JPH0379647A - Stabilized diene-based polymer composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized diene-based polymer composition improved in heat resistance and colorability by adding a specific organic cyclic phosphite compound and a specified phenolic compound to diene-based polymer. CONSTITUTION:A composition obtained by adding (B) 0.001-5 pts.wt. organic cyclic phosphite compound expressed by formula I (R1 is 1-9C alkyl; R2 is H or 1-4C alkyl; R3 is 1-30C alkyl) and (C) 0.001-5 pts.wt. phenolic compound expressed by formula II (R4 is 1-4C alkyl; R5 is same as R2; R6 is 2-4C alkenyl) to (A) 100 pts.wt. diene-based polymer (e.g. styrene-butadiene copolymer), containing a conjugated diene compound as an essential component and prepared by polymerizing a monomer having polymerizable unsaturated double bond and, as necessary, further adding a sulfur-based antioxidant, an ultraviolet ray absorber, a hindered amine compound, etc., thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a stabilized diene-based polymer composition, and more particularly, the present invention relates to a stabilized diene-based polymer composition, which is stabilized by adding a specific organic cyclic phosphite compound and a specific phenol compound. The present invention relates to a diene-based polymer composition.

[Conventional technology and its problems]

Synthetic rubber latex, represented by styrene-butadiene latex, is used in a wide range of applications, including paper coating binders, carpets, backing binders, asbestos binders, cement mortar admixtures, paints, adhesives, and adhesives. .

In addition, thermoplastic elastomers, which are copolymers of conjugated dienes and vinyl aromatic compounds, are used as resin modifiers, asphalt modifiers, adhesives, H products, various molded products, other industrial products, miscellaneous goods, etc. Widely used.

Furthermore, impact-resistant resins containing diene polymers, such as ABS resins, have many uses as plastic molded products.

However, because diene-based polymers still have chemically active double bonds in their main chains, they are easily affected by ultraviolet rays, and are not only rapidly colored but also cross-linked and decomposed by the action of sunlight. This leads to a decrease in the physical properties of the polymer. Also, as a matter of course, it is easily oxidized by oxygen in the air, and this tendency is accelerated as the temperature increases. .

These physical properties are fatal drawbacks in fields where durability is required, and limit the uses of diene polymers. To this end, various methods have been studied so far. As a result, various effective ultraviolet absorbers or various light stabilizers have been developed to improve light resistance, and practical light resistance has been achieved. However, although studies on improving heat resistance and coloring properties have been made over the past many years, they have not yet reached a practical level.

For example, JP-A-63-146947 discloses a method of blending a methylene bisphenol derivative into a butadiene polymer, and JP-A-57-85833 describes a method of blending a methylene bisphenol derivative into a butadiene polymer.
- Method of using a bisphenol stabilizer and a thioether stabilizer in combination with polybutadiene, JP-A-62-18445
Each of the publications discloses a method of using a methylene bisphenol derivative and a thioether derivative of pentaerythritol in combination. However, although these methods slightly improve the heat resistance of diene polymers, they have not yet reached a level that is satisfactory from a practical standpoint.

[Means for solving problems]

In view of the current situation, the inventors of the present invention have conducted extensive studies, and have found that
The present invention was completed based on the discovery that excellent heat resistance can be achieved by simultaneously using a specific organic cyclic phosphite compound and a specific phenol compound in a diene polymer.

That is, the present invention is based on the following general formula (1) based on 100 parts by weight of a diene polymer obtained by polymerizing a monomer having a polymerizable unsaturated double bond and containing a conjugated diene compound as an essential component. A stabilized diene polymer obtained by adding ~5 parts by weight of an organic cyclic phosphite compound o, ooi and ~5 parts by weight of a specific phenol compound o, ooi represented by the following general formula (II) It provides something special.

t-Ualiq (wherein, R represents an alkyl group having 1 to 9 carbon atoms,
R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R8 represents an alkyl group having 1 to 30 carbon atoms.

R4 represents an alkyl group having 1 to 4 carbon atoms, Rs represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R
6 represents an alkenyl group having 2 to 4 carbon atoms.) In formula (1) above, the alkyl group having 1 to 9 carbon atoms represented by R1 includes methyl, ethyl, propyl, isopropyl, butyl, Nibutyl, tertiary butyl,
Examples include isobutyl, amyl, tertiary aryl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, and an alkyl group having 1 to 4 carbon atoms represented by R2. Examples include methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl, isobutyl, etc.
As the alkyl group having 1 to 30 carbon atoms,
Methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl, isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, inoctyl, 2
- Ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, tocosyl, tetradecyl, triacontyl and the like.

Further, examples of the alkyl group having 1 to 4 carbon atoms represented by R4 and R3 in formula (II) include an alkyl group that is the same as or different from R2 described above.

Next, as representative examples of the organic cyclic phosphite compound represented by the above-mentioned formula (I) used in the present invention, the following compounds can be mentioned.

t-C & -CaHq t -Ca II w t-C4) 19 The amount of the organic cyclic phosphite compound represented by the above formula (I) used in the present invention is 100% of the diene polymer.
The amount is from o, ooi to 5 parts by weight.

Further, as representative examples of the phenol compound represented by the above-mentioned formula (II) used in the present invention, the following compounds can be mentioned.

1;H.

L;N5 C.I.

C.F.I.

In addition, the amount of the phenol compound represented by the above-mentioned formula (II) is o, o, or
oi~5 parts by weight.

The method of adding the above-mentioned organic cyclic phosphite compound represented by the formula (1) and the phenol compound represented by the general formula (II) to the diene resin of the present invention is not particularly limited, and generally used methods can be used. It can be applied as is.

For example, methods include tri-blending resin powder or pellets with additive powder, spraying a solution or melt of the additive onto resin powder or pellets, mixing a dispersion of the additive into resin latex, and then salting out. method etc. can be used.

The diene compounds used in the present invention include butadiene, isoprene, chlorobrene, 2゜3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1.3
-Hexadiene, ethylidenenorbornene, dicyclopentadiene, etc., and particularly -butadiene and isoprene are mentioned as those used by boats.

These may be used not only alone, but also as a mixture of two or more.

Moreover, these diene compounds can be copolymerized with a copolymerizable ethylenically unsaturated monomer.

Examples of these ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene, and arsolic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and 2-ethylhexyl acrylate. Examples include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and octyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride, and vinyl acetate. Furthermore, vinyl monomers having a functional group can be used, and examples of such vinyl monomers include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid, β-hydroxyethyl acrylate, and hydroxypropyl acrylate. Examples include hydroxyalkyl methacrylates such as hydroxyalkyl methacrylates, diene compounds having a glycidyl group such as glycidyl methacrylate and glycidyl acrylate, and compounds having an amide group such as acrylamide and tomethylol acrylamide.

Therefore, examples of the diene copolymer stabilized by the combination of the phosphite compound and the tjunol compound of the present invention include styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, Examples include vinylidene chloride-styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and ethylene-propylene-ethylidene norbornene copolymer.

It is also possible to further add a sulfur-based antioxidant to the composition of the present invention to improve its oxidative stability.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl, simiristyl, and distearyl esters of thiodipropionic acid, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecylmercaptoprobionate). Examples include propionate esters.

By adding a light stabilizer such as an ultraviolet absorber or a hindered door compound to the composition of the present invention, its light resistance can be further improved.

Examples of the light stabilizer include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenone i[:2-(2°-hydroxy-5”-methylphenyl)benzotriazole, 2-(2′-hydroxy-
5′-tertiary octylphenyl)benzotriazole, 2
- (2'-hydroxy-3', 5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2 -(2°-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5
°-Dicumylphenyl)benzotriazole, 2.2'
-2-(2'-hydroxyphenyl)benzotriazoles such as methylenebis(4-tert-octyl-6-benzotriazolyl)phenol; phenyl salicylate, resorcinol monobenzony-t-12,4-di-tert-butylphenyl- Benzony 11 such as 3',5'-di-tert-butyl-41-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc.
Substituted oxanilides such as 2-ethyl-2°-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide: ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3- Methyl-3-(p-
2,2,6.6-tetramethyl-4-piperidyl stearate, 1,2.2.6.6-bentamethyl-4-piperidyl stearate, 2,2.6. 6-tetramethyl-4-piperidylbenzoate, bis(2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-bentamethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-
Tetramethyl-4-piperidyl)butanetetracarboxylate, tetrakis(1゜2.2.6.6-bentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2 , 6゜6-bentamethyl-4-piperidyl) di(tridecyl)-1,
2,3,4-butanetetracarboxylate, bis(1
,2,2,6,6-bentamethyl-4-piperidyl)-
2-Butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2゜2,6,6-tetramethyl-4-piperiditur/diethyl succinate condensate, 1,6-bis(2,
2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate, 1,6-bis(2,
2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tertiary octylamino-
5-) riazine polycondensate, 1,6-bis(2,2,6,
6-tetramethyl-4-piperidylamino)hexane/
Examples include hindered amine compounds such as 2,4-dichloro-6-morpholino-3-triazine polycondensate.

In addition, if necessary, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, a pigment, a filler, an organic tin compound, a plasticizer, an epoxy compound, a blowing agent, an antistatic agent, and a flame retardant. , lubricants, processing aids, and the like.

〔Example〕

Next, the present invention will be specifically explained using examples.

However, the present invention is not limited to these examples.

Example 1 First, 100 parts by weight of water, 0.2 parts by weight of sodium dodecylbenzenesulfonate, and seed latex (styrene/butadiene = 70/3) were placed in a pressure-resistant polymerization vessel equipped with a dropping device and a stirrer.
0 copolymer latex) 3 parts, 0.05 parts by weight of sodium ethylenediaminetetraacetate, 2 parts by weight of sodium persulfate, and 0.2 parts by weight of sodium hydroxide, and then 47 parts by weight of styrene and 1,3-butadiene. 50 parts by weight, 3 parts by weight of acrylic acid, 0.2 parts by weight of the phenol compound described in 1-6 above, and 0.7 parts by weight of t-dodecyl mercaptan, and after sufficiently purging with nitrogen, heated to 90°C. The reaction was allowed to proceed for 6 hours. As a result, a latex with a solid content of 50% was obtained. The pH of the obtained latex was adjusted to 8.0 with an aqueous sodium hydroxide solution, and then steam distillation and nitrogen blowing were performed to remove residual monomers. Next, 0.3 parts by weight of a dispersion of a cyclic phosphite compound (50%) listed in Table 1 below was added to 100 parts by weight of the solid content of this latex, and after thorough stirring, this latex was Pour onto a Teflon plate and lllll1
A sheet of 1-thickness was prepared and dried overnight. Further 120℃
After drying for 10 minutes, the sample was hung in a gear oven at 160°C, and the time until it became brittle was measured to determine its heat resistance.

The results obtained are shown in Table 1 below.

Table-1 Example 2 25 parts by weight of the 1-2 phosphite compound, the following Table-2
25 parts by weight of phenol compound, 0.5 parts by weight of sodium ethylenediaminetetraacetate, 2 parts by weight of polyoxyethylene nonylphenyl ether, 0.5 parts by weight of calcium alkylbenzenesulfonate, 11 parts by weight of potassium oleate, 0.
2 parts by weight and 44.5 parts by weight of distilled water were homogenized using a homogenizer to obtain an antioxidant dispersion.

Carboxylated styrene-butadiene rubber latex (
solid content 50%) 200 parts by weight, heavy calcium carbonate 30
0 parts by weight of titanium oxide, 40 parts by weight of 5% sodium polyacrylate aqueous solution, and 0.1 part of antifoaming agent, 2 parts by weight of the above antioxidant dispersion (50%) was added, After sufficient stirring, heat resistance was measured in the same manner as in Example 1.

The results are shown in Table-2.

Table 2 Example 3 (Formulation) Styrene monomer 92.5 Potassium persulfate 0.1 Chiral rosin acid sodium 1.0 Dodecyl mercaptan 0.05 Distilled water
200 phosphite compounds (Table-3)
0.45 After thoroughly stirring distilled water, initiator, and emulsifier, put the synthetic rubber into the polymerization tank. Subsequently, styrene monomer and phosphite compound are added. Polymerization is 10 at 70°C.
The polymer thus obtained is salted out with calcium chloride, dehydrated by centrifugation, thoroughly washed with water, and then dried at 80°C for 5 hours. The obtained rubber-modified polystyrene resin (
00 parts by weight were pulverized, 1.0 parts by weight of calcium stearate and 0.11 parts by weight of the phenol n-3 compound were mixed, and a pellet was produced by extrusion molding at 200°C. This pellet was injection molded at 230°C to prepare a test piece. This test piece was heated in a gear oven at 135°C for 20 hours, and the whiteness was measured using a Hunter colorimeter.

The results are shown in Table-3.

Table 3 Example 4 cis-1.4-isoprene rubber (average molecular weight 6800
00) 100 parts by weight, phosphite) I-5 compound 0.1
5 parts by weight, 0.1 parts by weight of a phenol compound and 250 parts by weight of isooctane were taken in Table 4, and after uniformly dissolving them, the solvent was removed. The obtained rubber composition was heated in an oven at 100° C. for 3 hours, and the intrinsic viscosity before and after heating was measured.

The results are shown in Table 4.

Table 3 [Effects of the invention] As is clear from the above examples, by using the specific cyclic phosphite compound of the present invention and the specific phenolated compound in combination, the heat resistance of the diene polymer can be improved.
Colorability can be improved.

Claims (1)

[Scope of Claims] The following general formula ( I
) Organic cyclic phosphite compound represented by 0.001~
5 parts by weight and 0.001 to 5 parts by weight of a phenol compound represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkyl group having 1 to 9 carbon atoms, R_2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_3 represents an alkyl group having 1 to 4 carbon atoms. represents an alkyl group having 1 to 30 carbon atoms; R_4 represents an alkyl group having 1 to 4 carbon atoms;
R_5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_6 represents an alkenyl group having 2 to 4 carbon atoms. )