JPH06220075A - Phosphinopropionate compound, its production and use - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful as a stabilizer for preventing the thermal deterioration and photooxidative deterioration of various organic materials. CONSTITUTION:The compound of formula I [R1 is H, 1-10C alkyl (e.g. methyl), 1-10C alkoxy (e.g. methoxy), 3-IOC cycloalkyloxy (e.g. cyclohexyloxy), 7-18C arylalkoxy (e.g. benzyloxy), etc., (R1 is preferably H, 1-13C alkyl, 6-10C alkoxy, etc., especially H, methyl, etc.); R2 is H or methyl; Ar is 6-18C aryl or 7-18C alkylaryl (preferably phenyl); n is 1-3 (preferably 1)], e.g. 2,2,6,6-tetramethyl-4- piperidyl 2-methyl-3-(diphenylphosphino)propionate. The compound of formula I can be produced by reacting a compound of the formula HnP-(Ar)3-n with a compound of formula II preferably in an organic solvent such as toluene at 50-120 deg.C for 2-3hr.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel phosphinopropionate compounds, a process for their preparation and their use as stabilizers for organic materials.

[0002]

2. Description of the Related Art Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubbers, mineral oils, lubricating oils, adhesives, paints, etc., are exposed to heat, light, oxygen during production, processing and use. It is known that the product value is significantly deteriorated due to deterioration due to the action such as the above, and molecular breakage and cross-linking, as well as softening, embrittlement, discoloration and the like phenomena. For the purpose of solving such problems as thermal deterioration, photooxidation deterioration and thermal oxidation deterioration, it has been conventional to add various phosphorus-based antioxidants, hindered piperidine-based photooxidants, phenol-based antioxidants, etc. In this way, the organic material is stabilized.

Conventionally, in order to exert a stabilizing effect against both thermal deterioration and photooxidation deterioration, it has been generally practiced to use a phosphorus antioxidant and a hindered piperidine photooxidant together. It is being appreciated.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a compound which simultaneously exhibits a high stabilizing effect against both heat deterioration and photooxidation deterioration of organic materials.

Another object of the invention is to provide a process for the preparation of such compounds.

Yet another object of the present invention is to stabilize organic materials with such compounds.

The inventors of the present invention have continued their research to develop compounds that exhibit a plurality of stabilizing effects against the thermal deterioration and photooxidation deterioration of organic materials, which are not found in conventionally known stabilizers.
As a result, they have found a phosphinopropionate compound having a specific structure and completed the present invention.

[0008]

That is, the present invention provides a phosphinopropionate compound represented by the following formula (I).

[0009]

[Chemical 3]

In the formula, R ¹ represents hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, cycloalkyloxy having 3 to 10 carbons, arylalkoxy having 7 to 18 carbons, or a hydroxyl group, R ² represents hydrogen or methyl, Ar represents an aryl having 6 to 18 carbons or an alkylaryl having 7 to 18 carbons, and n represents an integer of 1 to 3.

The present invention also provides the following formula (II)

H _n P- (Ar) _3-n (II)

(Wherein Ar and n have the above-mentioned meanings)

A phosphine compound represented by the following formula (II
I)

[0015]

[Chemical 4]

(Wherein R ¹ and R ² have the above-mentioned meanings)

The present invention provides a method for producing the phosphinopropionate compound represented by the above formula (I) by reacting with the piperidine compound represented by the formula (I).

The phosphinopropionate compound represented by the formula (I) is useful as a stabilizer for an organic material, particularly an organic material which is easily deteriorated by the action of heat or light. Therefore, the present invention further provides a stabilizer for an organic material containing the phosphinopropionate compound as an active ingredient, and by adding a stabilizing and effective amount of the phosphinopropionate compound to the organic material, the organic compound The present invention provides a method for stabilizing a material, and further provides an organic material composition comprising an organic material containing the phosphinopropionate compound.

In the formula (I), R ¹ is hydrogen and has 1 carbon atom.
To alkyl of 10 to alkoxy having 1 to 10 carbon atoms,
Cycloalkyloxy having 3 to 10 carbon atoms, 7 carbon atoms
To 18 arylalkoxy or hydroxyl groups. Specific examples of alkyl include methyl, ethyl, propyl,
Examples thereof include butyl, pentyl, hexyl, octyl and decyl. When the carbon number is 3 or more, it may be linear or branched. Specific examples of alkoxy include methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, decyloxy, and the like.
When the number of carbon atoms is 3 or more, it may be linear or branched. Specific examples of cycloalkyloxy include cyclohexyloxy, and specific examples of arylalkoxy include benzyloxy and phenethyloxy. Especially preferred R ¹
Is hydrogen, alkyl having 1 to 3 carbons, and 6 to 1 carbons
Alkoxy and cyclohexyloxy of 0, particularly hydrogen, methyl, octyloxy and the like are more preferable.

Ar in the formula (I) has 6 to 18 carbon atoms.
Or aryl having 7 to 18 carbon atoms, and preferred examples include phenyl and 2,4-di-t-
Butylphenyl, 2,4-di-methylphenyl and the like can be mentioned. Ar is particularly preferably phenyl.
Further, n in the formula (I) is an integer of 1 to 3, and a compound in which n = 1 is particularly preferable.

The phosphinopropionate compound represented by the formula (I) can be produced by the addition reaction of the phosphine compound represented by the formula (II) and the piperidine compound represented by the formula (III) as described above. .

Examples of the phosphine compound of the formula (II) used here include phosphine, phenylphosphine, diphenylphosphine, 2,4-dialkylphenylphosphine and bis (2,4-dialkylphenyl) phosphine. Especially, diphenylphosphine and bis (2,4-dimethylphenyl) phosphine are preferably used.

Further, examples of the piperidine compound of the formula (III) include 2,2,6,6-tetramethyl-4-piperidyl acrylate and 2,2,6,6-tetramethyl-4.
-Piperidyl methacrylate, 1,2,2,6,6-
Pentamethyl-4-piperidyl acrylate, 1,
2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl acrylate, 2,2
6,6-tetramethyl-1-octyloxy-4-piperidyl methacrylate and the like can be mentioned. Above all,
Since it is easily available, 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 1,2,2,2
6,6-Pentamethyl-4-piperidyl methacrylate is preferably used.

In the reaction of the phosphine compound of the formula (II) with the piperidine compound of the formula (III), when a compound in which n in the formula (I) is 1 is prepared, It is preferable to use the piperidine compound of the formula (III) in an amount of about 1 to 1.2 mol, more preferably about 1 to 1.05 mol. When a compound in which n in the formula (I) is 2 is prepared, the compound of the formula (I) is used per mol of the phosphine compound of the formula (II).
The piperidine compound of II) is preferably used in an amount of about 2 to 2.5 mol, more preferably about 2 to 2.2 mol. When producing a compound in which n in the formula (I) is 3, it is preferable to use about 3 to 4 mol of the piperidine compound of the formula (III), and more preferably 1 mol of the phosphine compound of the formula (II). Is about 3 to 3.3 mol of the piperidine compound.

This reaction is generally carried out in an organic solvent. Examples of organic solvents that can be used include aromatic hydrocarbons, aliphatic hydrocarbons, oxygen-containing hydrocarbons, halogenated hydrocarbons and the like. Specific examples of aromatic hydrocarbons are:
Examples thereof include benzene, toluene, xylene, etc., specific examples of the aliphatic hydrocarbons are n-hexane, n-heptane, n-octane, etc., and specific examples of the oxygen-containing carbon hydrogen are tetrahydrofuran, tetrahydropyran, etc. Specific examples of the halogen-based hydrocarbon include chloroform and carbon tetrachloride. Among these, aromatic hydrocarbons, especially toluene, are preferably used.

The reaction proceeds at a temperature of about 50 to 120 ° C. and is carried out for about 2 to 3 hours. This reaction proceeds under normal pressure, but may be performed under pressure. After completion of the reaction, the solvent can be distilled off to isolate the phosphinopropionate compound of the formula (I), or the compound can be subjected to a known purification method such as recrystallization or column chromatography to obtain the compound of the formula ( It is also possible to obtain the phosphinopropionate compounds of I).

Specific examples of the phosphinopropionate compound thus obtained are as follows.

Compound A: 2,2,6,6-tetramethyl-4-piperidyl 2-methyl-3- (diphenylphosphino) propionate

Compound B: 1,2,2,6,6-pentamethyl-4-piperidyl 2-methyl-3- (diphenylphosphino) propionate

Compound C: 2,2,6,6-tetramethyl-4-piperidyl 3- (diphenylphosphino) propionate

Compound D: 1,2,2,6,6-pentamethyl-4-piperidyl 3- (diphenylphosphino) propionate

Compound E: 2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl 2-methyl-3- (diphenylphosphino) propionate

Compound F: 2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl 3- (diphenylphosphino) propionate

The phosphinopropionate compound represented by the formula (I) is effective for stabilizing an organic material from heat deterioration, thermo-oxidation deterioration and photo-oxidation deterioration. Examples of the organic material that can be stabilized by the present invention include the followings, which can be used alone or as a mixture of two or more kinds, but are not limited to these organic materials. It is not something that will be done.

(1) Polyethylene, for example low density polyethylene (LD-PE), high density polyethylene (HD-P)
E), linear low density polyethylene (LLD-PE); (2) polypropylene; (3) methylpentene polymer; (4) EEA (ethylene / ethyl acrylate copolymer) resin; (5) ethylene / vinyl acetate copolymer resin (6) Polystyrenes such as polystyrene, poly (p
-Methylstyrene), poly (α-methylstyrene); (7) AS (acrylonitrile / styrene copolymerization) resin; (8) ABS (acrylonitrile / butadiene / styrene copolymerization) resin; (9) AAS (special acrylic rubber / (Acrylonitrile / styrene copolymerization) resin; (10) ACS (acrylonitrile / chlorinated polyethylene /
Styrene copolymer) resin;

(11) Chlorinated polyethylene, polychloroprene, chlorinated rubber; (12) Polyvinyl chloride, polyvinylidene chloride; (13) Methacrylic resin; (14) Ethylene / vinyl alcohol copolymer resin; (15) Fluorine resin (16) Polyacetal; (17) Grafted polyphenylene ether resin and polyphenylene sulfite resin; (18) Polyurethane; (19) Polyamide; (20) Polyethylene terephthalate, Polybutylene terephthalate; (21) Polycarbonate; (22) Polyacrylate (23) Polysulfone, polyetheretherketone, polyethersulfone; (24) Aromatic polyester resin; (25) Epoxy resin; (26) Diallyl phthalate prepolymer; (27) Silicone resin; (28) Unsaturated polyester resin (29) Acrylic modified benzoguanamine resin; (30) Benzo Anamin / melamine resins; (31) urea resins;

(32) polybutadiene; (33) 1,2-polybutadiene; (34) polyisoprene; (35) styrene / butadiene copolymer; (36) butadiene / acrylonitrile copolymer; (37) ethylene / propylene copolymer Polymer; (38) Silicone rubber; (39) Epichlorohydrin rubber; (40) Acrylic rubber; (41) Natural rubber;

(42) Chlorine rubber paint; (43) Polyester resin paint; (44) Urethane resin paint; (45) Epoxy resin paint; (46) Acrylic resin paint; (47) Vinyl resin paint; (48) Amino Alkyl resin paint; (49) Alkyd resin paint; (50) Nitrocellulose resin paint; (51) Oil paint; (52) Wax; (53) Lubricating oil.

The phosphinopropionate compound according to the present invention is a thermoplastic resin among these organic materials.
Especially, it exerts an excellent effect on polyolefins such as polypropylene and polyethylene. When using this phosphinopropionate compound as a stabilizer,
A stabilizing effective amount is blended with the organic material, and the preferable blending amount naturally changes depending on the type of the target organic material, but normally, it is 0.01% with respect to 100 parts by weight of the organic material.
It is preferably used in the range of 5 to 5 parts by weight.

The organic material composition containing the phosphinopropionate compound of the formula (I) according to the present invention may further contain other additives, if necessary, such as a phenolic antioxidant, a sulfuric antioxidant and phosphorus. It may also contain a system antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, a lubricant, a plasticizer, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, a pigment, an inorganic filler and the like. These additives can, of course, be compounded at the same time as the phosphinopropionate compound of the formula (I), or can be compounded at a stage separate from the phosphinopropionate compound.

In formulating the phosphinopropionate compound of formula (I), or any other optional additives, into the organic material, any known method and apparatus for obtaining a homogeneous mixture should be used. You can
For example, when the organic material is a solid polymer, it can be blended directly or can be blended with the solid polymer in the form of a masterbatch. In addition, when the organic material is a synthetic polymer, it can be compounded in the form of a solution or a dispersion in a polymer solution during or immediately after the polymerization. On the other hand, when the organic material is a liquid such as oil, it can be directly added and dissolved, or can be added in a state of being dissolved or suspended in a liquid medium.

[0042]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts in the examples are by weight unless otherwise specified.

Example 1 Preparation of 2,2,6,6-tetramethyl-4-piperidyl 2-methyl-3- (diphenylphosphino) propionate (Compound A)

In a 200 ml four-necked flask, 5.0 g (26.8 mmol) of diphenylphosphine, 2, 2, 6,
6.2 g (27.5 mmol) of 6-tetramethyl-4-piperidyl methacrylate and 100 ml of toluene were charged. This mixture was reacted at 60 ° C. for 3 hours. After completion of the reaction, the solvent was distilled off, and recrystallization from hexane resulted in the precipitation of white crystals. This was separated by filtration and dried to obtain the title compound.

Mass spectrometry (FD-MS): m / z 411 (M) ⁺ elemental analysis: C ₂₅ H ₃₄ NO 2 P calculated value C 73.0%; H 8.3%; N 3.4%; P 7.5% measured value C 73.1%; H 8.7%; N 3.3%; P 7.9% Melting point: 88-90 ° C

Example 2: Preparation of 1,2,2,6,6-pentamethyl-4-piperidyl 2-methyl-3- (diphenylphosphino) propionate (Compound B)

Instead of 2,2,6,6-tetramethyl-4-piperidyl methacrylate in Example 1, 1,
The title compound was obtained by the same procedure as in Example 1 using 6.5 g (27.1 mmol) of 2,2,6,6-pentamethyl-4-piperidyl methacrylate.

Mass spectrometry (FD-MS): m / z 425 (M) ⁺ Elemental analysis: C ₂₆ H ₃₆ NO 2 P Calculated value C 73.4%; H 8.5%; N 3.3%; P 7.3% Measured value C 73.6%; H 8.0%; N 3.1%; P 7.7% Melting point: 64-67 ° C

Example 3

Compounds C to F listed above can be produced by performing the same operations as in Example 1 except that the starting material piperidine compound and the amount thereof are changed.

Example 4: Thermal stability test of polypropylene

(Combined) Unstabilized polypropylene 100 parts Calcium stearate 0.05 parts Test compound 0.1 parts

The above mixture was melt-kneaded at 230 ° C. by a 30 mmφ single-screw extruder and pelletized. According to JIS K 7210, the obtained pellets have fluidity after being retained in a melt indexer at 270 ° C for 5 minutes (M
The I value: g / 10 minutes) was measured to evaluate the thermal stability. Since polypropylene undergoes molecular cleavage by heat to increase fluidity, a smaller MI value after retention for 5 minutes means better thermal stability. The results are shown in Table 1.

[0054]

[Table 1]

Example 5: Weathering test of polypropylene

(Composition) Unstabilized polypropylene 100 parts Calcium stearate 0.05 parts Test compound 0.1 parts

The above mixture was melt-kneaded at 230 ° C. by a 30 mmφ single-screw extruder and pelletized. The pellets were molded by an injection molding machine at 230 ° C. to form a 1 mm thick sheet, which was used as a test piece. This test piece was put in a sunshine weather ometer (light source: carbon arc), and light irradiation was performed under the conditions of a black panel temperature of 63 ° C. and a spray cycle of 12 minutes / 60 minutes, and a crack was generated on the light irradiation surface of the test piece. The weather resistance was evaluated by the time taken to complete. The results are shown in Table 2.

[0058]

[Table 2]

Example 6: Thermal stability test of polyethylene

(Compounding) Unstabilized linear low density polyethylene 100 parts Calcium stearate 0.1 part n-Octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.05 parts Test compound 0.05 part

The above mixture was melt-kneaded at 250 ° C. by a 30 mmφ single-screw extruder and pelletized. According to JIS K 7210, the obtained pellets were evaluated for thermal stability by measuring the fluidity (MI value: g / 10 minutes) after retaining at 250 ° C for 15 minutes in a melt indexer. It was Polyethylene causes molecular crosslinking by heat,
Since the fluidity decreases, a higher MI value after 15 minutes of retention means better thermal stability. The results are shown in Table 3.

[0062]

[Table 3]

[0063]

INDUSTRIAL APPLICABILITY The phosphinopropionate compound of the present invention exhibits excellent performance as a stabilizer for various organic materials including thermoplastic resins such as polyolefin.
In particular, it is effective for an organic material having a property of being deteriorated by heat and light. For example, a resin containing this compound is stable against heat deterioration and photooxidation deterioration,
It will be a high quality product.

Front page continuation (72) Inventor Tetsuo Yamaguchi 3-1-198 Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. (72) Kanako Ida, 3-1-198 Kasugade, Konohana-ku, Osaka No. Sumitomo Chemical Co., Ltd.

Claims (10)

[Claims] 1. A compound represented by the formula (I): (Wherein R ¹ represents hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, cycloalkyloxy having 3 to 10 carbons, arylalkoxy having 7 to 18 carbons, or R ² Represents hydrogen or methyl, Ar represents aryl having 6 to 18 carbons or alkylaryl having 7 to 18 carbons, and n represents an integer of 1 to 3). 2. R ¹ is hydrogen, alkyl having 1 to 3 carbons,
The compound according to claim 1, which is alkoxy having 6 to 10 carbon atoms or cyclohexyloxy. 3. The compound according to claim 1 or 2, wherein Ar is phenyl and n is 1. 4. Formula (II) H _n P- (Ar) _3-n (II) (wherein Ar represents aryl having 6 to 18 carbons or alkylaryl having 7 to 18 carbons, and n is 1 To the phosphine compound represented by the formula (III) (Wherein R ¹ represents hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, cycloalkyloxy having 3 to 10 carbons, arylalkoxy having 7 to 18 carbons, or R ² Is hydrogen or methyl) and a piperidine compound represented by the formula (1) is reacted with the piperidine compound. 5. A stabilizer for an organic material comprising the phosphinopropionate compound according to claim 1 as an active ingredient. 6. A method for stabilizing an organic material, which comprises compounding the phosphinopropionate compound according to claim 1 in a stabilizing effective amount. 7. A stabilized organic material composition comprising an organic material containing the phosphinopropionate compound according to claim 1. 8. The composition according to claim 7, wherein the organic material is a thermoplastic resin. 9. The composition according to claim 8, wherein the thermoplastic resin is polypropylene. 10. The composition according to claim 8, wherein the thermoplastic resin is polyethylene.