JPS6118579B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermoplastic polymer composition with improved thermal stability, which is made by blending a chroman derivative with a polyolefin. Molding of thermoplastic resins such as polyolefins is usually carried out at temperatures of 200°C or higher, and sometimes close to 300°C. In such cases, the molecular weight of these polymers decreases due to heat, chemical effects such as oxygen, and mechanical effects such as shearing force, and desirable physical properties are often not obtained. In order to prevent such quality deterioration during molding, various stabilizers have been conventionally blended, but satisfactory results have not yet been obtained. The present invention aims to provide a thermoplastic polymer composition with improved thermal stability,
General formula for polyolefin (In the formula, R ¹ is a hydrocarbon group having 1 to 16 carbon atoms,
R ² to R ⁷ , R ⁹ and R ¹⁰ are hydrogen or have 1 carbon number
to 7 alkyl groups, R ⁸ is

[expression] or

A group represented by the formula [where n is a positive integer of 1 to 3,
R ¹¹ and R ¹³ are hydrogen or alkyl groups, R ¹² and R ¹⁴ are hydrogen, alkyl groups or The present invention relates to a thermoplastic polymer composition containing a chroman derivative represented by the following formula (wherein R ¹ to R ⁷ , R ⁹ and R ¹⁰ are the same as the general formula described above). The polyolefins used in the present invention include ethylene and its homologs propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-
Liquid, jelly-like, wax-like, resin-like, and rubber-like synthetic polymers obtained by monopolymerizing or copolymerizing monomers selected from ethylene such as pentene and styrene, and α-olefins having usually 10 or less carbon atoms. It is a copolymer. In the case of a copolymer, the copolymer component may contain polyunsaturated compounds such as conjugated dienes and non-conjugated dienes, or other copolymerizable monomer components. Specifically, liquid polyethylene, liquid polypropylene, liquid polyisobutene, jelly polyethylene, jelly polypropylene, jelly polyisobutene, jelly ethylene/propylene copolymer, waxy polyethylene, waxy polypropylene, waxy ethylene/propylene, or ethylene. -1-butene copolymer, polypropylene, poly-1-butene, polyisobutene, poly-3-methyl-1-butene, poly-
4-methyl-1-pentene, polystyrene, poly-α-methylstyrene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, propylene-1- These include resinous and rubbery polymers such as butene copolymers and 1-decene-4-methyl-1-pentene copolymers. When discussing various polymers made of ethylene, liquid polymers usually have a viscosity average molecular weight of 250.
to 400, a polymer with a crystallinity of 10% or less,
Jelly-like polymers usually have a viscosity average molecular weight of 300
to 4000, crystallinity 10 to 60%, consistency (JIS
K-2524-1961) It is usually a polymer with a viscosity average molecular weight of 250 or less.
400 to 15000, crystallinity 20 to 95%, hardness (JIS K-2530 penetration) 0 to 50, resinous polymer has a viscosity average molecular weight, usually 7000 or more,
A polymer having a crystallinity of usually 30 to 97% and a Young's modulus of 10 ³ to 10 ⁵ Kg/cm ² , while a rubbery polymer has a Mooney viscosity of ML ₁₊₄ in an unvulcanized state, usually 10
100 to 100, crystallinity usually 1 to 5% by X-ray diffraction, and Young's modulus at room temperature usually 10 to 10 ² Kg/cm ² . Thermoplastic elastic polymers have properties intermediate between thermoplastic resins and rubber-like polymers, and their X-ray crystallinity is usually 10 to 20%.
Young's modulus is typically 10 ² to 10 ³ Kg/cm ² of the polymer. What is the viscosity average molecular weight? The intrinsic viscosity [η] of a solution in decalin at 135℃ is Mv=2.51×10 ⁴ [η] ^1
．． This is the value obtained by substituting it into ²³⁵ . These polymers may be acid-modified,
For example, polymers graft-modified with α,β-unsaturated fatty acids, alicyclic carboxylic acids, or derivatives thereof are also included. In the present invention, two or more of these polymers may be used in combination, and a composition of an unmodified polymer and an acid-modified polymer may be used. The chroman derivative blended into the polyolefin is represented by the above general formula. In the formula, R ¹ is a methyl group, CH ₃ C (CH ₃ )=CHCH ₂ CH ₂ − group, CH ₃ [CH
(CH ₃ )CH ₂ CH ₂ CH ₂ ] ₃ groups, CH ₃ [C(CH ₃ )=
A carbon hydrogen group having 1 to 16 carbon atoms such as CHCH ₂ CH ₂ ] ₃ group, particularly preferably a hydrocarbon group having 16 carbon atoms. R ² to R ⁷ , R ⁹ and R ¹⁰ are hydrogen or an alkyl group having 1 to 7 carbon atoms. this house
R ² to R ⁶ are preferably hydrogen or a methyl group,
It is preferable that at least two or more of R ⁷ , R ⁹ and R ¹⁰ are methyl groups or tert-butyl groups. ^R8
is a group containing oxygen, sulfur, phosphorus and/or nitrogen, such as an alkanoyl group, an aroyl group, an alkoxycarbonyl group, an alkanesulfonyl group, an arenesulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group and a phosphorus oxoacid residue. There is. Specific examples of these include formyl, acetyl, propionyl, isopropionyl, butyl, isobutyryl, pentanoyl, and hexanoyl as lower alkanoyl groups, and heptanoyl, octanoyl, and higher alkanoyl groups.
Nonanoyl, decanoyl, undecanoyl, dodecanoyl (lauroyl), tridecanoyl, tetradecanoyl (myristoyl), pentadecanoyl, hexadecanoyl (valmitoyl), heptadecanoyl, octadecanoyl (stearoyl)
Aroyl groups include benzoyl, toluoyl, xyloyl, and naphthoyl, and alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, and hexyloxycarbonyl. Alkanesulfonyl groups include mesyl, ethanesulfonyl, propanesulfonyl, 1-methylethanesulfonyl, butanesulfonyl, 1-methylpropanesulfonyl, pentasulfonyl, hexanesulfonyl, and arenesulfonyl groups include benzenesulfonyl, toluenesulfonyl, There are xylene sulfonyl, naphthalene sulfonyl, etc.Alkylcarbamoyl groups include methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, isobutylcarbamoyl, tert-butylcarbamoyl, pentylcarbamoyl, hexylcarbamoyl, and arylcarbamoyl groups include These include phenylcarbamoyl, naphthocarbamoyl, tolylcarbamoyl, xylylcarbamoyl, mesitylcarbamoyl, and cumenylcarbamoyl. In the chroman derivative preferably used in the present invention, R ⁸ in the general formula is a phosphorus oxoacid residue,

[expression] or

It is a chroman derivative consisting of a group represented by the formula:
[In the formula, n is a positive integer of 1 to 3, R ¹¹ and R ¹³ are hydrogen or an alkyl group R ¹² and R ¹⁴ are hydrogen, an alkyl group, or There is a group represented by (in the formula, R ¹ to R ⁷ , R ⁹ and R ¹⁰ are the same as in the above general formula). These R ⁸ groups include phosphinic acid, phosphonic acid, diphosphonic acid which is a condensation product of these,
There are residues such as triphosphonic acid, or phosphorus oxoacid residues in which part or all of these are esterified. In addition, as R ⁸ , (In the formula, R ¹ to R ⁷ , R ⁹ and R ¹⁰ are the same as in the above general formula, and R ¹⁵ is an alkylene group or an arylene group). The amount of these compounds added to polyolefin is 0.005 to 100 parts by weight of polyolefin.
0.5 part by weight is preferred, especially 0.01 to 0.2 part by weight. If the amount is less than 0.005 part by weight, there is almost no thermal stabilizing effect, and if it is added in excess of 0.5 part by weight, there is not much difference in the effect, and other physical properties are deteriorated on the contrary, which is not preferable. The composition of the present invention may contain
Other additives, such as process oils, plasticizers, lubricating oils, organic or inorganic fillers, dyes, pigments, nucleating agents, antistatic agents, mold release agents, fungicides, antioxidants, UV absorbers, A refueling agent can be added. When used in combination with other stabilizers, synergistic effects may be observed. Examples of these are phenolic stabilizers. c-tert-butyl-p
-Methoxyphenol (BHA), Tetrakis [methylene-3-(3,5-di-tert-butyl-4-
hydroxyphenyl) propionate] methane (Irgancx 1010), 4,4'-butylidene bis(6-
tert-butyl-m-cresol), 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-
tert-butyl-4-hydroxybenzyl)benzene, styrenated cresol, 6-hydroxychroman derivatives such as tocopherols, and the amine stabilizer N,N'-di-sec-butyl-p-
Phenyldiamine, 6-ethoxy-2,2,4-
Trimethyl-1,2-dihydroquinoline, phenothiazine, N,N'-diphenyl-p-phenylenediamine, dilaurylthiodipropionate,
Thiodialkanoic acid esters such as dimyristylthiodifuropionate, phosphites such as triotadecyl phosphite, triphenyl phosphite, tri(octadecylthio) phosphite, ascorbic acid, fatty acid monoglycerides,
Benzophenone, 2-(2'-hydroxy-3',
Benzotriazole compounds such as 5′-di-tert-butylphenyl)-5-chlorobenzotriazole, 4-benzoyloxy-2,2,6,6-
There are piperidine core-containing compounds such as tetramethylpiperidine, and piperazine core-containing compounds such as 2,2,6,6-tetramethylpiperazine. Depending on the application, one or more of these compounds may be used in combination, and the amount of each compound may vary depending on the polyolefin.
The amount is usually 0.01 to 1 part by weight per 100 parts by weight. Other additives include magnesium oxide,
Magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc, clay, barium sulfate, gypsum, glass fiber, wood flour, synthetic wood fiber, titania, calcium carbonate,
carbon black, mica, petroleum resin, rosin,
An example is natural rubber. These compounding amounts are 1 to 50 parts by weight, respectively, per 100 parts by weight of polyolefin.
Parts by weight are usual. In the present invention, additives particularly preferably used in combination include phosphoric acids, organic oxyacids, imidazole compounds, and tetrakis[methylene-
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane. Phosphoric acids include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, such as triphosphoric acid, tetraphosphoric acid, and polymetaphosphoric acid, such as trimetaphosphoric acid and tetrametaphosphoric acid, and organic oxyacids include glycolic acid and malic acid. , cumenoic acid, isocitric acid, tartaric acid, etc. are used.
Imidazole compounds include 2-undecanyl imidazole and 2-heptadecylinimidazole. It is preferable to use one or more kinds of these, particularly two or more kinds in combination. The amount of phosphoric acid compounded is preferably 0.005 to 0.1 part by weight, particularly 0.01 to 0.05 part by weight, per 100 parts by weight of polyolefin. Similarly, the amount of the organic oxyacid or imidazole compound is preferably 0.005 to 0.5 parts by weight, particularly 0.01 to 0.1 parts by weight. When polyolefin obtained by polymerization using a Ziegler type catalyst is used without deashing, it is more effective to use an alcohol or polyhydric alcohol having an ether bond, ester bond, or amino bond in addition to the above stabilizer. becomes noticeable. Examples of such compounds include:
Polyhydric alcohols such as glycerin, sorbitan, bentaerythritol, partial esters of these polyhydric alcohols and fatty acids having 8 to 22 carbon atoms, polyethylene glycol, polypropylene glycol, citric acid mono- or distearate, propylene glycol, sucrose, polyester Glycerin, polyethylene glycol, polypropylene glycol, polyoxyethylene glycerin,
C8 to C22 fatty acid partial esters of polyhydric alcohols such as polyoxyethylene sorbitan,
Monoether of polyethylene glycol and aliphatic alcohol having 12 to 22 carbon atoms or phenol having an alkyl group having 4 to 22 carbon atoms, aliphatic amine having 8 to 22 carbon atoms or N,N-bis(2 -hydroxyethyl) substituted products. These are preferably blended in an amount of 0.01 to 5% by weight, particularly preferably 0.05 to 1.0% by weight, based on the polyolefin. Any method suitable for obtaining a uniform composition can be adopted as a method for blending the chroman derivative or the above-mentioned additives together with the polyolefin. For example, there are methods in which these compounds are dissolved or dispersed in a low boiling point solvent, mixed with polyolefin powder, and then the solvent is evaporated off, and methods in which the polyolefin is heated above its melting point on a hot roll and then these compounds are added. There are methods such as mixing, using a Banbury mixer, Henschel mixer, etc. Examples are shown below. Examples 1 to 20 and Comparative Examples 1 to 3 Polypropylene (Mitsui Petrochemical Polypropylene)
0.1 part by weight of calcium stearate and 100 parts by weight of powder of B200) The chroman derivatives shown in Table 1 were added in the proportions shown in Table 1, and pelletized using a granulator at a resin temperature of 300°C. The melt index (MI) of this pellet was measured according to ASTM-D-1238-65T and the results are shown in Table 1. A press sheet with a thickness of 2 mm was produced from this pellet by preheating at 200°C for 10 minutes and cooling at 20°C for 3 minutes. Layer these two press sheets together to obtain a wavelength of 700 mμ.
and reflectance (%) R ₇₀₀ at wavelength 400mμ and
R ₄₀₀ was measured, and the value obtained using the following formula was defined as whiteness and used as a guideline for hue. Whiteness (%)=(1- _R700 - _R400 / _R700 )
×100 The results are shown in Table 1. The larger the whiteness value, the better the hue.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. A polyolefin having the general formula (In the formula, R ¹ is a hydrocarbon group having 1 to 16 carbon atoms,
R ² to R ⁷ , R ⁹ and R ¹⁰ are hydrogen or have 1 carbon number
to 7 alkyl groups, R ⁸ is a group represented by [Formula] or [Formula] [where n is a positive integer of 1 to 3,
R ¹¹ and R ¹³ are hydrogen or alkyl groups, R ¹² and R ¹⁴ are hydrogen, alkyl groups or A thermoplastic polymer composition containing a chroman derivative represented by the following formula (wherein R ¹ to R ⁷ , R ⁹ and R ¹⁰ are the same as the general formula described above). 2. The thermoplastic polymer according to claim 1, wherein 0.005 to 0.5 parts by weight of a chroman derivative is blended into 100 parts by weight of polyolefin.