JPS61221284A - Macromolecular antioxidant and is preparation - Google Patents

Abstract

PURPOSE:To provide an antioxidant consisting of specified two p-cresol-contg. structural units in liner arrangement, which is easy to prepare without causing scattering and coloration in manufacturing process and imparts light and heat stability to synthetic fiber and synthetic resin. CONSTITUTION:The macromolecular antioxidant consists of structural units of formulas I and II in linear arrangement. It imparts light and heat stability to synthetic fiber and synthetic resin and prevents their deterioration. It does not cause decrease of the effect due to scattering in processing and coming-off nor coloration in processing and use. It is readily prepared by reaction of p- cresol with p- and/or m-chloromethylstyrene in the presence of a Friedel-Grafts catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel antioxidant that provides stability to synthetic fibers and synthetic resins against deterioration caused by light and heat, and a method for producing the same.

(Prior art) Synthetic fibers or synthetic resins made of polyurethane, polyether/polyester, polyamide, polyethylene, polypropylene, polystyrene, polyacetal, etc.
It is well known that when a polymer is used alone, it undergoes oxidation and deterioration due to the action of light or heat during processing or use, resulting in problems with its stability such as discoloration and deterioration of mechanical properties.

In order to solve such problems, it is well known that various phenolic antioxidants are added during the manufacturing and processing steps of synthetic fibers or synthetic resins. For example, 2. 6-di-1-butyl-4-methylphenol, 4,4'-butylidenebis(3-methyl-6
-t-butylphenol), tetrakis-[methylene-
3-(3-5'-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1.3.5-)dimethyl-2,4,6-tris(3,5-di-t-butyl- 4
-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris(2,6-dimethyl-4-t-butyl-3
-Hydroxybenzyl)in cyanurate and the like are known to be used.

(2) Furthermore, in recent years, antioxidants with increased molecular weight and their use have been proposed. For example, polyurethane elastic yarn containing a polyadduct of p-cresol and divinylbenzene (
(Japanese Patent Publication No. 47-6510), acrylic acid ester polymer of phenols (Japanese Patent Publication No. 49-34667), isopropenylphenol oligomer C%
-20247 Publication), an antioxidant containing 〇-substituted phenol novolak as an active ingredient (I# Kaisho 58-7191)
Publication No. 2), etc.

(Problems to be solved) However, the conventional method +11 has drawbacks such as scattering of the antioxidant during the processing process and discoloration of the product, and its performance is not always satisfactory, especially when used for synthetic fibers. It's not a kimono. In addition, the above-mentioned conventional method +21 is effective in suppressing the scattering properties of low-molecular-weight antioxidants and improving the durability of the antioxidant itself, but the purification and production of raw materials are complicated, and the antioxidant itself is extremely difficult to use. It has disadvantages such as limited use because it is colored.

(Means for Solving the Problems) As a result of various studies to solve these drawbacks, the present inventors have found that a specific new high molecular weight antioxidant is easier to obtain and superior to conventional antioxidants. The present invention was achieved based on the discovery that it has antioxidant properties. That is, the present invention is a polymeric antioxidant characterized by consisting of structural units represented by the formulas CD and (ID), and in which these units are arranged substantially linearly.

The novel polymeric antioxidant of the present invention is obtained by reacting p-cresol with p- and/or m-chloromethylstyrene, preferably in solution in the presence of a Riedel-Krauch catalyst. .

p- and/or m-chloromethylstyrene 1 The method described in U.S. Pat. No. 2,981,758 or JP-A-48
It can be produced by reacting the corresponding methylstyrene or ethyltoluene with chlorine according to the method described in Japanese Patent No.-103528.

Commercially available glue tetramethylstyrene is manufactured by Seimi Chemical Company MC.
MSC product name) can be used.

As a Friedel Krach catalyst, George A., Oler, 7 Friedel Krach & Fist Related.
Reactions■, par) 1.116-404 pages (Interscience Publishers, 1964) K
Catalysts described may be used, but preferred catalysts include boron trifluoride etherate, zinc chloride, aluminum chloride, and mixtures thereof in molar ratios of romethylstyrene of 0.
8 to 1.25, preferably 1.06 to 1.11, which is on the excess p-cresol side.

As a solvent for the reaction, benzene, toluene, chlorobenzene, 0-dichlorobenzene, 0-chlorotoluene, p-
The chlorotoluene etc. are gone, good! Lut chlorobenzene, 0-dichlorobenzene.

The reaction is carried out in two steps using a solvent such that the total concentration of p-cresol and p- and/or m-chloromethylstyrene is 20 to 80% by weight, preferably 40 to 60% by weight. It is preferable. That is, p
- While maintaining the solution of cresol and catalyst at 50°C or lower, preferably 20 to 35°C, p- and/or m-tetrameromylstyrene solution is added dropwise and mixed to
- React with cresol, then 50°C or higher,
Preferably, the chloromethyl group and p are heated to 60 to 90°C.
- Carry out a dehydrochlorination reaction with one cresol group.

In each of the two-stage reactions described above, the type of catalyst can be changed or two or more types can be used in combination. Further, the two-stage reaction described above is a preferred embodiment for producing the antioxidant of the present invention having a relatively high molecular weight, and can also be compressed into one stage.

The amount used is not particularly limited, but is usually 0.1 to 5 parts per 100 parts of p-cresol, but it may depend on the solubility in the reaction system depending on the catalyst species.

The progress of the reaction was determined by infrared absorption analysis of the reaction mixture.
This can be seen by the reduction in the absorption peak of 8611 and the reduction in hydrogen chloride generation. The total reaction usually takes 24
substantially completed within hours.

The reaction product can be used as an antioxidant as a solution or after the solvent has been removed depending on the purpose by subjecting the solution to a catalyst removal operation such as washing with water or aqueous alkali solution.

The antioxidant of the present invention includes p-cresol and p- and H/-! Alternatively, by utilizing the difference in reactivity between the vinyl group and the chloromethyl group in m-chloromethylstyrene, the chemical structure can be given a degree of regularity.
1] and formula [I] are not particularly defined, and may be partially block-like or random.

The number average molecular weight of the antioxidant of the present invention is preferably 1.
000~s, ooo, more preferably 2,000~s
, ooo. If the number average molecular weight is less than 1.000, it will not meet the purpose of the present invention, and if the number average molecular weight exceeds 8.000, d1 p-cresol and p-
and/or the reaction with m-chloromethylstyrene takes a long time to complete, the product tends to become insolubilized, or the product solution has a high viscosity, making the washing process difficult.

In the antioxidant of the present invention, when the terminal residue consists of a p-cresol residue, the ortho-position hydrogen may be substituted by addition of another vinyl compound, and the terminal residue may be chloromethyl When consisting of a group, the chlorine may be substituted with a thio group or an amino group, or may be left as is as a reactive group.

Such modification can be carried out before or after the completion of the reaction of p-cresol with p- or m-chloromethylstyrene.

The antioxidant of the present invention is a new high molecular weight type antioxidant, which is easily obtained, and has excellent antioxidant performance and resistance to discoloration.

The present invention will be explained below with reference to examples, but the present invention is not limited to these examples.

(Example) Example 1 CMS-P (product name, chloromethylstyrene mixture of 96% purity, 40% loose body, and 60m pure chloromethylstyrene) manufactured by Seimichem Cal Co., Ltd. 200% K2.6-t-phthyl-4-methylphenol ppm and a mixed aqueous solution of 3 and 0.5 h each of caustic soda and sodium hyde tetrasulfide, followed by washing with water to remove the colored polymerization inhibitor, and then dehydrating through a Molecular Sieves 3A packed column @ Stirrer, temperature In total, 90 parts of p-cresol, 90 parts of chlorobenzene, and 0.4 part of 47 boron trifluoride etherate were charged into a glass reactor equipped with a nitrogen gas inlet, an outlet, and a dropping funnel. Above mentioned chlorine Methylstyrene 1
40 parts, p-cresol 10 parts and chlorobenzene 1
Add 50 parts of the mixed solution at an internal temperature of 30 to 35°C while stirring.
It dripped over time. Further, the reaction was carried out at 30 to 35°C for 10 hours. During the test, the absorption peak #1 of out-of-plane bending vibration for the vinyl group C-H of 986♂ in the infrared absorption analysis of the reaction mixture disappeared.

Nitrogen gas was introduced, and the exhaust gas was introduced into a caustic soda aqueous solution. Add 0.1 part of zinc chloride and bring the internal temperature to 70-80.
The temperature was raised to ℃. This temperature was maintained for 7 hours.

During this time hydrogen chloride gas evolved and substantially ceased. The reaction product solution was washed with water and aqueous caustic soda solution.

After removing most of the chlorobenzene under reduced pressure using a rotary evaporator, the viscous liquid bottom was washed four times with 500 parts of methanol.

Drying under reduced pressure gave a white solid substance. The melting point of this substance measured by heating at a rate of 10°C/min is 141-153°C.
Met. The yield was 98 cm.

This material was subjected to infrared analysis and 13C-nuclear magnetic analysis.

FIG. 1 shows an infrared absorption spectrum. Approximately 3550c
The absorption peak at m indicates the presence of hindered phenolic hydroxyl groups.

A deuterated chloroform solution (0,25
17d'), the chemical shift (ppm) of the tetramethylsilane standard measured at room temperature was as follows.

CH.

The integral values (■+■) and (■+■) showed substantially equal values. Further, the integral value ratio of ■:■:■ for the main chain was approximately 1.0:0.8:1.1. The methylene group and 7 etheride groups adjacent to ■, ■ or 0.0 are ■
And I am a priest to ■ and ■.

Therefore, the formula El or the formula [Formula [■] expressed as an old repeating unit, and the formula [I] and the formula [I] expressed as a bonding unit of 2m) [7R ratio in this example of Wato Nirin is approximately So 1.0: 0.8: 1.1. The lack of methylene groups in (1), (2) and (2) is due to the presence of methylene groups as terminal groups.

Formula (I3 or repetition of two cries, or formula [1] and formula t...
] Depending on the bonding method of the phenolic group, the formula (nl
), has the structure of formula (lV) and formula [■].

The novel polymeric antioxidant of the present invention has a peak absorption of about 3550'' and Hydroxyl groups were confirmed by absorption of several shielders at shorter wavelengths, and lIC-
Nuclear magnetic resonance analysis confirms the structures represented by formula [13], formula (II), or the above formula [■] and formula [V], which are generated from the way these are bonded.

Hitachi BirkinElmer 115 Molecular Weight Apparatus (BirkinElmer Paver Pressure Osmometer) Journal of Physical and Colloid Chemistry Volume 55, 304
The molecular weight was determined to be 4,500 using toluene as a solvent by the method described on page I951.

Example 2 The experiment was carried out under the same conditions as in Example 1 except that CMS-14 (trade name, p-chloromethylstyrene with a purity of 95%) was used instead of CM S-P manufactured by Seimi Chemical.

A slightly yellowish solid material with a melting point of 121-138°C was obtained. The yield was 98%. Figure 2 shows the infrared absorption spectrum of this material. The molecular weight was 4500.

Example 3 100 parts of p-cresol, 0.2 parts of zinc chloride, and 100 parts of chlorobenzene were charged into the same reactor as in Example 1. A mixed solution of 118 parts of chloromethylstyrene purified in Example 1 and 118 parts of chlorobenzene was added dropwise over 5 hours at an internal temperature of 35 to 45°C.

The reaction was further continued at the same temperature for 10 hours. The absorption of 986c1r1 in infrared absorption analysis of the reaction mixture almost disappeared. After raising the internal temperature to 70 to 80°C and reacting for 7 hours in the same manner as in Example 1, the product was taken out. Melting point 127-1
A white solid material was obtained at 34°C.

The yield was 97 cm, and the molecular weight was 1,500.

Example 4 80 parts of p-/resol, 80 parts of chlorobenzene and 4
One part of 7-trifluoroborous etherate was charged to the same reactor as in Example 1. A mixture of 144 parts of chloromethylstyrene purified in Example 1, 20 parts of p-cresol, and 164 parts of chlorobenzene was added dropwise over 5 hours while stirring at an internal temperature of 28 to 30°C. The reaction was further continued at the same temperature for 7 hours.

The absorption of 9863-'' in the infrared absorption analysis of the reaction mixture almost disappeared.The internal temperature was raised by 70 to 80'CVc and the reaction was carried out for 7 hours in the same manner as in Example 1 to obtain a viscous solution.Chlorobenzene After adding 200 parts of chlorobenzene and diluting it, the solution was washed with water and an aqueous alkali solution.After distilling off 300 parts of chlorobenzene using a rotary evaporator, methanol was added in the same manner as in Example 1 to precipitate the product, followed by washing and drying. A white solid substance with a melting point of 145-160°C was obtained. Yield: 9
7%, and the molecular weight was 7,500.

Example 5 Polytetramethylene ether cream with a molecular weight of 1950
: 1950 parts of 1-l and 500 parts of 484'-diphenylmethane diisocyanate were reacted at 70'C for 90 minutes to obtain a prepolymer having incyanate groups at both ends. Next, after cooling this to room temperature, 4478 parts of dry dimethylformamide was added and dissolved to obtain a prepolymer solution.

Separately, 74 parts of 1,2-propylene diamine and 9.5 parts of dichloromethane were added to 983 parts of dried dimethylformamide.
The prepolymer solution was added thereto at room temperature to obtain a polyurethane solution with a viscosity of 2400 voids (30° C.).

A small amount of blue tint was obtained by dispersing 145 parts of a 46% paste of titanium oxide pigment containing pigments and 117 parts of a solution of poly(N,N-diethyl-β-inoethyl methacrylate) in 32 tidimethylformamide. It was added to the above polyurethane solution and mixed.

This dissolved MK and the antioxidant obtained in Examples 1 to 4 were uniformly stirred and mixed at a ratio of 1 part to 100 parts of polyurethane (as solid content), and then dry spun by a conventional method to form a 40 denier 15 filament. A polyurethane elastic yarn was obtained. This was heated to 60℃ in a fade-o-meter and exposed to ultraviolet light at 40℃.
After irradiating for a time, determine the breaking strength retention rate of the elastic yarn t41
Shown in the table.

For comparison, Japanese Patent Publication No. 47-6510, Example IK
An elastic yarn in which a resinous fastener with divinylbenzene tolu-cresol synthesized by the method described above was added at a ratio of 1 part of polyurethane 100sK (Comparative Example 1), and an elastic yarn in the case where these compounds were not added (Comparative Example) 2) The results obtained by removing K are also shown in Table 1.

Table 1 (Effects of the Invention) If the polymeric antioxidant according to the present invention is used, the effect of preventing oxidation due to scattering during the processing process, which was a drawback of the conventional technology, will be reduced, and the anti-oxidation effect will be reduced during the processing process or during use. This prevents it from falling off.

In addition, the polymeric antioxidant of the present invention itself is white or nearly white and is resistant to coloring, thereby preventing coloring of products during processing and use.

Furthermore, according to the production method of the present invention, the raw materials can be easily purified and produced, and the desired polymeric antioxidant can be easily produced.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an infrared absorption spectrum of the antioxidant obtained in Example 1 of the present invention. FIG. 2 is a diagram showing an infrared absorption spectrum of the antioxidant obtained in Example 2 of the present invention.

Claims (1)

[Scope of Claims] 1. A polymeric antioxidant comprising structural units represented by formula (I) and formula (II), characterized in that these units are arranged substantially linearly. . ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) 2. The polymeric antioxidant according to claim 1, which has a number average molecular weight of 1,000 to 8,000. 3. Consisting of structural units represented by formula (I) and formula (II), characterized in that p-cresol and p- and/or m-chloromethylstyrene are reacted in the presence of a Friedel-Crafts catalyst. , a method for producing a polymeric antioxidant in which these units are arranged substantially linearly. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) 4. The polymeric antioxidant according to claim 3, characterized in that the Friedel-Crafts reaction is carried out in a substantially inert solvent. manufacturing method.