 °C of toluene was added over 1 hour, during which time the temperature was maintained at 5° C. using a water bath. After adding triethylamine solution, toluene 200
2,4-di-t-butylphenol 2ob dissolved in d
, s t (1 mol) was added and the mixture was stirred for 14 hours.

The mixture was separated to remove triethylamine hydrochloride and F
The liquid was concentrated in vacuo to remove most of the toluene. Upon cooling the concentrate in a water bath, a crystal slurry was seen which was collected, washed with cold toluene and dried to yield the desired phosphite 119.3F. Melting point 175-1
77.5°C, trivalent phosphorus 9.86% by titration (theoretical value of trivalent phosphorus 10.24%).

Examples of alkylmonoalkanolamines belonging to the preferred aliphatic amines include pal, methylethanolamine, stearylethanolamine, oleylethanolamine, myristylethanolamine, behenylethanolamine and eicosylethanolamine; stearylpropaturamine, palmityl. Propanolamine, distearyl monoethanolamine.

There are cibalmityl monoethanolamine, cimyristyl monoethanolamine, and myristyl ethanolamine.

Examples of alkyl dialkanolamines belonging to preferred aliphatic amines include palmityl diethanolamine, stearyl jetanolamine, oleyl jetanolamine, myristyl jetanolamine, behenyl jetanolamine, eicosyl jetanolamine; stearyl dibro These include banolamine, palmityldiglobanolamine and myristyldiglobanolamine.

Examples of trialkylamines are stearyldiethylamine, myristyldiethylamine, palmityldiethylamine, stearyldecyloctylamine, stearylbutyldecylamine, distearylethylamine, divalmitylglobilamine, behenyldimethylamine, and isooctyldibutylamine. .

Examples of dialkylamines include stearylethylamine, myristylethylamine, palmitylethylamine, and stearyldecylamine.

These include stearylbutylamine, stearylmethylamine, palmitylbrobylamine, behenylmethylamine, and eicosylmethylamine.

Examples of monoalkylamines include stearylamine,
Mention may be made of myristylamine, palmitylamine, oleylamine and behenylamine.

The following example illustrates a pentaerythritol-spiro-bis-phosphite composition with improved hydrolysis resistance in accordance with the present invention.

Examples 1 to 4 Examples! To the distearyl-pentaerythritol-bis-phosphite prepared according to the method was added N-n-octadecyljetanolamine ('ill 90%, remainder mostly 016) in the amount shown in Table 1 (below).

Heat the mixture to a hot molten state at 1 and then immediately at 25
Poured onto a metal surface at ~27°C and quenched. In each case, one composition resulted in a single-phase melt that solidified on the metal surface within 2 minutes and could be easily pulled apart. All compositions flaked easily, had some odor, and had good color.

Table 1 30% RH, sample amount 10F As shown in Table 1, the hydrolysis resistance improved in proportion to the amount of amine additive. Example 1/li, a composition containing 5% N-n-octadecyljetanolamine, provided adequate hydrolytic resistance for normal use. Example 2, a composition containing 10% amine, provided excellent resistance even under harsh conditions. Example 4, a composition containing 30% amine, improved tolerance without exhibiting side effects, whereas amine 10
It seems unnecessary to add more amine, since the improvement in hydrolytic resistance is not noticeable compared to compositions containing 25% or 25%.

The hydrolysis resistance of phosphite was expressed as the time required for 50% of the phosphite to decompose after being placed in a constant humidity chamber under constant conditions. Samples of the exposed phosphite were taken periodically and analyzed by liquid chromatography. The operating method used is shown below.

Constant humidity room The constant humidity room is a large desiccator with two stacked plates (5G
AA12! i0,250).

The following composition solution 1500- was put inside the desiccator.

a) 37% NaOH relative humidity (R11) approximately 25% is obtained.

b) 25% NaOR approximately 60% RE C) 100 R11l of water Sample Preparation Weighed the appropriate amount of specimen (or mixture) into a 1 oz wide loss screw capped jar and melted the contents with a heat gun. The melt was stirred to ensure complete homogenization. After crystallization, the mixture was ground in a mortar and pestle to a fine powder. The phosphite to be tested as is without any additives was added without melting.

A specified amount of ground powder was placed in an aluminum weighing pan (SGAA9000), and the time when the pan was placed in the indoor room was defined as 0 o'clock. At the same time, liquid chromatography analysis was started at 0 o'clock. Thereafter, each time a sample for liquid chromatography analysis was taken out, the powder was sufficiently stirred in the aluminum dish using a spatula just before sampling.

22 people, 100 kg of full (8 GA/a5250) VC samples were accurately weighed, and a micro magnetic stirring bar and liquid chromatography solvent (below) 51 (accurately weighed) were also added.

The mixture was stirred for 10 minutes on a magnetic stirring plate and stirred for sample purification (Waters Catalog 268).
65). Exactly 10μ of filtrate! ,
Injections were made using liquid chromatography parameters as shown below.

Liquid chromatographyLiquid chromatography operation uses improved DuPont-Silica-Zor
-bax -ON column (Dupont A350952-
705). A solvent consisting of a 10=1 (v/■) mixture of isooctane-THF (liquid chromatography grade) was pumped at a rate of 11 Lt/ml. Chart speed = 0.5"/min s Detector: 4x refractive index attenuation and UV spectrum (at 254 m ><0.1x AUFEI).

Calculations All calculations were performed on the observed refractive index trace. Peak height was measured from baseline (in units). The response factor f was calculated for each peak using the following formula.

Weight (nominal) x 2 This formula dissolves the sample in a 5-solvent and calculates its 10ρj
It holds true only when 7 is injected.

Changes in "f" over time were tracked. After total hydrolysis.

The f value of the sample at 0 o'clock was set to 100, and the f value was standardized. When the standardized values are plotted against time (in hours or days) K, 50% resolution time is changed.

When two or more peaks appear in a gram of % phosphite chromatography, as in the case of the isomer of distearyl pentaerythritol diphosphite, and the peaks show different decomposition rates, each peak is analyzed separately. The measured 50% degradation times were averaged.

For comparison, a portion of the distearyl pentaerythritol-spiro-bis-phosphite of Example was taken and mixed with tri-inglopanolamine in the proportions shown in the following Table 7 by hot melting.

The results observed are as follows: Table π The 5% and 10% amine containing compositions of Experiments S1 and 2 formed a homogeneous melt when poured onto a cold metal surface at 25-27°C. Although it solidified, the product was sticky and could not be easily separated from the metal surface. Amine level 25%
In Experiment 3, two phases were formed during melting, the -phase being a mixture of amici and phosphite, and the -phase consisting of amine. The composition solidified slowly when in contact with a cold metal surface, and the resulting product was extremely sticky.

Examples 5-7 To di(2,4-di-1-butylphenyl)pentaerythritol-bis-phosphite prepared according to Example π, a long chain aliphatic amine was added as described in Table m below: 100% RH, sample amount 1.25F, mixed amine and phosphite as a solution. Dry mixing of amine and phosphite. Ami/
was dramatically improved by the addition of

The phosphite/amine composition of the present invention is effective in increasing the resistance of polyvinyl chloride resins to deterioration due to light and heat, and the effect is particularly remarkable when used in combination with other known stabilizers. Here, the term ``1 polyvinyl chloride'' means:
A polymer having at least a portion of the repeating unit and containing 40% or more of chlorine is included. In the above group, each X group may be either hydrogen or chlorine, n being the number of this unit in the polymer chain. In the case of polyvinyl chloride homopolymer,
Each X group is hydrogen. Therefore, this term includes not only polyvinyl chloride homopolymers, but also the post-chlorinated polyvinyl chloride disclosed in British Patent No. 895,288, as well as other copolymerizable monomers with vinyl chloride as the main component. Vinyl chloride copolymers having as a subcomponent, such as copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and maleic acid or fumaric acid or their esters, and copolymers of vinyl chloride and styrene. It also includes merging. The stabilizer composition is also effective for mixtures containing polyvinyl chloride as a main component and other synthetic resins as secondary components such as chlorinated polyethylene or copolymers of acrylonitrile, butadiene and styrene.

It is applied to the stabilization of resin compositions to be blended so that they can be processed, but it can also be used to stabilize commonly blended soft plasticized polyvinyl chloride resin compositions that do not require heat deformation resistance.

Common plasticizers well known in the art include, for example, dioctyl phthalate, octyl diphenyl phosphate, and epoxidized soybean oil.

Particularly useful plasticizers are epoxy higher esters containing 20 to 150 carbon atoms. This is because esters of this type initially have an unsaturated group in the alcohol or acid portion of the molecule, which is eliminated by the formation of an epoxy group.

Typical unsaturated acids are acrylic acid, oleic acid, linoleic acid, lylinic acid, erucic acid, lysyllic acid, and placidic acid, which are esterified with organic or polyhydric alcohols to form acids and alcohols. The total number of carbon atoms may be set within the above range. Typical monohydric alcohols are haftyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, inoctyl alcohol, stearyl alcohol, and oleyl alcohol. Octyl alcohols are excellent. Representative polyhydric alcohols hapentaerythritol, glycerin, ethylene glycol, 1,2-propylene glycol, 1
．． 4-7" ethylene glycol, neopentyl glycol, lysyl alcohol, erythritol, mannitol, and sorbitol. Glycerin is superior. These alcohols are partially or completely esterified with epoxidizing acids. Also useful are epoxidized mixtures of higher fatty acid esters in naturally occurring fats and oils, such as epoxidized soybean oil, epoxidized olive oil, epoxidized coconut oil, epoxidized cottonseed oil, and epoxidized toll. There are oil fatty acid esters and epoxidized beef tallow.Among these, epoxidized soybean oil is superior.0 Alcohols may contain epoxy groups and may be either long or short chains.Acids are long chain Examples include epoxy stearyl acetate, epoxy stearyl stearate, glycidyl stearate, and glycidyl methacrylate polymers.

Polyvinyl chloride resins can be in any physical form, including powders, films, sheets, molded articles, foams, filaments, and yarns.

With a sufficient amount of phosphite/amine stabilizer composition,
It serves to enhance the resistance to deterioration of the physical properties of polyvinyl chloride, such as discoloration, brittleness, and fading due to heat and/or light conditions to which the polymer is subjected. Usually a very small amount is appropriate. The weight of polyvinyl chloride is about 0.01 to about 5% phosphite.

Amounts ranging from 0.01 to about 10% are sufficient for other species. Preferably from about 0.05% to about 2% phosphite
Optimal stabilizing effects can be obtained by using about 0.1 to about 5% of other stabilizers.

The phosphite/amine stabilizer compositions of this invention can be used alone. It can also be used with other common heat and light stabilizers for polyvinyl chloride, such as polyvalent metal salts and alkaline earth metal salts of phosphorous acid, and epoxy compounds.

Particularly useful stabilizer systems have the following component composition: (a) from about 25 to about 45 parts by weight of phosphite;
(b) about 0.01 to about 1 part by weight of a phenolic antioxidant; (c) about 25 to about 45 parts by weight of a polyvalent metal salt of an aliphatic carboxylic acid or alkylphenol; and (e) about 0.5 to about 5 parts by weight of an acidic phosphite.
Department.

Additionally, the usual polyvinyl chloride resin additives, such as lubricants, emulsifiers, antistatic agents, flame retardants.

Pigments and fillers may also be added.

Preferably, the stabilizer system is for polyvinyl chloride resin.
About 0.2 to about 1% phosphite; about 0.1 to about 2% phenolic antioxidant;
A total of 0 to about 1% of the above may be added as described above.

The stabilizer system is added to the polymer in a suitable mixer such as a mill or Banbury mixer.

If the polymer has a melt viscosity that is too high for the intended use, it may be helpful to work to reduce the melt viscosity to the desired range before adding the stabilizer. The mixing operation continues until the mixture is substantially homogeneous. The resulting composition is then removed from the mixer and made into the desired size and shape for marketing or use.

The stabilized polyvinyl chloride resin can be formed into the desired form by kneading, calendering, extrusion or injection molding, or fiber formation. During such operations, it is found that it has significantly improved resistance to discoloration and embrittlement when exposed to heat and light.

The phosphite/amine stabilizer compositions of this invention are particularly effective thermal stabilizers for olefin polymers such as polyethylene, polypropylene, polybutylene, polybenzene, and even higher polyolefins.

Olefin polymers decompose when exposed to high temperatures, causing embrittlement and discoloration.

The phosphite/amine stabilizer composition can be made from low density polyethylene, high density polyethylene, Ziegler-Natsuta (Zi
, Egler-Natta) method, polypropylenes produced by the Zieg-Zutume method and other propylene polymerization methods, poly(butene-1), poly(pentene-1), poly(3-methylbutene-1) , poly(4-methylpentene-1), polystyrene, and mixtures of polyethylene and polypropylene with other compatible polymers, such as mixtures of polyethylene and polypropylene, and copolymers of olefins, such as mutual ethylene, propylene, butylene. It can be used for various olefin polymers including copolymers with other types of copolymerizable monomers. The term "olefin polymer" is intended to include both homopolymers and copolymers.

Polypropylene solid polymer has a density of 0.86 to 0.
．． It can be distinguished from other polyolefins in that it has a melting point of about 150°C. The phosphite of the present invention can be applied to all polypropylenes other than liquid or semi-solid gel polypropylene used in greases and waxes.

The phosphite/amine stabilizer compositions of the present invention are applicable to polypropylene made using any manufacturing method. This is because molecular weight and toughness are irrelevant for this stabilizer system. It is commercially available under the trade name PRO-FAX and is an example of polypropylene resin.

Mixtures of polypropylene with other compatible polymers, as well as copolymers of propylene with non-reactive monomers copolymerizable therewith, such as bosphite or other stabilizer compositions, can also be stabilized. Examples are mixtures of polyethylene and polyglobylene, copolymers of propylene and ethylene.

The phosphite/amine stabilizer composition consists of polystyrene:
Polydienes, such as polybutadiene and polyimprene; and copolymers of olefins and dienes with other ethylenically and acetylenically unsaturated monomers, such as ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, etc.
All types of synthetic rubbers such as acrylonitrile-styrene-butadiene copolymers, polychloroprene; polyvinylidene chloride; copolymers of vinyl chloride and vinylidene chloride; vinyl chloride and vinyl acetate; other ethylenically unsaturated Monomers; polyacetals such as polyoxymethylene and polyoxyethylene; polycarbonates; polyphenylene oxides; polyesters such as polyethylene terephthalate; polycaprolactam; polyamides such as polyhexamethylene adipamide and polydecamethylene adipamide; The synthetic polymer, which is also effective in improving the heat deterioration resistance of epoxy resins, can be in any physical form. Examples include filaments, yarns, films, sheets, moldings, latex and foams.

The use of sufficient amounts of stabilizer compositions containing phosphites and amines can reduce the deterioration of the physical properties of synthetic polymers, such as discoloration, reduction of melt viscosity, and brittleness under various experimental conditions to which the polymer is expected to be subjected. It is possible to improve the resistance to corrosion. Usually very small amounts are useful.

0.001 to about 5 total stabilizers by weight of polymer
It is sufficient to use it within a range of %. For optimal stabilization, use of 0.01 to 3% appears to be appropriate.

The phosphite/amine compositions of this invention may be used alone or, for certain olefin polymers, in conjunction with other commonly used heat and light stabilizers.

By way of example, fatty acid salts of polyvalent metals and higher aliphatic alkyl esters of thiodipropionic acid, such as diracryl thiodigropionate, can be used.

In polyamide resin compositions, copper salts can be used in combination with iodides and/or other sulfur compounds, and polyamide stabilizers such as divalent manganese salts can be used.

For synthetic rubber and acrylonitrile-butadiene-styrene terpolymer, polyvalent metal salts of higher fatty acids can be used.

In addition, other additives commonly used for synthetic polymers can be used, such as plasticizers, lubricants, emulsifiers, antistatic agents, flame retardants, pigments and fillers.

The stabilizer composition is incorporated into the polymer in mobile mixing equipment such as a mill or Banbury mixer. If the melt viscosity of the polymer is too high to handle, the polymer can be co-treated to reduce its melt viscosity to the desired range before adding the stabilizer. Continue mixing until the mixture is approximately homogeneous. The composition is then discharged from the mixing device and finished into a size and form convenient for commercial sale or use.

Stabilizing polymers can be processed into the desired form by, for example, kneading, calendering, extrusion or injection molding, or spinning. It can be seen that through such operations, the resistance to a decrease in melt viscosity due to heating, and the resistance to discoloration and brittleness due to aging or heating are significantly improved.

The following example shows the pentaerythritol spiro-
This figure shows an advantageous embodiment of a synthetic resin composition containing a composition of bis-phosphite and an amine.

Examples 8 and 9 Three types of polyvinyl chloride resin compositions were prepared with the following formulations: Parts by weight dialkyl phthalate (5 anticizer 711)
"Epoxidized soybean oil 7 7 7 Phosphite of Example 1/., 2--Amine composition Phosphite of Example 6/-0,2-Amine composition Zinc stearate 0°15 0.15 0.25 Calcicum stearate 0.12 0.12 0.
192.6-di-t-butyl-. , 05B 0.03
B 0.06 p-cresol was combined, and then the sheet was taken out. Cut the kneaded sheet into strips and place them in the open at 177°C (
550? ) or 190°C (375?) until dark edges appeared on the sample. After 10 minutes each sample was cut from the strip and placed on a card.

The time until the sample turned yellow and dark edges appeared was recorded.

The results are shown in Table W below.

Samples were also molded into o, oso inch thick panels and tested using a Hunter colorimeter to ASTM D 1925-
The yellowing index was determined according to 70. The results are shown below.

Table N o, oso "color yellowing index of molded product, AEITMD1925-70 2.02
3.51 5.94 A low yellowing index indicates a low degree of yellowing and therefore a good sample. Examples 8 and 9 are clearly superior.

Three types of polyglopylene compositions with the following formulations were made: Part by weight Calcium stearate 0.1 0.1 0
．． 1 Distearylthiodigropio 0.3 0
．． 5 Phosphite of 0.5 nate Example 5/-. , 2-amine composition was kneaded and then formed into a panel sample with a thickness of 0.04 inch, and using a Hunter colorimeter, A8TMDI9
The yellowing index was determined according to 25-70. The results are shown in the table below.

Molding for 5 minutes at 204℃ 7.16 5.34
10.2 Molding at 1288℃ for 15 minutes 17.24
17.56 18.69 Examples 10 and 11 are clearly superior 0 Applicant's agent Takashi Furuya Kaorimizobe Hikoko Satoshi Tani

Claims (1)

[Scope of Claims] 1 (1) Pentaerythritol spiro- of the following formula I
Bis-phosphites: ▲Mathical formulas, chemical formulas, tables, etc.▼ I (wherein R_1 and R_2 are selected from the group consisting of alkyl groups and alkylaryl groups having from 14 to about 36 carbon atoms); and (2 ) A long chain aliphatic amine of the following formula II in an amount sufficient to improve the hydrolysis resistance of the phosphite: ▲ Numerical formula, chemical formula, table, etc. ▼II (where R_3, R_4 and R_5 are hydrogen; selected from the group consisting of aliphatic groups having about 36 carbon atoms; and hydroxyalkyl groups having from 2 to about 6 carbon atoms; one of R_3, R_4 and R_5 has at least 14 carbon atoms; aliphatic group, R_3, R_4
and the remainder of R_5 is selected from hydrogen, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups. 2. Pentaerythritol-spiro-bis- according to claim 1, wherein R_1 and R_2 are alkyl groups.
Phosphite composition. 3. The pentaerythritol-spiro-bis-phosphite composition according to claim 1, wherein R_1 and R_2 are alkylaryl groups. 4 Claim 1, wherein the amine is an aliphatic amine
The pentaerythritol-spiro-bis-phosphite composition described in Section 1. 5. The pentaerythritol-spiro-bis-phosphite composition of claim 1, wherein the amine is an aliphatic amine having at least one hydroxyalkyl group. 6 Claim 1, wherein the amine is an aliphatic amine in which one of R_3, R_4 and R_5 is hydrogen.
The pentaerythritol-spiro-bis-phosphite composition described in Section 1. 7 The amine is two of R_3, R_4 and R_5
2. The pentaerythritol-spiro-bis-phosphite composition of claim 1, which is an aliphatic amine in which each is hydrogen. 8 The amine is one of R_3, R_4 and R_5
A pentaerythritol-spiro-bis-phosphite composition according to claim 1, wherein each of the pentaerythritol-spiro-bis-phosphites is an aliphatic amine in which each group is an alkyl group having 1 to 4 carbon atoms. 9 The amine is two of R_3, R_4 and R_5
A pentaerythritol-spiro-bis-phosphite composition according to claim 1, wherein each of the pentaerythritol-spiro-bis-phosphites is an aliphatic amine in which each group is an alkyl group having 1 to 4 carbon atoms. 10. The pentaerythritol-spiro-bis-phosphite composition of claim 1, wherein the amine is an aliphatic amine having two hydroxyalkyl groups. 11. The pentaerythritol-spiro-bis-phosphite composition according to claim 10, wherein the hydroxyalkyl group is a hydroxyethyl group. 12. The pentaerythritol-spiro-bis-phosphite composition of claim 1, wherein the amine is Nn-octadecyldiethanolamine. 13 (1) Pentaerythritol-spiro-bis-phosphite of the following formula I: ▲Mathematical formulas, chemical formulas, tables, etc.▼ I (Here, R_1 and R_2 are alkyl groups and alkyl groups having from 14 to about 36 carbon atoms. aryl group); and (2) a long chain aliphatic amine of formula II in an amount sufficient to improve the hydrolysis resistance of the phosphite: wherein R_3, R_4 and R_5 are selected from the group consisting of hydrogen; aliphatic groups having from 1 to about 36 carbon atoms; and hydroxyalkyl groups having from 2 to about 6 carbon atoms; One of R_5 is an aliphatic group having at least 14 carbon atoms, R_3, R_4
and the remainder of R_5 is selected from hydrogen, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups); and phenol. 1. A stabilizer composition comprising a synthetic antioxidant and capable of improving the resistance of a synthetic resin composition to deterioration due to heat and/or light. 14 (1) Pentaerythritol-spiro-bis-phosphite of the following formula I: ▲Mathematical formulas, chemical formulas, tables, etc.▼ I (Here, R_1 and R_2 are alkyl groups and alkyl groups having from 14 to about 36 carbon atoms. aryl group); and (2) a long chain aliphatic amine of formula II in an amount sufficient to improve the hydrolysis resistance of the phosphite: wherein R_3, R_4 and R_5 are selected from the group consisting of hydrogen; aliphatic groups having from 1 to about 36 carbon atoms, and hydroxyalkyl groups having from 2 to about 6 carbon atoms; R_3, R_4 and One of R_5 is an aliphatic group having at least 14 carbon atoms, R_3, R_4
and the remainder of R_5 is selected from hydrogen, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups); It is made of polyvinyl chloride resin that has some repeating groups ▲mathematical formulas, chemical formulas, tables, etc.▼, has a chlorine content of 40% or more, and X is hydrogen or chlorine, and is resistant to deterioration when heated to 177°C. A polyvinyl chloride resin composition with improved properties. 15. The polyvinyl chloride resin composition according to claim 14, wherein the polyvinyl chloride resin is a polyvinyl chloride homopolymer. 16. The polyvinyl chloride resin composition according to claim 14, wherein the polyvinyl chloride resin is a copolymer of vinyl chloride and vinyl acetate. 17 (1) Pentaerythritol-spiro-bis-phosphite of the following formula I: ▲Mathematical formulas, chemical formulas, tables, etc.▼ I (Here, R_1 and R_2 are alkyl groups and alkyl groups having from 14 to about 36 carbon atoms. aryl group); and (2) a long chain aliphatic amine of formula II in an amount sufficient to improve the hydrolysis resistance of the phosphite: wherein R_3, R_4 and R_5 are selected from the group consisting of hydrogen; aliphatic groups having from 1 to about 36 carbon atoms; and hydroxyalkyl groups having from 2 to about 6 carbon atoms; One of R_5 is an aliphatic group having at least 14 carbon atoms, R_3, R_4
and the remainder of R_5 is selected from hydrogen, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups); 2. An olefin polymer composition having improved resistance to deterioration, comprising an olefin polymer selected from the group consisting of an alpha olefin polymer having 6 carbon atoms and polystyrene. 18. The olefin polymer composition according to claim 17, wherein the polyolefin is polypropylene. 19. The olefin polymer composition according to claim 17, wherein the polyolefin is polyethylene.