RU2470067C2 - Liquid composition of styrene-containing phenol compounds and methods for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a stabilised composition containing thermoplastic, thermoplastic elastomer, rubber or lubricant, and a liquid composition of a styrene-containing phenol compound in amount ranging from about 0.01 wt % to about 10 wt % with respect to total weight of the stabilised composition, wherein said composition of a phenol compound contains: (a) at least one 2,6-distyrene-containing p-cresol in amount ranging from about 80% to about 95% per total gas-chromatographic area; (b) at least one monostyrene-containing p-cresol in amount of more than 1% per total gas-chromatographic area; and (c) at least one tristyrene-containing p-cresol in amount of more than 1% per total gas-chromatographic area, wherein the composition contains monostyrene-containing p-cresol and tristyrene-containing p-cresol in a combination in amount ranging from 5 to 20% per total gas-chromatographic area. The present invention also relates to a polymer article and a lubricant containing said composition of a phenol compound.

EFFECT: obtaining stabilisers for polymers and lubricants with high efficiency while maintaining the required fluidity and parameters for storage at normal transportation temperatures.

13 cl, 1 dwg, 19 tbl, 14 ex

Description

FIELD OF THE INVENTION

The present invention relates to liquid compositions of styrene-containing phenolic compounds. In particular, the present invention relates to liquid compositions of styrene-containing phenolic compounds, methods for producing compositions of styrene-containing phenolic compounds and their use for stabilizing polymers and lubricants.

State of the art

There is a continuing need for liquid phenolic antioxidants for a number of polymer markets, such as thermoplastics, thermoplastic elastomers, rubbers and lubricants. For many phenolic antioxidants, liquid physical form can be achieved by heating them to temperatures above their melting point. Examples include octadecyl-3,5-di-tert-butyl-4-hydroxycinnamate, whose melting point is in the range of 48 ° C to 58 ° C, and 2,6-di-tert-butyl-p-cresol, whose point melting point is approximately 69 ° C.

The main disadvantage associated with the use of a compound that is solid at room temperature in the molten state is that in order to keep it in liquid physical form, constant heating is required. Heating, however, cannot always be maintained, and therefore the molten product can cool and solidify. After curing, it becomes impossible to remove the compound from the storage container, which may be necessary to introduce it into the stabilized polymer. On the other hand, returning it to liquid physical form requires reheating, but reheating the solid material in a closed container can be a time-consuming and lengthy process. Thus, the situation can lead to technological delays and, as a result, to an unjustified increase in costs.

Thus, there is a need for the development of antioxidants or stabilizers, especially for polymers and lubricants, which will either equalize or exceed the effectiveness of stabilizers according to industry standards while maintaining the desired flow and storage parameters at normal transportation temperatures.

Another problem, especially for additives to polymers such as polyurethanes, especially polyurethanes, is the isolation of additives from the polymer. Products such as polyurethane foams are widely used in interior car parts, such as seats or dashboards, and increasing attention is being paid to the level of additives that can stand out from the plastics used for such products. Polyurethane foams are usually obtained from simple polyether polyols (polyols), which usually contain one or more antioxidants, and diisocyanates. Antioxidants are usually found in the polyol as one component to increase stability and reduce staining. The phenomenon of release of additives from plastics used in automotive interiors is sometimes known as fogging. Being precipitated in the form of droplets, they can cause clouding on the windshield or other windows. However, the problem of fogging inside the car is not just a safety issue due to reduced visibility, but rather a safety issue for the health of car passengers. Thus, there is also a need for polymers, for example polyurethanes, such as polyurethane foams, having low fogging parameters compared to industry reference standards.

US Pat. No. 3,956,247 discloses a solution whereby halogenation in an EPDM solution (EPDM, rubber based on ethylene terpolymer, alpha-monoolefin and a non-conjugated diene) in the presence of an epoxy compound, such as epoxidized soybean oil, with or without poly (alkylene ether) glycol gives halogenated EPDM with excellent viscosity stability and limited gel content. As an antioxidant, a mixture of two parts of nonyl-containing phenylphosphite and one part of styrene-containing p-cresol can be used.

US Pat. No. 5,100,055 discloses that a rubber composition containing a specifically limited imidazole compound or a compound of imidazole, benzimidazole or their specifically limited derivatives has a large tan δ in the high temperature range, and a tire having a tread made using this rubber composition is guaranteed to not be reduced tan δ values due to an increase in temperature during mileage and has improved adhesion to the road surface during high-speed traffic. The use of Bronsted acid in combination with imidazole, imidazoline or benzimidazole can eliminate the disadvantage associated with the low resistance to vulcanization of the rubber mixture containing imidazole, imidazoline or benzimidazole alone. The Bronsted acid used includes phenol derivatives, carboxylic acids¸ sulfonic acids, sulfuric acid and its derivatives, phosphoric acid and its derivatives, cyanuric acid and its derivatives, sulfinic acid, nitric acid and its derivatives, phosphorous acid and carboxylic acid, and their derivatives. Compounds listed as recommended for use include 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis-4-methyl-6-tert-butylphenol, 4,4'-thiobis-3-methyl -6-tert-butylphenol, styrene-containing p-cresol, phosphoric acid, esters of phosphoric acid, phosphorous acid and esters of phosphorous acid, among many others.

US Pat. No. 5,466,740 discloses a composition based on a halogen-containing resin which is stabilized against heat and light by introducing (a) a complex metal hydroxide based on calcium and a complex metal oxide based on calcium, (b) a β-diketone compound or a metal salt thereof, and optionally (c) a zinc salt of an organic acid. The halogen-containing resin composition may contain conventional additives such as organotin stabilizers, epoxy stabilizers, phosphorous esters, sulfur-based stabilizers, phenolic stabilizers and antioxidants, for example styrene-containing p-cresol, 2,6-di-tert-butyl- 4-methylphenol, butyl-containing anisole, 4,4'-methylenebis (6-tert-butyl-3-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 1,3,5-trimethyl -2,4,6-tris-3,5-di-tert-butyl-4-hydroxybenzyl) benzene and tetrakis [3- (4-hydroxy-3,5-di-tert-bu tilphenyl) propionyloxymethylene] methane.

US Pat. No. 6,242,562 discloses a method for producing a vinyl chloride polymer, which comprises the steps of: (A) suspension polymerizing vinyl chloride or a mixture of monomers containing vinyl chloride in an aqueous medium to obtain a polymer suspension; (B) distillation of unreacted monomers remaining in the polymer suspension; and (C) dehydrating the polymer suspension that has passed stage (B) at a temperature of from 80 ° C to 95 ° C, preferably within 60 minutes after distillation. In particular, first vinyl chloride or a monomer mixture containing vinyl chloride, an aqueous medium, a polymerization initiator and a dispersant is loaded into the polymerizer, mixed and the desired polymerization temperature (usually from 30 to 75 ° C.) is set to polymerize the vinyl chloride or monomer mixture. When the polymerization reaches a predetermined depth (usually from 60 to 98%), the polymerization is terminated, for example, by adding to the reaction mixture an antioxidant having a polymerization-inhibiting effect, for example phenolic antioxidants such as styrene-containing p-cresol, among others.

US Pat. No. 6,339,132 discloses a method for regenerating unreacted vinyl chloride monomers, comprising a compression step using a compressor of unreacted monomeric vinyl chloride recovered from a polyvinyl chloride production process, and compressing it in contact with a lubricating oil supplied to the compressor. In this method, a lubricating oil comprises a polymerization inhibitor having a polymerization-inhibiting effect on monomeric vinyl chloride. An example of this polymerization inhibitor is phenolic type inhibitors such as styrene-containing p-cresol, among others; amine type inhibitors; sulfur-containing type inhibitors and phosphorous type inhibitors that can be used individually or in combination of two or more of them.

US Pat. No. 6,391,065 discloses a water-dilutable UV absorber composition and a method for improving the light fastness of dyed textile materials. The composition is applied to textile materials and it contains an ultraviolet light absorber and an organic solvent capable of dissolving the ultraviolet light absorber. Example 5 of the patent discloses the addition of 10.0 g of benzyl benzoate to 20.0 g of a liquid antioxidant / solvent (alkyl styrene-containing p-cresol) “Naugard 529” to reduce viscosity.

SUMMARY OF THE INVENTION

In one embodiment, the present invention relates to a liquid composition of styrene-containing phenolic compounds containing (a) at least one distyrene-containing phenolic compound in an amount of from about 70 to about 98 percent of the total gas chromatographic area; (b) at least one monostyrene-containing phenolic compound in an amount of more than 1 percent, for example more than 5 percent, of the total gas chromatographic area; and (c) at least one tristyrene-containing phenolic compound in an amount of more than 1 percent, for example more than 5 percent, of the total gas chromatographic area. Optionally, the composition contains at least one monostyrene-containing phenolic compound in an amount of less than 10 percent of the total gas chromatographic area and at least one tristyrene-containing phenolic compound in an amount of less than 10 percent of the total gas chromatographic area. The composition preferably contains a monostyrene-containing phenolic compound and a tristyrene-containing phenolic compound in combination with each other in an amount of from 5 to 20 percent of the total gas chromatographic area. Preferably, the composition as obtained has an acid number of less than 0.1 mg KOH / gram and has an APHA color intensity index of less than 150, for example less than 100. The composition preferably has a viscosity of less than 40,000 centipoise at 25 ° C. The composition optionally further comprises (d) a diluent in an amount of from 0.5 to 20% of the mass. calculated on the total weight (a) - (d).

The composition may also contain a co-stabilizer, which may, for example, be selected from the group consisting of phenol phosphites, diarylamines and epoxidized vegetable oils. In one aspect, the co-stabilizer is an organophosphite, for example, tris (nonylphenyl) phosphite. One optional organophosphite is Weston® NPP 705. In another aspect, an additional stabilizer is dialkyl-containing diphenylamine.

In another aspect, the invention relates to a polymer product comprising a polymer and any of the styrene-containing phenolic compositions discussed above. The polymer may be selected, for example, from the group consisting of polyolefins, PVC, polyurethanes, polyols and elastomers. In another aspect, the polymer is styrene butadiene rubber. The polymer product preferably includes a polyol or polyurethane and a composition exhibiting low fogging.

In another aspect, the invention relates to a lubricant comprising a base component with a viscosity of the lubricant and the styrene-containing phenolic composition discussed above. The lubricant composition preferably contains a base component in an amount of more than 90% of the mass. and styrene-containing phenolic compound in an amount of more than 0.05% of the mass. based on the weight of the lubricant. The lubricant contains the main component of the lubricant in an amount of more than 95% of the mass. and styrene-containing phenolic compound in an amount of from 0.1 to 5% of the mass. based on the weight of the lubricant.

In a particularly preferred embodiment, the lubricant composition further comprises at least one antioxidant comprising one or more secondary diarylamines having the general formula

(R _four ) _a -Ar _one -NH-Ar ₂ - (R ₅ ) _b ,

where Ar ₁ and Ar ₂ are independent and include aromatic hydrocarbons, R ₄ and R ₅ are independent and include a hydrogen atom and hydrocarbon groups, and a and b are independent and equal to 0 and 3, provided that (a + b) is no more than 4.

In one aspect, the at least one monostyrene-containing phenolic compound includes a monostyrene-containing p-cresol, the at least one distyrene-containing phenolic compound includes a distyrene-containing p-cresol, and the at least one tristyrene-containing phenolic compound includes tristyrene-containing p-cresol.

In another aspect, the at least one monostyrene-containing phenolic compound comprises a mixture of monostyrene-containing o-cresol and the monostyrene-containing p-cresol, the at least one distyrene-containing phenol-compound includes a mixture of the distyrene-containing o-cresol and the distyrene-containing p-cresol, and at least one phenol-containing a mixture of tristirol-containing o-cresol and tristirol-containing p-cresol. For example, the composition may contain a distyrene-containing p-cresol in an amount of more than 1 percent of the total gas chromatographic area and a distyrene-containing o-cresol in an amount of more than 1 percent of the total gas chromatographic area.

In another aspect, at least one monostyrene-containing phenolic compound comprises a mixture of monostyrene-containing phenol and monostyrene-containing p-cresol, at least one distyrene-containing phenolic compound includes a mixture of distyrene-containing phenol and distyrene-containing p-cresol, and at least one tristyrene-containing phenolic compound and p-cresol. The composition may, for example, contain a monostyrene-containing phenolic compound in an amount of more than 1 percent in the total gas chromatographic area, a distyrene-containing phenolic compound in an amount of more than 1 percent in the total gas-chromatographic area, and a tristyrene-containing phenolic compound in an amount of more than 1 percent in the total gas-chromatographic area.

In another aspect, the at least one monostyrene-containing phenolic compound comprises a mixture of monostyrene-containing phenol and monostyrene-containing o-cresol, the at least one distyrene-containing phenolic compound includes a mixture of distyrene-containing phenol and the distyrene-containing o-cresol, and at least one tristyrene-containing phenolic compound tristyrene-containing o-cresol. The composition may, for example, contain a monostyrene-containing phenolic compound in an amount of more than 1 percent in the total gas chromatographic area, a distyrene-containing phenolic compound in an amount of more than 1 percent in the total gas-chromatographic area, and a tristyrene-containing phenolic compound in an amount of more than 1 percent in the total gas-chromatographic area.

In another aspect, the invention relates to a method for producing a liquid composition of a styrene-containing phenolic compound, comprising the steps of reacting styrene with at least one phenolic compound in the presence of a sulfonic acid catalyst in a reactor at an elevated temperature, to obtain a mixture of products containing at least one distyrene-containing phenolic compound in an amount of 70 to 98 percent of the total gas chromatographic area, monostyrene-containing phenolic compound in an amount of b more than 1 percent of the total gas chromatographic area and a tristyrene-containing phenolic compound in an amount of more than 1 percent of the total gas chromatographic area. In this embodiment, the phenolic compound preferably has the formula

where R ₁ represents a hydrogen atom or methyl. The product mixture is preferably a liquid at room temperature.

For example, at least one phenolic compound may include one or more phenols, p-cresol, o-cresol, a mixture of o-cresol and p-cresol, a mixture of phenol and p-cresol, a mixture of phenol and o-cresol, or a mixture of o-cresol , p-cresol and phenol. In one embodiment of the invention, the product mixture consists of a distyrene-containing p-cresol in an amount of more than 1 percent of the total gas chromatographic area and a distyrene-containing o-cresol in an amount of more than 1 percent of the total gas chromatographic area. In another embodiment, the product mixture contains monostyrene-containing phenol in an amount of more than 1 percent of the total gas chromatographic area, distyrene-containing phenol in an amount of more than 1 percent of the total gas chromatographic area and tristyrene-containing phenol in an amount of more than 1 percent in the total gas-chromatographic area. In another embodiment, the product mixture contains monostyrene-containing phenol in an amount of more than 1 percent of the total gas chromatographic area, distyrene-containing phenol in an amount of more than 1 percent of the total gas chromatographic area and tristyrene-containing phenol in an amount of more than 1 percent in the total gas-chromatographic area. The product mixture preferably contains at least one monostyrene-containing phenolic compound in an amount of more than 5 percent of the total gas chromatographic area and preferably contains at least one tristyrene-containing phenolic compound in an amount of more than 5 percent of the total gas chromatographic area. The product mixture preferably contains a monostyrene-containing phenolic compound in an amount of less than 10 percent of the total gas chromatographic area and a tristyrene-containing phenolic compound in an amount of less than 10 percent of the total gas chromatographic area. The product mixture preferably contains a monostyrene-containing phenolic compound and a tristyrene-containing phenolic compound in an amount of 5 to 20 percent of the total gas chromatographic area.

The sulfonic acid catalyst used in the process is preferably selected from the group consisting of trifluoromethanesulfonic acid and trichloromethanesulfonic acid. In another aspect, the sulfonic acid catalyst is selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, methyl trichloromethanesulfonic acid, methyl trifluoromethanesulfonic acid, ethyl trichloromethanesulfonic acid, and ethyl trifluoromethanesulfonic acid. The sulfonic acid catalyst is optionally contained in an amount ranging from 1 ppm by weight to 1000 ppm by weight, based on the total weight of styrene, phenolic compound and catalyst introduced into the reactor.

Styrene and a phenolic compound are preferably reacted in a molar ratio of from 1.85: 1 to 2.1: 1, respectively. Ideally, the product mixture has an acid number of less than 0.1 mg KOH / gram and preferably has an APHA color number of less than 150, for example less than 100.

In another embodiment, the invention relates to a method for producing a mixture of styrene-containing products, for example one or more phenols, o-cresol and / or p-cresol, which is liquid at room temperature and preferably has a viscosity of less than 40,000 centipoise at 25 ° C. The method makes it possible to obtain the corresponding distyrol-containing phenolic compounds constituting at least 70% of the total GC area. The method includes the steps of reacting styrene with one or more phenolic compounds, for example, one or more phenols, o-cresol and / or p-cresol, in a molar ratio of from 1.85 to 2.1: 1, respectively, in the presence of an acid catalyst, for example sulfonic acid, at an elevated temperature, where the mixture contains at least one monostyrene-containing phenolic compound, at least one distyrene-containing phenolic compound and at least one tristyrene-containing phenolic compound and has an acidic the number is less than 0.1 mg KOH / gram.

In another aspect, the present invention relates to a method for stabilizing a polymer composition, comprising introducing into the said composition an effective amount of a mixture of styrene-containing phenolic compounds, for example p-cresol, which is liquid at room temperature and has a viscosity of less than 40,000 centipoise at 25 ° C, where the mixture is obtained by a method leading to the formation of distyrene-containing phenolic compounds, for example, 2,5-distyryl-p-cresol, constituting at least 70% of the total GC area, and including the interaction of st irol with a phenolic compound, for example, p-cresol, in a molar ratio of from 1.85 to 2.1: 1, respectively, in the presence of an acid catalyst, for example, a sulfonic acid catalyst, at an elevated temperature, wherein said mixture contains at least at least one monostyrene-containing compound, for example, monostyrene-containing p-cresol, at least one distyrene-containing phenolic compound, for example, a distyrene-containing p-cresol, and at least one tristyrene-containing phenolic compound, for example, tristyrene-containing General p-cresol, and has an acid value of less than 0.1 mg KOH / gram.

In another aspect, the present invention relates to a composition containing a mixture of styrene-containing p-cresol compounds, which is liquid at room temperature, has a viscosity of less than 40,000 centipoise at 25 ° C and contains 2,6-distyrene-containing p-cresol, comprising at least 70% according to the total GC area, and obtained by a method involving the interaction of styrene with p-cresol in a molar ratio of from 1.85 to 2.1: 1, respectively, in the presence of an acid catalyst at elevated temperature, where this mixture contains monostyrene-containing nd p-cresol, p-cresol distirolsoderzhaschy tristirolsoderzhaschy and p-cresol and has an acid number of less than 0.1 mg KOH / gram.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The present invention relates to compositions of styrene-containing phenolic compounds that are liquid at room temperature. In one embodiment, the present invention relates to a liquid composition of styrene-containing phenolic compounds containing at least one distyrene-containing phenolic compound in an amount of from about 70 to about 98 percent of the total gas chromatographic area, at least one monostyrene-containing phenolic compound in an amount of more than 1 percent, for example, more than 5 percent of the total gas chromatographic area and at least one tristyrene-containing phenolic compound more than 1 percent, for example, more than 5 percent, of the total gas chromatographic area. Optionally, the composition contains at least one monostyrene-containing phenolic compound in an amount of less than 10 percent (but more than 1 percent) of the total gas chromatographic area and at least one tristyrene-containing phenolic compound in an amount of less than 10 percent (but more than 1 percent) of the total gas chromatographic area. The composition preferably contains a monostyrene-containing phenolic compound and a tristyrene-containing phenolic compound, in combination, in an amount of from 5 to 20 percent of the total gas chromatographic area. Compositions of styrene-containing phenolic compounds of the present invention preferably have a viscosity at room temperature of less than 40,000 centipoise.

It was unexpectedly discovered that the styrene-containing phenolic compounds of the present invention are highly stable liquids at room temperature (25 ° C) and usually have high desirable color and transparency characteristics, for example, have an APHA color intensity index of less than 150, for example, less than 100 or less than 80. As a result, the composition of styrene-containing phenolic compounds of the present invention are easily transported and are well suited for stabilizing polymer products and lubricants.

In another embodiment, the invention relates to a method for producing these compositions of styrene-containing phenolic compounds using a sulfonic acid catalyst. The invention also relates to polymer products and lubricants that are stabilized by these compositions of styrene-containing phenolic compounds.

Methods for preparing compositions of styrene-containing phenolic compounds

Compositions of styrene-containing phenolic compounds of the present invention are preferably prepared by reacting styrene with one or more phenolic compounds, preferably in a molar ratio of from about 1.85: 1 to about 2.1: 1, respectively, at elevated temperatures in the presence of an acid catalyst, preferably a catalyst based sulfonic acid, to obtain a mixture of styrene-containing phenolic compounds. The preferred molar ratio styrene: phenolic compound is from 1.75 to 2.2: 1, for example, from 1.85 to 1.98: 1, from 1.9 to 1.98: 1, or approximately 1.95: 1. The phenolic compound used in the reaction with styrene to produce the liquid styrene-containing phenolic compounds of the present invention can vary widely, but in preferred embodiments it is selected from one or more phenols, p-cresol, m-cresol and o-cresol.

Scheme 1 below depicts a specific reaction in which p-cresol is the phenolic compound. As shown, p-cresol is reacted with styrene in the presence of an acid catalyst, preferably a sulfonic acid catalyst, to produce monostyrene-containing p-cresol, distyrene-containing p-cresol and tristyrene-containing p-cresol.

Scheme 1

A specific way to obtain a composition of styrene-containing phenolic compounds, liquid at room temperature

The main product in the product mixture is a distyrene-containing phenolic compound (for example, 2,6-distyrene-containing p-cresol in Scheme 1), comprising not less than 70%, for example, not less than 75%, not less than 80% or not less than 90%, in total gas chromatographic (GC) area. The distyrene-containing phenolic compound in the product mixture and its various isomers are referred to herein as the product “Di." In terms of content ranges, the di-product may be contained in a mixture of products in an amount of about 70 to 98%, for example, from 80 to 95%, from 80 to 92%, from 80 to 85%, from 85 to 95% or from 90 to 95%, determined by the total area of the GC. Preferably, minor amounts of the corresponding monostyrene-containing phenolic compounds (“mono”) and tristyrene-containing phenolic compounds (“three”) are also formed during the reaction, as shown in Scheme 1 above for p-cresol. As will be apparent to those skilled in the art, many different “three” compounds and isomers can be formed during the reaction (only one tri-compound is illustrated), and the term “three,” as used herein, refers to each of these various compounds in together, if the corresponding phenolic compound has three styryl groups attached to it. Thus, the terms “mono,” “di,” and “three,” as used herein, refer to phenolic compounds (e.g., one or more phenols, p-cresol and / or o-cresol) substituted with one, two, or three styryl groups, respectively, including their various isomers.

As indicated above, the phenolic compound treated with styrene according to the method of the present invention can vary widely. Preferred phenolic compounds include phenol, o-cresol, p-cresol and mixtures thereof. Thus, the phenolic compound preferably has the general formula

where R ₁ represents a hydrogen atom or methyl.

In one embodiment, for example, the phenolic compound comprises p-cresol. In this aspect, the at least one monostyrene-containing phenolic compound includes a monostyrene-containing p-cresol, the at least one distyrene-containing phenolic compound includes a distyrene-containing p-cresol, and the at least one tristyrene-containing phenolic compound includes tristyrene-containing p-cresol.

In another aspect, the phenolic compound comprises a mixture of o-cresol and p-cresol. As a result, the at least one monostyrene-containing phenolic compound includes a mixture of monostyrene-containing o-cresol and the monostyrene-containing p-cresol, and the at least one distyrene-containing p-cresol and the mixture of distyrene-containing o-cresol and a distyrene-containing p-cresol, and at least one trisole-containing p-cresol includes a mixture of tristirol-containing o-cresol and tristirol-containing p-cresol. For example, a composition or mixture of products may contain distyrene-containing p-cresol in an amount of more than 1 percent, calculated on the basis of the total gas chromatographic area and distyrene-containing o-cresol in an amount of more than 1 percent, calculated on the basis of the total gas-chromatographic area.

In another embodiment, the phenolic compound comprises a mixture of phenol and p-cresol. Thus, at least one monostyrene-containing phenolic compound includes a mixture of monostyrene-containing phenol and monostyrene-containing p-cresol, at least one distyrene-containing phenolic compound includes a mixture of distyrene-containing phenol and distyrene-containing p-cresol, and at least one tristyrene-containing phenolic compound triphenol-containing p-cresol. The composition or mixture of products may, for example, contain monostyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area, distyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area and tristyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area .

In yet another embodiment, the phenolic compound comprises a mixture of phenol and o-cresol. In this aspect, at least one monostyrene-containing phenolic compound includes a mixture of monostyrene-containing phenol and monostyrene-containing o-cresol, at least one distyrene-containing phenolic compound includes a mixture of distyrene-containing phenol and distyrene-containing o-cresol, and at least one tristyrene-containing phenolic compound tristyrene-containing o-cresol. The composition or mixture of products may, for example, contain monostyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area, distyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area and tristyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area .

Similarly, a phenolic compound may include a mixture of phenol, o-cresol and p-cresol, in this case at least one monostyrene-containing phenolic compound includes a mixture of monostyrene-containing phenol, monostyrene-containing o-cresol and monostyrene-containing p-cresol. In this case, at least one distyrene-containing phenolic compound includes a mixture of distyrene-containing phenol, distyrene-containing o-cresol and distyrene-containing p-cresol, and at least one tristyrene-containing phenolic compound includes a mixture of tristyrene-containing o-cresol and tristyrene-containing t-cresol. The composition or mixture of products may, for example, contain monostyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area, distyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area and tristyrene-containing phenol in an amount of more than 1 percent based on the total gas chromatographic area .

Regardless of which phenolic compound is used in the process, the liquid physical form of the compositions of styrene-containing phenolic compounds of the present invention is achieved by introducing two additional reaction products, namely mono- and tri-products, into the resulting composition of a styrene-containing phenolic compound. In addition, the compositions of the styrene-containing phenolic compounds of the present invention preferably have enhanced transparency and have a color intensity index of less than 150 for ARHA, for example, less than 100 for ARHA or less than 80 for ARNA. Hereinafter, for convenience, the stabilizers of the present invention will be called for simplicity styrene-containing phenolic compositions; however, it should be understood that the real product is a composition of mixtures of mono-, di - and tri-products, as discussed above.

The relative amounts of mono-, di- and tri-compositions formed in the process can be controlled by selecting the relative proportions of the reactants. Typically, for example, an increase in the molar ratio styrene: phenolic compound will lead to a favorable formation of tri-compounds compared to mono-compounds. Conversely, a decrease in the molar ratios of styrene: phenolic compound will favor the formation of mono compounds as compared to tri compounds.

Typically, styrene is added to the phenolic compound, for example, one or more phenols, o-cresol and / or p-cresol, rather than the phenolic compound to styrene, which may undesirably lead to the polymerization of styrene before or at the time the phenolic compound is added. In one aspect, styrene is added to a heated phenolic compound that has been heated to a temperature in the range from 50 to 90 ° C, for example, from 55 to 85 ° C, from 60 to 80 ° C, or preferably to about 70 ° C.

In one embodiment, the reaction is isothermal, i.e. at one elevated temperature, during the entire reaction process. Preferably, the reaction is carried out at a temperature in the range of from about 40 ° C to about 150 ° C, more preferably in the range of from about 60 to about 80 ° C.

The formation of mono-compounds proceeds quickly, but the formation of di-compounds occurs more slowly. The rate of formation of di-compounds can be increased, however, by increasing the temperature of the reaction mixture. Thus, in another embodiment of the invention, a two-stage temperature increase scheme is used in which the reagents are heated to a first temperature for a first time period, and then the reaction mixture is heated to a second “final” temperature for a second time period. The first temperature is optionally in the range from 50 to 90 ° C., for example, from 55 to 85 ° C., from 60 to 80 ° C., or preferably it is about 70 ° C., and the first period of time can be in the range from 1 to 10 hours for example, from 1 to 4 hours, from 2 to 4 hours, or from 2.5 to 3.5 hours. For the purposes of the present invention, the first period of time begins from the moment the reactants initially contact each other, for example, when styrene is added to the phenolic compound. The second temperature is optionally in the range from 60 to 110 ° C., for example, from 70 to 110 ° C., from 80 to 100 ° C., or is preferably approximately 90 ° C., and the second period of time is in the range from 0.25 to 4 hours for example, from 1 to 4 hours, from 2 to 4 hours, or from 2.5 to 3.5 hours. Prolonged heating times may result in darkening of the resulting reaction mixture and, depending on the intended use, this may be undesirable. The difference between the second and first temperatures is preferably more than 10 ° C., for example, more than 15 ° C., and most preferably approximately 20 ° C. As for the intervals, the difference between the second and first temperatures is not necessarily from 10 to 70 ° C, for example, from 10 to 50 ° C or from 15 to 25 ° C. In the present embodiment, the reaction process can take place in one reactor, where the temperature can be raised from the first temperature to the second temperature, or, conversely, in two or more separate reactors. For example, the reactants may first be loaded into a first reactor, which is maintained at a first temperature, and then the resulting mixture is sent to a second reactor, which is maintained at a second temperature, to complete the process.

In another embodiment, the temperature can be gradually increased during the course of the reaction process or during part of the reaction process. For example, the temperature can be gradually increased, for example, at a speed of from 0.01 to 2 ° C / min, at a speed of from 0.02 to 1 ° C / min, or at a speed of 0.02 to 0.1 ° C / min, optionally over a period of time ranging from 0.5 to 8 hours, for example, from 2 to 8 hours or from 4 to 8 hours.

The total reaction time will usually be in the range of from about one to about seven hours, preferably in the range of from about three to about four hours. If desired, the reaction can be carried out in a solvent medium which is inert to the components of the reaction mixture and which will preferably be a hydrocarbon such as toluene, benzene, heptane, hexane and the like. The reaction can be carried out in the form of a continuous, semi-continuous or batch process.

Catalyst

The process of attaching styrene to phenolic compounds preferably proceeds in the presence of a catalyst. A suitable catalyst usually has acidic properties, for example, Bronsted acid or Lewis acid. However, it is known that some acid catalysts give yellow color to styrene-containing phenolic compositions, which may render them unsuitable for certain applications, for example, when introduced into polymers or lubricants, for which color is an important criterion. Examples of these catalysts include, but are not limited to, boron trifluoride etherate and sulfuric acid. For example, it is known that a catalyst based on boron trifluoride etherate gives a product with a color intensity index of more than 150 according to the classification of the American Public Health Association (ARNA). Color is usually less important for lubricants than for polymers.

On the other hand, it has been unexpectedly found that some acid catalysts do not substantially stain. Thus, in another embodiment of the invention, if desired, liquid compositions of styrene-containing phenolic compounds having very low color intensity can be especially preferred for use with polymers. A typical preferred APHA value for the liquid compositions of styrene-containing phenolic compounds of the present invention is an APHA color intensity of less than 150, preferably an APHA color intensity of less than 100 or less than 80. Examples of low-staining catalysts in this context include, but are not limited to, sulfonic acids and ion exchange pitches. Sulfonic acid may have the formula:

where R is selected from the group consisting of a hydrogen atom, an alkyl group, such as, for example, a C ₁ -C ₆ alkyl group (including, but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , sec-butyl, tert-butyl, phenyl, hexyl, heptyl and octyl), a halogen atom (i.e. F, Cl, Br, I or At), aryl (including, but not limited to, phenyl, benzyl, o-tolyl, m-tolyl and p-tolyl) and haloalkyl (including, but not limited to, trichloromethyl and trifluoromethyl). Preferred sulfonic acids include, for example, methanesulfonic acid, ethanesulfonic acid, trichloromethanesulfonic acid and trifluoromethanesulfonic acid (triflic acid).

The amount of acid catalyst used in the process will vary widely, depending, for example, on the strength of the acid. If triflic acid is used as the acid catalyst, then preferably its content will be in the range from 1 ppm by mass to 1000 ppm by mass, for example, from 1 ppm by mass to 100 ppm by mass, based on the total weight of styrene, phenolic compound and catalyst introduced into the reactor. Large quantities, for example, more than 0.1% of the mass., More than 1% of the mass., More than 3% of the mass. or potentially significantly higher amounts of catalyst may be needed for other catalysts, for example, ion exchange resins or weaker acids.

The optionally used catalyst includes a sulfonic acid catalyst, for example triflic acid, in combination with one or more phosphites. For example, the molar ratios of sulfonic acid to phosphites can range from, for example, 1 to 5 or 1 to 100. Examples of phosphites that can be used include trilauryl phosphite, diisodecyl phenyl phosphite, isodecyl diphenyl phosphite, triphenyl phosphite. Unexpectedly high conversions, for example, greater than 80 percent, greater than 90 percent, or greater than 95 percent, can be achieved using catalytic systems involving the use of a sulfonic acid catalyst in combination with phosphites.

In some aspects, it may be necessary to remove the acid catalyst from the resulting mixture of the styrene-containing phenolic product, for example, by contacting the product mixture with a neutralizing agent such as kaolin or soda ash. Preferably, however, the acid number of the initially formed mixture of styrene-containing phenolic products is sufficiently low (for example, less than 0.1 mg KOH / gram, as described below), so that it becomes necessary to remove the catalyst or use a neutralizing agent. This is especially true when very strong acids, such as triflic acid, are used as a catalyst in very small quantities, as discussed above.

New compositions of styrene-containing phenolic products

The above methods of the present invention form new compositions of styrene-containing phenolic compounds, which include a mixture of mono-, di- and tristyrene-containing phenolic compounds. In order to achieve the desired liquid physical form and the duration of the liquid form, each of the mono- and tri-components must be contained in an amount of more than 1% of the total area of the GC peaks, optionally at least 2%, at least 5%, or at least 10%, calculating the total GC area of the product mixture (including peaks corresponding to unreacted styrene and phenolic compounds). The typical mono component content is in the range of from more than 1 to about 15%, for example, from about 1 to about 10%, or from about 2 to about 5%, based on the total GC area of the product mixture. Typical tri-component contents are from about 1 to about 15%, and also, for example, from about 1 to about 10%, or from about 2 to about 5%, based on the total GC area of the product mixture. Preferably, the percentage of the combination of mono- and tri-components will be in the range of from about 2 to about 30 percent based on the total GC area of the product mixture, for example, from about 5 to about 30 percent, from about 5 to about 20%, from about 5 to about 10%, based on the total GC area of the product mixture.

As noted above, the composition of the styrene-containing phenolic compounds of the present invention (optionally containing a diluent, as discussed below) is preferably liquid. More preferably, the composition (optionally with a diluent) has a viscosity of less than 40,000 centipoise at 25 ° C, for example, less than 30,000 centipoise, less than 25,000 centipoise, or less than 15,000 centipoise at 25 ° C. From the point of view of intervals, the composition of styrene-containing phenolic compounds, in the presence or absence of a diluent, can have a viscosity in the range from 1000 to 40,000 centipoise, for example, from 1,500 to 30,000 centipoise or from 2,000 to 30,000 centipoise at 25 ° C. As used herein, unless otherwise indicated, the term “viscosity” refers to Brookfield viscosity at 25 ° C. as defined by ASTM D2393, which is incorporated herein by reference in its entirety.

Some traditional compositions of styrene-containing phenolic compounds are prone to solid form or are unstable diluted compositions containing a precipitate. Stirring and shaking of the compositions of styrene-containing phenolic compounds may further lead to the formation of a precipitate. In contrast, the styrene-containing phenolic compounds of the present invention are not diluted and preferably do not form any visible solid precipitates (precipitate) after 1 week, more preferably after 2 weeks, after 1 month, after 3 months, after 6 months or after 1 year of storage without noticeable mixing and optionally in a nitrogen atmosphere. The data on the amount of precipitate were calculated by the number of compositions of styrene-containing phenolic compounds at room temperature without significant movement, i.e. remaining in the container for storage on a flat surface for a significant period of time and preferably in a nitrogen atmosphere.

Although acid catalysts are preferably used in the methods of the present invention, the resulting composition of styrene-containing phenolic compounds preferably has a low acid number, since the presence of acid in the composition of styrene-containing phenolic compounds can undesirably contribute to the polymerization of styrene-containing phenolic compounds and reduce the lifetime of the liquid form. In some preferred embodiments, the styrene-phenolic compound composition has an acid value of less than 0.5 mg KOH / gram, for example, less than 0.2 mg KOH / gram, less than 0.1 mg KOH / gram, less than 0.05 mg KOH / gram or less than 0.01 mg KOH / gram. As used herein, the acid number is determined by titration with a KOH / methanol solution, where the substance to be titrated is dissolved in isopropyl alcohol. The acid number is the amount of mg KOH required per gram of sample to achieve a neutral solution.

Diluent

Although the mixtures of styrene-containing phenolic products of the present invention are liquids at room temperature even in the absence of any other components, their viscosity can be further reduced by adding a diluent to them. Thus, in a preferred embodiment, a diluent is added to the composition of styrene-containing phenolic compounds described above to further reduce its viscosity relative to the composition without the diluent. Thus, compositions of styrene-containing phenolic compounds of the present invention may or may not contain a diluent. In a preferred embodiment, the invention relates to a composition of styrene-containing phenolic compounds containing at least one distyrene-containing phenolic compound (for example, 2,6-distyrene-containing p-cresol), optionally in an amount of from 70 to 98 percent of the total gas chromatographic area, at least one monostyrene-containing the phenolic compound is optionally in an amount of more than 1 percent, for example, more than 5 percent, of the total gas chromatographic area, at least one tristyrene-containing its phenolic compound is optionally in an amount of more than 1 percent, for example, more than 5 percent, of the total gas chromatographic area, and the diluent is optional in an amount in the range from 0.5 to 20% by weight, for example, from 1 to 10% by weight, from 3 to 7% of the mass. or approximately 5 wt. -%, calculated on the total weight of styrene-containing phenolic compounds and diluent.

The composition diluent may be any liquid miscible with the styrene-containing phenolic compounds discussed above, which improves the transportability of the composition as described above. Examples of diluent materials may include, for example, lubricating oils, including base components obtained by isomerization of synthetic wax and wax, as well as base hydrocracking components obtained by hydrocracking (faster than solvent extraction) of aromatic and polar components of crude oil. Other possible diluents include mineral oils and oils derived from coal and shale. Natural materials suitable for use as diluents may include, for example, animal oils such as lard oil, tall oil, vegetable oils including canola oil, castor oil, flaxseed oil, and sunflower oil. In several preferred embodiments, the diluent comprises epoxidized vegetable oil, such as, but not limited to, epoxidized conola oils, epoxidized castor oils, epoxidized linseed oil, and epoxidized sunflower oil. In a preferred aspect, the lubricating oil comprises commercially available epoxidized soybean oil, such as DRAPEX® 6.8 (Chemtura Corp., Middlebury. Connecticut, USA).

The viscosity of the solvent can likewise vary widely, but is preferably not more than 5000, for example, not more than 1000 centipoise, not more than 500 centipoise, not more than 400 centipoise or not more than 350 centipoise. Within the ranges, the diluent preferably has a viscosity ranging from 100 to 500 centipoise, for example, from 200 to 400 centipoise or from 260 to 380 centipoise, most preferably about 320 centipoise. The diluent preferably has a molecular weight of less than 10,000, for example, less than 5,000, less than 2,500 or less than 1,500 and optionally ranges from 500 to 1500, for example, from 250 to 1250, and most preferably is about 1000. Unless otherwise specified, the molecular weights indicated in this description, determined by gel permeation chromatography using polystyrene standards.

Depending on its composition, the diluent may slowly hydrolyze and / or polymerize in the presence of acids, alkalis, water or water vapor. Thus, the diluent preferably has a low acid number, preferably less than 1.5, for example less than 1.0, and preferably about 0.5, as determined by AOTS-Te-2a, which is incorporated herein by reference in its entirety. The diluent also ideally has a very high degree of saturation (low degree of unsaturation) and preferably has an iodine number (HANUG) of less than 2.0, for example, less than 1.8 or less than 1.5, as determined according to AOCS-Tgl-64T, which in its entirety, incorporated herein by reference.

The amount of diluent added to the composition of styrene-containing phenolic compounds for processing purposes depends on factors such as the end use of the composition of styrene-containing phenolic compounds. In some preferred embodiments, the diluent is added to the composition of styrene-containing phenolic compounds in an amount of less than 20% by weight, for example, less than 10% by weight. or less than 8 wt. -%, calculated on the total weight of the composition of styrene-containing phenolic compounds and diluent. Within the limits of the intervals, a diluent is optionally added to styrene-containing phenolic compounds in an amount in the range from 0.5 to 20% by weight, for example, from 1 to 10% by weight, from 3 to 7% by weight. or approximately 5 wt. -%, calculated on the total weight of styrene-containing phenolic compounds and diluent.

Polymer stabilization

The invention further relates to stabilized thermoplastics or polymer resins, where one component contains a composition of styrene-containing phenolic compounds, and the other contains a thermoplastic and / or elastic polymer, such as polyolefin, polyvinyl chloride, BSC (SBR), nitrile rubber and the like.

The thermoplastic polymers that can be stabilized with the styrene-containing phenolic compounds of the present invention can be any thermoplastic known in the art, such as polyolefin homopolymers and copolymers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrene polymers and copolymers , polycarbonates, acrylic polymers, polyamides, polyacetals and halogen-containing polymers. Mixtures of various polymers can also be used, such as polyphenylene ether / styrene resin, polyvinyl chloride / ABS (ABS), or other impact resistant polymers such as methacrylonitrile and alpha-methyl styrene containing ABS, and polyester / ABS or polycarbonate / ABS and polyester plus some other impact modifier. These polymers are commercially available or can be obtained by means known in the art. The stabilizers of the present invention are particularly suitable for use in polyolefins, polyurethanes and halogen-containing polymers.

Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example cyclopentene or norbornene, polyethylene (which may optionally be cross-linked), for example, can be used, for example. high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). Mixtures of these polymers can also be used, for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of various types of polyethylene (e.g. LDPE / HDPE). Also suitable for use are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene / propylene, LLDPE and mixtures thereof with LDPE, propylene / butene-1, ethylene / hexene, ethylene / ethylpentene, ethylene / heptene, ethylene / octene, propylene / isobutylene, ethylene / butene-1, propylene / butadiene, isobutylene, isoprene, ethylene / alkyl acrylates, ethylene / alkyl methacrylates, ethylene / vinyl acetate (EVA) or ethylene / acrylic acid (EAA) copolymers and their salts (ionomers) and ethylene terpolymers with propylene and a diene such as hexadium , Dicyclopentadiene or ethylidene-norbornene; as well as mixtures of these copolymers and mixtures thereof with the polymers described above, for example, polypropylene / ethylene propylene copolymers, LDPE / EVA, LDPE / EAA, LLDPE / EVA and LLDPE / EAA.

Halogen-containing polymers, such as PVC, can also be used. As used herein, it is intended that the terms “poly (vinyl) chloride” and “PVC” include both homopolymers and copolymers of vinyl chloride, i.e. vinyl resins containing vinyl chloride units in their structure, for example, copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate; copolymers of vinyl chloride with esters of acrylic and methacrylic acid with acrylonitrile; copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride; postchlorinated polymers and copolymers of vinyl chloride; copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones, and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether, and the like.

The terms "poly (vinyl) chloride" and "PVC", as used herein, also include grafted polymers based on PVC with EVA (EVA), ABS (ABS) and MBS (MBS). Mixtures of the above homopolymers and copolymers, in particular homopolymers based on vinyl chloride with other thermoplastics and / or rubbers, in particular mixtures with ABS (ABS), MBS (MBS), BNK (NBR), SAN (SAN), EVA, are also preferred substrates. (EVA), HSP (CPE), MBAS (MBAS), PMA (PMA), PMMA (PMMA), EPDK (EPDM) and polylactones.

Vinyl acetate, vinylidene chloride, acrylonitrile, chlorofluoroethylene and / or esters of acrylic, fumaric, maleic and / or itaconic acids can be mentioned as preferred examples of monomers that are copolymerized with vinyl chloride. In addition, polyvinyl chloride can be chlorinated and have a chlorine content of up to 70% by weight. The present invention particularly relates to vinyl chloride homopolymers.

In the scope of the present invention, PVC should be understood as including halogen-containing polymers of secondary use that have undergone changes during processing, use or storage. The polymers may also include styrene polymers such as polystyrene, poly (p-methyl styrene), poly (α-methyl styrene), copolymers of styrene or α-methyl styrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / maleic anhydride, styrene / maleimide, styrene / butadiene / ethyl acrylate, styrene / acrylonitrile / methyl acrylate, mixtures with high impact strength from styrene copolymers with another polymer, such as, for example, polyacrylate, diene polymer or /etc sawdust / diene; and styrene block copolymers such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

Styrene polymers may additionally or alternatively include graft copolymers of styrene or α-methyl styrene, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and their copolymers; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene-acrylate-acrylate and acrylonitriol-acrylate polymers indicated above.

Nitrile polymers can also be used in the polymer composition of the present invention. These include homopolymers and copolymers of acrylonitrile and its analogues, such as polymethacrylonitrile, polyacrylonitrile, polymers of acrylonitrile / butadiene, polymers of acrylonitrile / alkyl acrylate, polymers of acrylonitrile / alkyl methacrylate / butadiene, and various ABS compositions as indicated above with respect to styrene.

Acrylic acid based polymers such as acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid and their esters can also be used. These polymers include polymethyl methacrylate and graft copolymers of the ABS type, where all or part of the acrylonitrile type monomer is replaced by an acrylic ester or acrylic acid amide. Polymers including other acrylate-type monomers such as acrolein, methacrolein, acrylamide and methacrylamide can also be used.

Other suitable polymers include homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycyl ethers; polyacetals such as polyoxymethylene and polyoxymethylene-based polyacetals that contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, ABC containing acrylates or methacrylonitrile; polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene or polyamides; polycarbonates and polyester carbonates; polysulfones, polyethersulfones and polyethersetones; and polyesters that are formed by dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, poly-2- (2,2,4- (4-hydroxyphenyl) propane ) terephthalate and polyhydroxybenzoates, as well as block copolymers based on simple and complex polyesters formed by simple polyesters having hydroxyl end groups.

Polyamides and copolyamides can be used which are formed by bisamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6 , polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylenebisamine and adipic acid; polyamides derived from hexamethylene bisamine and isophthalic and / or terephthalic acid, and optionally rubber as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide. Other copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers, or chemically bonded or grafted rubbers can be used; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycols, and polyamides or copolyamides modified with EPDM or ABS.

Representative examples of suitable rubbers include styrene butadiene rubber (SSBR), styrene butadiene rubber (SBR), natural rubber (NR), polybutadiene (BR), ethylene propylene co and terpolymers (EP, EPDM) and butadiene acrylonitrile rubber (NBR, BNK). The rubber composition consists of at least one diene or rubber based elastomer. Suitable conjugated dienes are isoprene and 1,3-butadiene, and styrene and α-methylstyrene are suitable vinyl aromatic compounds. Thus, rubber is sulfur vulcanization rubber. Such a diene-based elastomer, or rubber, can be selected, for example, from at least one cis-1,4-polyisoprene rubber (natural and / or synthetic, and preferably natural rubber), a rubber based on a styrene / butadiene copolymer obtained emulsion polymerization, styrene-butadiene rubber, solution-polymerized rubber, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis-1,4-polybutadiene, medium butadiene rubber Vinyl (35 to 50 percent vinyl), high vinyl butadiene rubber (50 to 75 percent vinyl), styrene / butadiene / acrylonitrile copolymers based on emulsion polymerization, and rubber based butadiene / acrylonitrile copolymer. As styrene-butadiene rubber obtained by emulsion polymerization (e-SBR), rubber having a relative styrene content of from 20 percent to 28 percent bound styrene can be used, for some applications e-SBR has a moderate to relatively high bound styrene content, namely, the styrene content is from 30 percent to 45 percent. Rubbers based on the styrene / butadiene / acrylonitrile thermopolymer obtained by emulsion polymerization, containing from 2 to 40% of the mass. bound acrylonitrile in a copolymer are also included among diene rubbers for use in the present invention.

SBR obtained by solution polymerization (s-SBR) typically has a bound styrene content in the range of 5 to 50 percent, preferably 9 to 36 percent. Polybutadiene rubber can be conveniently characterized, for example, by a content of at least 90% by weight. cis-14 links.

Regardless of which polymer or polymers are used, one or more polymers preferably contain a stabilizing amount of the composition of styrene-containing phenolic compounds of the present invention. As used herein, a “stabilizing amount” or “effective amount” of a composition of styrene-containing phenolic compounds of the present invention implies that a polymer composition containing this composition of styrene-containing phenolic compounds shows improved stability of any of its physical properties or color compared to a similar polymer composition , which does not include styrene-containing phenolic compounds.

Examples of improved stability include improved stability, for example, of molecular weight against degradation, color deterioration and the like, for example, from melt processing, exposure to weather conditions and / or prolonged exposure to heat, light and / or other factors. In one example, improved stability refers to one or both of these factors, such as a lower intensity of the original color or additional resistance to atmospheric aging, measured, for example, by the initial yellowness index (YI) or by the resistance to yellowing and color change compared to the composition without the addition of a stabilizer .

Although the desired stabilizing amount of the composition of styrene-containing phenolic compounds will vary widely, depending on the polymer used and the intended use of the polymer product, in some example embodiments, the composition of styrene-containing phenolic compounds is present in an amount of less than 5 wt.%, For example, less than 1 weight percent. less than 1000 ppm by mass, less than 500 ppm by mass, or less than 100 ppm by mass, based on the total weight of the polymer and styrene-containing composition phenolic compounds. From the point of view of intervals, the composition of styrene-containing phenolic compounds may be present in the polymer in an amount of from 10 ppm by weight to 5% by weight, for example, from 100 ppm by weight to 1 weight percent, from 100 to 5000 ppm by weight weight or from 150 ppm by weight to 1000 ppm by weight, based on the total weight of the polymer and the composition of styrene-containing phenolic compounds.

Grease stabilization

In addition to being used in polymers, the compositions of styrene-containing phenolic compounds of the present invention can also be used to stabilize lubricants, such as base components of lubricating oils. Thus, in one embodiment, the invention relates to a lubricating composition containing a base component of the lubricant in an amount of more than 90 wt. -%, for example, more than 95% of the mass. or more than 99% by weight, based on the weight of the lubricant composition; and a composition of styrene-containing phenolic compounds, preferably in an amount of more than 0.05 wt. -%, for example, more than 0.5% of the mass. or more than 1 weight percent, based on the weight of the lubricating composition. From the point of view of intervals, the lubricating composition preferably contains a composition of styrene-containing phenolic compounds in an amount of from 0.05 to 10% by weight, for example, in an amount from 0.1 to 5% by weight. or in an amount of from 0.5 to 1 weight percent, based on the weight of the lubricating composition. As described above, the composition of styrene-containing phenolic compounds preferably contains distyrene-containing phenolic compounds (for example, 2,6-distyrene-containing p-cresol) in an amount of from about 70 to 98%, for example, from 80 to 95%, from 80 to 92%, from 80 up to 85%, from 85 to 95% or from 90 to 95%, by total gas chromatographic area, monostyrene-containing phenolic compounds in an amount of more than 1 percent, for example, more than 5 percent, by total gas-chromatographic area, and tristyrene-containing phenolic compounds in an amount of more than 1 percent , n example, more than 5 percent, based on the total area of the gas chromatograph. The styrene-containing phenolic compounds composition optionally further comprises a diluent, as discussed above.

The base component of the lubricating oil can be any natural or synthetic base component of the lubricating oil based on a fraction having a kinematic viscosity at 100 ° C. of from about 2 to about 200 centistokes, more preferably from about 3 to about 150 centistokes, and most preferably from about 3 to about 3 100 centistokes. The base component of a lubricating oil can be formed, for example, by natural lubricating oils, synthetic lubricating oils, or mixtures thereof. Suitable base components of lubricating oils include base components obtained by isomerization of synthetic wax or wax, as well as base components of hydrocracking obtained by hydrocracking (rather than solvent extraction) of aromatic and polar components of crude oil. Natural lubricating oils include animal oils, such as lard oil, tall oil, vegetable oils, including canola oils, castor oils, linseed oils and sunflower oils, for example, petroleum lubricants, mineral oils, and oils derived from coal or shale. In several preferred embodiments, the lubricating oil is an epoxidized vegetable oil, such as, but not limited to, epoxidized canola oils, epoxidized castor oils, epoxidized linseed oils, and epoxidized sunflower oils (e.g., DRAPEX® 6.8, Chemtura Corporation, Middlebury, Connecticut, USA).

Synthetic oils include mineral oils and halogen-substituted mineral oils such as polymerized and copolymerized olefins, gas-in-liquids obtained by the Fischer-Tropsch technology, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogues, homologues, etc. Synthetic lubricating oils also include alkylene oxide polymers, copolymers and derivatives thereof, where the terminal hydroxyl groups, for example, are modified by the esterification reaction of the simple and ester types.

Another suitable class of synthetic lubricants includes dicarboxylic acid esters with various alcohols. Esters used as synthetic oils also include those compounds which are formed by C ₅ -C ₁₈ monocarboxylic acids and polyols, and polyol ethers. Other esters used as synthetic oils include those compounds which are formed by copolymers of α-olefins and dicarboxylic acids, esterified with short or medium chain alcohols.

Silicon-based oils, such as polyalkyl, polyaryl, polyalkoxy, or polyaryloxy siloxane oils and silicate oils, include another valuable class of synthetic lubricating oils. Other synthetic lubricating oils include liquid phosphate esters, polymeric tetrahydrofurans, poly-α-olefins, and the like.

Lubricating oil can be obtained from crude, refined, refined oils or mixtures thereof. Crude oils are obtained directly from a natural source or synthetic source (e.g., coal, oil shale, tar or bitumen) without further purification or processing. Examples of crude oils include distillate shale oil, distillation oil, or ester oil obtained directly from the esterification process, each of which is then used without further treatment. Refined oils are similar to crude oils, except that refined oils are processed in one or more stages of refining to improve one or more properties. Suitable purification methods may include distillation, hydrogenation, dewaxing, solvent extraction, acid or alkali extraction, filtering, straining, and the like, which are all well known to those skilled in the art. Re-refined oils are obtained by treating refined oils with methods similar to those used to produce refined oils. These refined oils are also known as regenerated absorption or refined oils, and are often further processed by methods for removing spent additives and oil degradation products.

The base components of lubricating oils obtained by hydroisomerization of wax can also be used individually or in combination with the above natural and / or synthetic base components. Such an oil obtained by isomerization of a wax is obtained by hydroisomerization of natural or synthetic waxes or mixtures thereof in the presence of a hydroisomerization catalyst. Natural waxes are usually paraffin waxes, extracted with a solvent during the dewaxing of mineral oils; Synthetic waxes are typically Fischer-Tropsch waxes. The resulting isomerized product is usually subjected to dewaxing in solution and fractionation to extract various fractions having a certain range of viscosity values. Isomerized waxes are also characterized by very high viscosity indices (VI), usually after dewaxing of VI, at least 130, preferably at least 135 or higher, as determined according to ASTM D2270, which is incorporated herein by reference in its entirety, and an oil flow loss temperature of about −20 ° C. or lower.

The lubricating oil used in the practice of the present invention can be selected from any of Group I-V base oils as broadly specified in the American Petroleum Institute (API) base oil interchangeability reference. Five groups of base oils are described in table 1.

Table 1
API Base Oil Category Category Sulfur (%) Saturated (%) Viscosity index Group I > 0.03 and / or <90 80-120 Group II <0.03 and > 90 80-120 Group III <0.03 and > 90 > 120 Group IV All poly alpha olefins Group V All others not included in groups I, II, III or IV

Compositions of styrene-containing phenolic compounds of the present invention are particularly suitable as components of many different lubricating oil compositions. Additives can be incorporated into various lubricating viscosity oils, including natural and synthetic lubricating oils and mixtures thereof. Additives can be introduced into gear oils for internal combustion engines with spark ignition and compression ignition. The compositions can also be used in gas engine lubricants, steam and gas turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metalworking equipment lubricants, hydraulic fluids and other lubricating oils and greases.

Although the desired stabilizing amount of the composition of styrene-containing phenolic compounds in the lubricating composition will vary widely, depending on the base component of the lubricant used and the purpose of the lubricating composition, in some example embodiments, the composition of styrene-containing phenolic compounds will be present in the lubricating composition in an amount of less than 10% by weight. , for example, less than 1 mass percent, less than 0.5% of the mass. or less than 0.1 weight percent, based on the total weight of the base component of the lubricant and the composition of styrene-containing phenolic compounds. From the point of view of intervals, the composition of styrene-containing phenolic compounds may be contained in the base component of the lubricant in an amount of from 0.01 to 10% by weight, for example, from 0.1 to 5% by weight. or from 0.1 to 2% wt., calculated on the total weight of the base component of the lubricant and the composition of styrene-containing phenolic compounds.

When mixed with a base component of a lubricant, the composition of styrene-containing phenolic compounds preferably has a high degree of oxidative stability. Oxidative stability can be quantified by scanning differential pressure calorimetry (PDSC). PDSC evaluates the oxidative stability of oils under oxidation conditions in a thin film in isothermal mode. When the temperature during the PDSC is maintained at a predetermined value, the oxidative stability of the test oil is evaluated by the induction oxidation period (OIT) corresponding to the exothermic heat generation caused by the onset of oil oxidation. Oil giving a longer OIT is generally considered more resistant to oxidation. In PDSC testing, each test oil is preheated with 50 ppm oil soluble iron formed by iron naphthenate. Preferably, the lubricant compositions of the present invention have an OIT determined by PDSC at 160 ° C for more than 20 minutes, for example, more than 30 minutes, more than 40 minutes, more than 50 minutes, or more than 55 minutes. The lubricant does not necessarily have an OIT at 185 ° C. determined by the PDSC method for more than 2 minutes, for example more than 5 minutes, more than 8 minutes or more than 10 minutes. Oxidative stability can also be quantified by the Rotating Bomb Method (RPVOT) according to ASTM D2272, which is incorporated herein by reference in its entirety. In some preferred embodiments, the lubricant composition has an RPVOT OIT determined to be greater than 100 minutes, for example, greater than 200 minutes, or greater than 300 minutes.

The lubricant compositions of the present invention also preferably have a reduced tendency to form deposits compared to a similar lubricant composition without the styrene-containing phenolic compounds of the present invention. Scale formation can be quantified, for example, by modeling the thermal oxidation of engine oil (TEOST) at a moderately high temperature (MHT) according to ASTM D7097, which is incorporated herein by reference in its entirety. TEOST models the effects of running engine conditions on oxidation and the tendency to form deposits of lubricant compositions. In some illustrative embodiments, the lubricant compositions of the present invention provide TEH values of MHTs of less than 100 mg, for example, less than 75 mg, less than 60 mg, or less than 55 mg.

Co-stabilizers and additives

The invention further relates to stabilized thermoplastics and / or rubbers and / or lubricant compositions, where one component contains a composition of styrene-containing phenolic compounds of the present invention, and the other contains a polymer or base component of a lubricant, such as discussed above, and where the composition of styrene-containing phenolic compounds is used with -stabilizer, for example, phenolic compounds, aromatic amines, phosphites and phosphonites, hydroxylamines, alkylamine-N-oxides, lactones, simple thioethers, ep oxidized vegetable oils, e.g., epoxidized soybean oil and the like.

Thus, thermoplastic resins and lubricants stabilized by the composition of styrene-containing phenolic compounds of the present invention may optionally contain an additional stabilizer or a mixture of stabilizers selected from the group consisting of phenolic antioxidants, hindered amine stabilizers, ultraviolet light absorbers, phosphites, phosphonites, fatty alkali salts acids, hydrotalcites, metal oxides, epoxidized soybean oils, hydroxylamines, tertiary amine oxides, lactones, thermal interaction products of tertiary amine oxides and thiosynergists. Particularly preferred are phenolic compounds, diarylamines and organophosphites.

Phenolic compounds that can be used as optional co-stabilizers in the practice of the present invention include, but are not limited to:

1. Alkylated monophenols, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2.6 di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol.

2. Alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol .

3. Hydroxylated thiodiphenyl ethers, for example, 2,2-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol).

4. Alkylidene-bisphenols, for example, 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 2, 2'-methylene bis (4-methyl-6- (α-methylcyclohexyl (phenol), 2,2'-methylene bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene bis (6- nonyl-4-methylphenol), 2,2'-methylene bis (6-nonyl-4-methylphenol), 2,2'-methylene bis (6- (α-methylbenzyl) -4-nonylphenol), 2,2 '-methylene bis (6- (α, α-dimethylbenzyl) -4-nonylphenol), 2,2'-methylene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis ( 6-tert-butyl-4-isobutylphenol), 4,4'-methylene bis (2,6-di-tert-butylphenol), 4,4'-methylene bis (6-tert-butyl-2-methylphenol) 1,1-bis (5-tert-butyl -4-hydroxy-2-methylphenol) butane, 2,6-di (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl- 4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-dodecylmercaptobutane, ethylene glycol bis (3,3-bis (3'-tert- butyl-4'-hydroxyphenyl) butyrate) di (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, di (2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) - 6-tert-butyl-4-methylphenyl) terephthalate and other phenolic compounds, such as bisphenol monoacrylate esters, such as ethylidene bis-2,4-di-tert-butyl monoacrylate ester phenol.

5. Benzyl compounds, for example, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis (3,5-di-tert-butyl -4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl-3,5-di tert-butyl-4-hydroxybenzylphosphonate, calcium salt of monooctyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) iso cyanurate.

6. Acylaminophenols, for example, 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octyl mercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenol) propionic acid with monohydric or polyhydric alcohols, for example, methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris -hydroxyethyl isocyanurate, thioethylene glycol, dihydroxyethyl oxalic acid diamide.

8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, for example, methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tri -hydroxyethyl isocyanurate, thioethylene glycol, dihydroxyethyl oxalic acid diamide.

9. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, for example, methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol , tris- (hydroxyethyl) isocyanurate, thioethylene glycol, diamide N, N-bis (hydroxyethyl) oxalic acid.

10. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenol) propionic acid, for example N, N'-di (3,5-di-tert-butal-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine; N, N'-di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

Aromatic amines that can be used as co-stabilizers in the practice of the present invention can be represented by the general formula

R _one -NH-R ₂ ,

where R ₁ and R ₂ may be, but not necessarily, the same. Thus, in a preferred embodiment, R ₁ and R ₂ can be independently selected from the group consisting of (i) aromatic carbon atom, (ii) carbon atoms of aliphatic R ₁ and aromatic R ₂ and (iii) aromatic carbon atom connected to the second nitrogen atom to form phenylenediamine.

When R ₁ is aliphatic, it may be a linear or branched chain and may contain from one to twelve carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their isomers. Preferably, when R ₁ is aliphatic, it is a linear or branched chain of an aliphatic group containing from one to eight carbon atoms, more preferably, it contains from one to four carbon atoms.

Amine antioxidants can be hydrocarbon-substituted diarylamines, such as aryl, alkyl, alkaryl and aralkyl-substituted diphenylamine antioxidants. A non-limiting list of commercially available hydrocarbon-substituted diphenylamines includes substituted octyl-containing, nonyl-containing and heptyl-containing diphenylamines and para-substituted styrene-containing or α-methylstyrene-containing diphenylamines. Sulfur-containing hydrocarbon-substituted diphenylamines such as p- (p-toluenesulfonylamide) diphenylamine, i.e.

also considered as part of this class.

Hydrocarbon-substituted diarylamines that can be used in the practice of the present invention can be represented by the general formula

Ar-NH-Ar ',

where Ar and Ar 'are independently selected aryl radicals, at least one of which is preferably substituted by at least one alkyl radical. Aryl radicals may be, for example, phenyl, biphenyl, triphenyl, naphthyl, antril, phenanthryl, and the like. Alkyl substituents can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, their isomers and the like.

In one embodiment, a particularly preferred lubricant co-stabilizer comprises at least one antioxidant comprising one or more secondary diarylamines having the general formula

(R _four ) _a -Ar _one -NH-Ar ₂ - (R ₅ ) _b ,

where Ar ₁ and Ar ₂ are independent and include aromatic hydrocarbons, R ₄ and R ₅ are independent and include a hydrogen atom and hydrocarbyl groups, and a and b are independent and are 0 to 3, provided that (a + b) not more than 4. As described in US Patent Application Serial No. 11/825449, filed July 6, 2007, incorporated herein by reference in its entirety, a combination of the styrene-containing phenolic compounds of the present invention and the above secondary diarylamines, especially when used in lubricants gives blue cal effect of antioxidants. In this aspect, the oxidative stability of a lubricating oil comprising one or more basic components of a synthetic lubricant of group I, group II, group III, group IV of various types of viscosity can be enhanced by adding to it (i) the composition of styrene-containing phenolic compounds of the present invention (for example, in from about 0.01 to about 10% by weight based on the total weight of the lubricant, including antioxidants) and (ii) one or more diarylamines of the above structure (e.g., in an amount of approximately about 0.01 to about 10% by weight, based on the total weight of the lubricating composition, including antioxidants). The compositional ratio of styrene-containing phenolic compounds to secondary diarylamines can be almost anything. In examples of embodiments, the ratio will be in the range of from 1:99 to 00: 1 parts by weight, more preferably from 90:10 to 10:90 parts by weight.

Preferred hydrocarbon-substituted diarylamines are those disclosed in US Pat. Nos. 3,452,056 and 3,505,225, which are incorporated herein by reference in their entireties. Preferred hydrocarbon-substituted diarylamines can be represented by the following general formula

Where

R _{11 is} selected from the group consisting of radicals such as phenyl and p-tolyl;

R ₁₂ and R _{13 are} independently selected from the group consisting of radicals such as methyl, phenyl and p-tolyl;

R _{14 is} selected from the group consisting of radicals such as methyl, phenyl, p-tolyl and neopentyl;

R _{15 is} selected from the group consisting of radicals such as methyl, phenyl, p-tolyl and 2-phenyl isobutyl; and

R ₁₆ represents a methyl radical.

Where

R ₁₁ -R ₁₅ radicals are independently selected from the number of radicals defined in formula I, and R _{17 is} selected from the group consisting of radicals such as methyl, phenyl and p-tolyl;

X is a radical selected from the group consisting of methyl, ethyl, C ₃ -C ₁₀ sec-alkyl, α, α-dimethylbenzyl, α-methylbenzyl, chlorine, bromine, carboxyl and metal salts of carboxylic acids, where the metal is selected from the group consisting of zinc, cadmium, nickel, lead, tin, magnesium and copper; and

Y represents a radical selected from the group consisting of a hydrogen atom, methyl, ethyl, C ₃ -C ₁₀ sec-alkyl, a chlorine atom and a bromine atom.

Where

R _{11 is} selected from the group consisting of radicals such as phenyl and p-tolyl;

R ₁₂ and R _{13 are} independently selected from the group consisting of radicals such as methyl, phenyl and p-tolyl;

R ₁₄ represents a radical selected from the group consisting of a hydrogen atom, primary, secondary and tertiary C ₃ -C ₁₀ alkyl and C ₃ -C ₁₀ alkoxyl, which may be linear or branched; and

X and Y are radicals selected from the group consisting of a hydrogen atom, methyl, ethyl, C ₃ -C ₁₀ sec-alkyl, a chlorine atom and a bromine atom.

Where

R _{18 is} selected from the group consisting of phenyl and p-tolyl radicals;

R ₁₉ represents a radical selected from the group consisting of methyl, phenyl, p-tolyl and 2-phenylisobutyl radicals; and

R ₂₀ represents a radical selected from the group consisting of methyl, phenyl and p-tolyl radicals.

Where

R _{21 is} selected from the group consisting of a hydrogen atom, radicals α, α-dimethylbenzyl, α-methylbenzhydryl, triphenylmethyl and α, α-p-trimethylbenzyl;

R _{22 is} selected from the group consisting of phenyl and p-tolyl radicals;

R _{23 is} selected from the group consisting of methyl, phenyl and p-tolyl radicals; and

R _{24 is} selected from the group consisting of methyl, phenyl, p-tolyl and 2-phenylisobutyl radicals.

Additional co-stabilizers used in combination with the compositions of styrene-containing phenolic compounds of the present invention to stabilize polymers and lubricants are as follows:

Type I

R _eleven R ₁₂ R ₁₃ R _l14 R _fifteen R ₁₆ phenyl methyl methyl phenyl methyl methyl phenyl phenyl methyl phenyl phenyl methyl phenyl phenyl phenyl neopentyl methyl methyl p-tolyl methyl methyl p-tolyl methyl methyl

Type II

R _eleven R ₁₂ R ₁₃ R _fourteen R _fifteen R ₁₇ X Y Phenyl methyl methyl phenyl methyl methyl α, α-dimethylbenzyl hydrogen Phenyl methyl methyl phenyl methyl methyl bromine bromine Phenyl methyl methyl phenyl methyl methyl carboxyl hydrogen Phenyl methyl methyl phenyl methyl methyl nickel carboxylate hydrogen Phenyl methyl methyl phenyl methyl methyl 2-butyl hydrogen Phenyl methyl methyl phenyl methyl methyl 2-octyl hydrogen Phenyl phenyl phenyl phenyl phenyl phenyl 2-hexyl hydrogen

Type III

R _eleven R ₁₂ R ₁₃ R _fourteen X Y phenyl methyl methyl isopropoxy hydrogen hydrogen phenyl methyl methyl hydrogen 2-octyl hydrogen phenyl phenyl phenyl hydrogen 2-hexyl hydrogen

The second class of amine antioxidants includes the products of the interaction of diarylamine and aliphatic ketone. The reaction products of diarylamine and aliphatic ketone, which are used in the present invention, are disclosed in US patent 19069356; US patent 1975167; US Pat. No. 2002,642 and US Pat. No. 2,562,802. Briefly, these products are prepared by reacting diarylamine, preferably diphenylamine, which, if desired, may have one or more substituents in any of the aryl groups, with an aliphatic ketone, preferably acetone, in the presence of a suitable catalyst. In addition to diphenylamine, other suitable diarylamine reagents include dinaphthylamines; p-nitrodiphenylamine; 2,4-dinitrodiphenylamine; p-aminodiphenylamine; p-hydroxydiphenylamine and the like. In addition to acetone, other ketone reagents suitable for use include methyl ethyl ketone, diethyl ketone, monochloracetone, dichloroacetone and the like.

A preferred diarylamine-aliphatic ketone reaction product is obtained by the condensation reaction of diphenylamine and acetone (NAUGARD A, Chemtura Corporation), for example, in accordance with the conditions described in US Pat. No. 2,562,802. The commercial product is supplied as a light tan brown powder or as greenish-brown flakes and has a melting point in the range from 85 ° C to 95 ° C.

A third class of suitable amines includes N, N'-hydrocarbon-substituted p-phenylenediamines. The hydrocarbon substituent may be alkyl or aryl groups, which may be substituted or unsubstituted. As used herein, the term “alkyl” is intended to include cycloalkyl, unless otherwise indicated. Representative examples are

N-phenyl-N'-cyclohexyl-p-phenylenediamine;

N-phenyl-N'-sec-butyl-p-phenylenediamine;

N-phenyl-N'-isopropyl-p-phenylenediamine;

N-phenyl-N ' - (1,3-dimethylbutyl) p-phenylenediamine;

N, N'-bis (1,4-dimethylphenyl) p-phenylenediamine;

N, N'-diphenyl-p-phenylenediamine;

N, N'-di-beta-naphthyl-p-phenylenediamine;

mixed diaryl-p-N, N'-bis (1-ethyl-3-methylphenyl) p-phenylenediamines and

N, N'-bis (1-methylheptyl) -p-phenylenediamine.

A fourth class of amine antioxidants includes quinoline-based materials, especially the polymerized 1,2-dihydro-2,2,4-trimethylquinoline (Naugard Super Q, Chemtura Corporation). Representative examples also include 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline; 6-epoxy-2,2,4-trimethyl-1,2-dihydroquinoline and the like.

Secondary amines that are particularly preferred for use in the practice of the present invention are 4,4'-bis (α, α-dimethylbenzyl) diphenylamine (Naugard 445, Chemtura Corporation), octyl-containing diphenylamine (Naugard Octamine, Chemtura Corporation), polymerized 1,2 -dihydro-2,2,4-trimethylquinoline (Naugard Super Q, Chemtura Corporation); and p- (p-toluenesulfonylamido) diphenylamine (Naugard SA, Chemtura Corporation).

The phosphites and phosphonites used as co-stabilizers in the practice of the present invention include, for example, triphenylphosphite, diphenylalkylphosphites, phenyl dialkylphosphites, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, diphosphoryl distearylpentaerythritol-triethyltritol, phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite.

Lactones that can be used as co-stabilizers in the practice of the present invention include lactones of the structure

Where

R ₁ and R _{2 are} independently selected from the group consisting of a hydrogen atom; chlorine atom; hydroxy; C ₁ -C ₂₅ alkyl; C ₇ -C ₉ phenylalkyl; unsubstituted or C ₁ -C ₄ alkyl substituted phenyl; unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkyl; C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkylthio; C ₁ -C ₄ alkylamino; di (C ₁ -C ₄ alkyl) amino; C ₁ -C ₂₅ alkanoyloxy; C ₁ -C ₂₅ alkanoylamino; C ₃ -C ₂₅ alkenolyoxy; C ₃ -C ₂₅ alkanoloxy, which is interrupted by oxygen, sulfur or> NR ₈ ; C ₆ -C ₉ cycloalkylcarbonyloxy; benzoyloxy or C ₁ -C ₁₂ alkyl-substituted benzoyloxy;

R ₈ represents a hydrogen atom or C ₁ -C ₈ alkyl; and

R ₃ and R _{4 are} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₈ alkyl, C ₁ -C ₄ alkoxy, halogen atom, group

in which n is 1 or 2, or groups

in which the radicals A are independently selected from the group consisting of C ₁ -C ₈ alkyl and C ₁ -C ₈ alkoxy.

One suitable example of these lactones is 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, which has the structural formula

This compound is commercially available from Ciba Specialtics under the brand name HP 136.

Simple thioethers, which can be used as co-stabilizers in the practice of the present invention, can have the structural formula

where p is 1 or 2, q is 0 or 1, and p + q is 2, R ₁₈ is a linear or branched alkyl fragment containing from 1 to 20 carbon atoms, and R ₁₉ is a linear or branched alkylene fragment containing from 1 to 8 carbon atoms. Thus, R ₁₈ may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and their isomers; and R ₁₉ may be, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and their isomers. Preferably, R ₁₈ is a linear or branched alkyl fragment containing from 8 to 18 carbon atoms, and R ₁₉ is a linear or branched alkylene fragment containing from 1 to 4 carbon atoms. More preferably, R ₁₉ is ethylene, i.e. -CH ₂ -CH ₂ -.

Other simple thioethers that can be used in the practice of the present invention may have the structural formula

where a is 0-3, b is 1-4, and a + b is 4, R ₁₈ is as defined above, and R ₁₉ and R _{20 are} independently selected from linear or branched alkylene fragments containing from 1 to 8 carbon atoms . Preferably, R ₁₉ and R _{20 are} independently selected from linear or branched alkylene fragments containing from 1 to 4 carbon atoms. More preferably, R ₂₀ is methylene, i.e. -CH ₂ -, and R ₁₉ is ethylene, i.e. -CH ₂ -CH ₂ -.

Examples of preferred thioethers that are used in the practice of the present invention are products such as distearyl thiodipropionate (Naugard DSTDP, Chemtura Corporation), dilauryl thiodipropionate (Naugard DLTDP, Chemtura Corporation), tetrakis (β-lauryl thiopropionate) Pentaerythritol 4 octylthiopropionate pentaerythritol (Naugard 2140, Chemtura Corporation).

Possible co-stabilizers of the present invention can also be trialkylamine oxides, such as, for example, GENOX ™ EP (commercially available from Chemtura Corporation) and described in US patent 6103798; U.S. Patent 5,922,794; US patent 5880191 and US patent 5844029, which are fully incorporated into this description by reference.

Another co-stabilizer may be hydroxylamine, such as, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-N-ditetradecylhydroxylamine, N, N, d N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dioctylhydroxylamine, N, N-di-tert-butylhydroxylamine, N-cyclohexyl-cyclohexyl N, N-didetsilgidroksilamin, N, N-di (cocoalkyl) hydroxylamine, N, N-di (C ₂₀ - ₂₂ alkyl) hydroxylamine, and N, N-dialkylhydroxylamine derived from hydrogenated tallow amine (i.e., N, N-di (talloalkil) hydroxylamine), as well as mixtures containing any of the above listed compounds.

The co-stabilizers described herein and intended for use in combination with the styrene-containing phenolic compounds of the present invention are preferably contained in an effective amount to enhance oxidative stability. When using one of the above co-stabilizers, its amount is usually less than about 5% of the mass. calculated on the total weight of the polymer or lubricant and is preferably at least about 50 ppm by weight of the polymer or lubricant. The combination of stabilizers of the present invention stabilizes polymers and lubricants, especially during high temperature processing or high temperature applications with a relatively small change in the melt index and / or color, even if the polymer itself can undergo a number of extrusion processing when applied to polymers. These stabilizers can be easily incorporated into polymers by conventional methods, at any convenient stage, prior to the production of a shaped article from it. The stabilized compositions of the present invention may optionally contain from about 0.001 to about 5%, preferably from about 0.0025 to about 2%, and especially from about 0.005% to about 1%, by weight of various conventional additives, such as those described above, or mixtures thereof .

EXAMPLES

The present invention will be easier to understand from the point of view of the following non-limiting claims.

Fogging data was obtained after the test, designated “Parameters of fogging the windshield with residual materials in automobiles”, on suitable test specimens made of polyurethane foam. The test method is also known as DIN 75201 Method B. Diisodecylphthalate (DIDP) was used as a reference standard. Typically, in accordance with the test conditions, the sample is exposed at 100 ° C. for 16 hours.

Surprisingly, it has been found that compositions of styrene-containing phenolic compounds (e.g., styrene-containing p-cresol compositions) of the present invention include two key features when polyurethane foams are used in the compositions: (1) they act as low fogging additives and (2) give better stability. As used herein, the term "low fogging" is defined as the deposition of fog after heating for 16 hours at 100 ° C in an amount of from about 0.01 to about 0.4 mg, preferably from about 0.02 to about 0.1 mg

The reasons for the above surprise are as follows: the compositional volatility of styrene-containing p-cresol correlates with its molar mass (MM), and a rule of thumb in this area is that the lower the molar mass of the molecule, the higher its volatility.

Thus, pure 2,6-distyryl-p-cresol (MM = 316) is less volatile than pure 2,6-di-tert-butyl-p-cresol (MM = 220). At the same time, based on their respective molar masses, 2,6-distiryl-p-cresol is more volatile than octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (MM = 531) .

However, in products such as polyurethane foams, the rule of thumb does not work. Thus, a composition containing 2,6-distyryl-p-cresol has significantly less fogging (i.e. volatility) than the corresponding composition containing an additive with a higher molar mass, octadecyl-3,5-di-tert-butyl -4-hydroxyhydrocinnamate.

Samples for testing polyurethane foam type were prepared according to the following recipe:

table 2 Material Weight percent Polyol (Bayer LG56, 56 OH Index) 100.0 H ₂ O 4.4 Dabco 8264 (amine catalyst) 0.5 L-620 (Silicone Surfactant) 1,0 Kosmos 29 (tin catalyst) 0.28 TDI (110 index) 56.77 Antioxidant 0.5

Differential scanning calorimetry (DSC) analysis was performed on a Mettler Toledo instrument. Induction oxidation temperature (OIT) was recorded as the initial heating temperature of the test sample in oxygen from 30 to 300 ° C at a rate of 8 ° C / min.

Example 1. Synthesis of 2,6-distyryl-p-cresol

151.3 grams (1.4 moles) of p-cresol were charged into a one-liter round-bottom flask equipped with a stirrer, a thermometer and a dropping funnel. The mixture was heated to 70 ° C. and then 5 μl of trifluoromethanesulfonic acid was added using a 100 μl syringe. Under a nitrogen atmosphere, 284.5 grams (2.73 mol) of styrene was placed in a funnel and then added dropwise with stirring for three hours. After the addition of styrene, the temperature in the flask did not exceed 80 ° C. Stirring was continued at a temperature in the flask of 70 ° C for 1.5 hours after the introduction of styrene. The resulting styrene-containing p-cresol composition was analyzed as follows:

Table 3 The results of the study by gas chromatography (GC) (area%) Styrene 0.13 p-cresol 0,03 Monostyrene-containing p-cresol 7.23 2,6-distyrene-containing p-cresol 86.31 Tristirol-containing p-cresol 4.75 total area 98.45

ARNA value = 50

Acid number = 0.01 mg KOH / g

Brookfield viscosity = 29900 centipoise (25 ° C)

Mass yield = 94%

Example 2

This example illustrates the volatility of pure 2,6-distyryl-p-cresol measured by the TGA method. TGA test results are presented in Table 4. Unless otherwise specified, thermogravimetric analysis (TGA) of pure materials was carried out using a Mettler Universal V2.5H TA instrument. The mass loss was recorded after isothermal exposure of the sample at 160 ° C in a nitrogen atmosphere.

Table 4 TGA Volatility of Pure 2.6-Distyryl-p-Cresol Antioxidant (AO) Molar mass of AO Weight loss (%) after 1 hour at 160 ° C Weight loss (%) after 4 hours at 160 ° C 2,6-di-tert-butyl-p-cresol 230 one hundred n.d. 2,6-di-tert-butyl-4-sec-butylphenol 262 99 n.d. 2,6-distyryl-p-cresol 316 40 94 C ₁₃ -C ₁₅ alkyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate 471 * 8 twenty octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate 531 0.5 2.5 * at the rate
nd not determined

These results show that the volatility of the pure additive measured by the TGA method correlates with the molar mass of the additive.

Example 3

This example illustrates the release of volatile compounds from polyurethane foam to which 2,6-distyryl-p-cresol, measured by fog deposition, is added. The test results for fogging are presented in table 5.

Table 5 Deposition of fog from polyurethane foam samples Antioxidant (AO) Molar mass of AO Deposition of fog (mg) at 160 hours / 100 ° C No 0.04 2,6-di-tert-butyl-4-sec-butylphenol 262 0.71 2,6-distyryl-p-cresol 316 0.04 C _13-15 alkyl-3,5-ditret-butyl-4-hydroxyhydrocinnamate 471 * 0.31 octadecyl-3,5-ditret-butyl-4-hydroxyhydrocinnamate 531 0.35 * at the rate

These results show a surprisingly low emission for samples of the polyurethane foam type into which 2,6-distiryl-p-cresol is introduced. Thus, the total amount of fog deposition for the composition with 2,6-distyryl-p-cresol was comparable to the control composition without additives. In other words, the deposition of fog for this composition was unexpectedly lower than for two control materials, each of which had a higher molar mass. Moreover, it unexpectedly turned out that the deposition of fog does not correlate with the order determined by the molar mass of the additive.

Example 4

This example illustrates the stabilizing effect of 2,6-distyryl-p-cresol on a polyol measured by induction oxidation temperature. The test results are presented in table 6.

Table 6 OIT measurement results for 2,6-distiryl-p-cresol stabilized polyol Polyol LG (Bayer) + AO (1000 ppm) OIT (° C) di-tert-butyl-4-sec-butylphenol 173 2,6-di-tert-butyl-4-sec-butylphenol 179 2,6-distyryl-p-cresol 177 C _13-15 alkyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate 176 octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate 175

These test results show good stabilizing properties of 2,6-distyryl-p-cresol in polyol-based formulations, measured by OIT. In this test, several control phenolic antioxidants were used.

Example 5. Evaluation of the operational properties of 2,6-distyrene-containing p-cresol in LLDPE. Preservation of the melt flow index during multiple extrusion

This example illustrates the stabilizing efficacy of 2,6-distyrene-containing p-cresol in the presence of a phosphite stabilizer compared to a control comprising a mixture of octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate and a phosphite stabilizer.

The base polymer was a powdered C4 copolymer linear low density polyethylene with a melt index (MI) of 1 and a density of 0.918 g / cm ³ . The base formulation also contained 500 ppm zinc stearate as an acid acceptor. All formulations were prepared by adding trisnonylphenyl phosphite in combination with 2,6-distiryl-p-cresol or octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate to the base composition (see table 7 for details). Thus stabilized polymer compositions were then extruded from a Brabender single-screw extruder with a diameter of 19 mm at a speed of 60 rpm and a temperature of 230 ° C. The first extrusion pass was carried out in an inert atmosphere. The extrudate was cooled by passing it through an ice bath, and then granulated. The resulting granules were re-extruded in air using the same machine, temperature and granulation conditions as described above for five passes through the extruder. The results of this test are shown in table 7.

Table 7 MFI Results Stabilizer (ppm) MFI after 1 extrusion pass (g / 10 min) at 190 / 2.16 MFI after 6 extrusion passes (g / 10 min at 190 / 2.16) Control octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (200) + PI (1200) 0.98 0.66 2,6-distyryl-p-cresol (200) + PI (1200) 1.01 0.94 PI stands for Tris (nonylphenyl) phosphite.

A relatively small decrease in the melt flow index indicates excellent stabilizing efficiency. Thus, the results of this test show that 2,6-distiryl-p-cresol in combination with PI phosphite gives superior melt stabilization compared to the control composition.

Example 6

This example illustrates the stabilizing efficacy of 2,6-distyryl-p-cresol in the presence of a phosphite stabilizer, which was evaluated by measuring color retention. The results were compared with a control composition containing a mixture of octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate with a similar phosphite stabilizer.

The base polymer was a powdered C4 copolymer linear low density polyethylene with a melt index (MI) of 1 and a density of 0.918 g / cm ³ . The base formulation also contained 500 ppm zinc stearate as an acid acceptor. All formulations were prepared by adding tris-nonylphenylphosphite in combination with 2,6-distyryl-p-cresol or octadecyl-3,5-ditret-butyl-4-hydroxyhydrocinnamate to the base composition (see table 8 for further details). The polymer composition thus stabilized was then extruded from a Brabender single screw extruder with a diameter of 19 mm at 60 rpm and a set temperature of 230 ° C. The first extrusion pass was carried out in an inert atmosphere. The extrudate was cooled by passing it through an ice bath, and then granulated. The resulting granules were re-extruded in air using the same machine, temperature and granulation conditions as described above for five additional passes through the extruder. The results of this test are shown in table 8.

Table 8 Yellowness Results Stabilizer (ppm) The yellowness index after 1 extrusion pass The yellowness index after 6 extrusion pass Control octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (200) + PI (1200) -2.47 1.88 2,6-distyryl-p-cresol (200) + PI (1200) -2.39 1.18 PI stands for Tris (nonylphenyl) phosphite.

A relatively small increase in the yellowness index indicates excellent stabilizing effectiveness. Thus, the results of this test show that 2,6-distiryl-p-cresol in combination with PI phosphite gives excellent color retention compared to the control composition.

Example 7. Evaluation of the performance properties of styrene-butadiene rubber in the presence of 2,6-distiryl-p-cresol by the change in Mooney viscosity during aging in an air thermostat at 100 ° C

This example illustrates the stabilizing efficacy of 2,6-distyryl-p-cresol as such, and in combination with a phosphite stabilizer, as compared to an unstabilized material (control).

A polymer of type e-SBR 1502 was used. The coagulating agents were as follows: 7.5% mol. H ₂ SO ₄ and 5% mol. Al ₂ (SO ₄ ) ₃ in water. Samples of e-SBR were prepared containing the stabilizer (s) shown in Table 9, and then placed in a thermostat at 100 ° C. for aging experiments in an air thermostat.

Mooney viscosity values were measured on a viscTech Moony viscometer on samples weighing 30 grams (temperature: 100 ° C; 1 min preheating in the absence of rotation; measurement time 4 minutes after preheating). Mooney viscosity was determined for each composition before air aging and then at equal intervals from the moment of exposure of the samples for testing from SBR in a thermostat at 100 ° C. The test results are shown in table 9.

Table 9 Mooney Viscosity Stabilizer (m.h.) Mooney viscosity (before aging) Mooney viscosity after aging for 14 days Mooney viscosity after aging for 21 days Mooney viscosity after aging for 42 days Control (no) 63 120 124 n.d. 2,6-distyryl-p-cresol (1) 38 72 75 n.d. 2,6-distyryl-p-cresol (0.2) + PI (0.8) 49 57 70 82 PI stands for Tris (nonylphenyl) phosphite.

A relatively small increase in Mooney viscosity indicates excellent stabilizing effectiveness. Thus, the results of this test show that 2,6-distiryl-p-cresol, as such, and in combination with PI phosphite, provides excellent stabilization compared to the control composition without additives.

Example 8: Synthesis of 2,6-distiryl-p-cresol (two-reactor system)

This example illustrates a reaction system comprising two reactors and providing a two-stage temperature profile for the formation of styrene-containing p-cresol. 50 kg (110.2 pounds, 462.2 moles) of p-cresol was pumped from a preheated tank into a glass lined steel reactor with a 50 gallon jacket, equipped with a stirrer, a thermowell and a discharge loop for sampling and injecting acid. p-Cresol was heated to approximately 60 ° C and then 1.6-8.3 g (5.53e-05 to 1.07e-02 moles) of trifluoromethanesulfonic acid were added through a syringe in the injection portion of the injection loop. 93.9 kg (207 pounds, 901.6 moles) of styrene was charged through the flow meter at a constant rate for a 3-4-hour reaction time, while the temperature in the reactor was maintained at 70 ° C. The molar ratio of styrene to p-cresol was maintained at 1.95. After the styrene feed was completed, the contents of the reactor were pumped into a second glass-lined steel reactor with a 50 gallon jacket and heated to 90 ° C. Approximately 1.5 pounds (0.7 kg) of acid bentonite clay (Filtrol 20X) was introduced through a nozzle into a second reactor and mixed for 15 minutes. Then the product was pumped into a filter bag and in a container for the product. The results for a specific product sample of this production, based on the total GC area, are presented below in table 10.

Table 10 Component % of total GC area Styrene 0 p-cresol 0 Mono 4.8 Di 91.9 Three 3.3

Example 9: Synthesis of 2,6-distiryl-p-cresol (one reactor)

This example illustrates a reaction system comprising a single reactor for producing styrene-containing p-cresol. Example 9 was carried out analogously to example 8, except that one reactor was used to carry out the reaction at 70 ° C and 90 ° C to complete the reaction and introduce clay. The original styrene was supplied over a period of time ranging from 2.5 to 4 hours. The amount of triflic acid used was in the range of 1.7 to 2.6 g. The molar ratio of styrene to p-cresol was maintained at 1.95. The composition of the obtained composition styrene-containing p-cresol in the calculation of the total GC area was as follows:

Table 11 Component % of total GC area Styrene 0 p-cresol 0,03 Mono 6.9 Di 87.5 Three 5,4

Using the conditions of examples 8 and 9, it is possible to calculate the amount of the di-component according to the formula for grams of injected triflic acid:% Di = (5.159) (ln (X)) + 115.01, where X = g triflic acid / mol of cresol.

Example 10: Study of the stabilization of PCMO mixtures

This example illustrates the stabilizing ability of the compositions of styrene-containing phenolic compounds (p-cresol) of the present invention in the motor oil of a passenger car. The stabilizing ability of the two styrene-containing p-cresols compositions (COM 1 and COM 2) of the present invention was determined. Compositions COM 1 and COM 2 calculated on the basis of the total GC area are presented below.

Table 13 Component COM 1 COM 2 Mono 5,6 22.8 Di 89.2 60 Three 4,5 11.3

COM 1 and COM 2 were mixed, respectively, with passenger car engine oil (RSMO), in particular, the prototype 5W20 ILSAC GF-4 (0.6% by weight P) containing the base component of group II. Mixtures 1A and 2A contained 0.5% of the mass. COM 1 and COM 2 compositions of styrene-containing p-cresol, respectively, based on the total weight of the respective mixtures. Two additional mixtures were also prepared (mixtures 1B and 2B, respectively) containing 1.5% of the mass. COM 1 and COM 2 compositions of styrene-containing p-cresol, respectively, based on the total weight of the respective mixtures. Mixtures 1A and 2A, as well as PCMO without an antioxidant (comparative), were analyzed by differential scanning pressure difference calorimetry (PDSC) at 160 ° C, and the results were compared. Mixtures 1B and 2B were analyzed by PDSC at 185 ° C. The approximate PDSC at 185 ° C for the PCMO comparative sample was determined by the OIT PDSC at 160 ° C by reducing the OIT PDSC at 160 ° C by 50% with an increase of every 10 ° C. Table 14 below presents the results of this analysis, which clearly show that the oxidative stability of these mixtures significantly exceeds this value for comparative RSMO.

A model thermal oil oxidation test (TEOST) (at a moderately high MNT temperature) was performed according to ASTM D7099, which is hereby incorporated by reference in its entirety to simulate the effect of engine operating conditions on oxidative stability and the tendency to form soot mixtures 1B and 2B. and comparative oil RSMO. The results, also presented in Table 14, clearly show that reduced carbon was formed from lubricant mixtures containing the styrene-containing p-cresol compositions of the present invention, compared to the TEOST test for a comparative PCMO sample.

Table 14 Sample The composition of styrene-containing p-cresol % of the mass. styrene-containing p-cresol PDSC OIT 160 ° C (min) PDSC OIT 185 ° C (min) TEOST (mg) PCMO (No AO) N / a 0 5.65 one* 132 Mixture 1A COM1 0.5 52.90 - - Mixture 2A COM2 0.5 55.96 - - Mixture 1B COM1 1,5 - 10.66 51.0 Mixture 2B COM2 1,5 - 10.62 65.3 * at the rate

Example 11: Study of the stabilization of mixtures of industrial turbine oils

This example illustrates the stabilizing properties of the styrene-containing p-cresol compositions of the present invention in industrial turbine oil. The stabilizing ability of the styrene-containing p-cresol compositions COM 1 and COM 2 of the present invention was determined in the base component of industrial turbine oil (ITO) (not containing AO, base component of group II). The resulting mixtures, designated mixture 1C and mixture 2C, contained 1.0 weight percent of COM 1 and COM 2, respectively, based on the total weight of the respective mixtures. Mixtures of 1C and 2C, as well as ITO without an antioxidant (comparative), were analyzed by rotational bomb oxidation (RPVOT) according to ASTM D2272, which is incorporated herein by reference in its entirety. The results presented in table 15 show that the oxidative stability of each of the mixtures of 1C and 2C were more than an order of magnitude higher than that of comparative ITO mixtures without an antioxidant.

Table 15 Sample The composition of styrene-containing p-cresol % of the mass. styrene-containing p-cresol RPVOT OIT (min) ITO (No AO) N / a 0 24 Mixture 1C COM1 1,0 338 Mixture 2C COM2 1,0 305

Example 12. The effect of color stabilization with styrene-containing phenols in the polyol

In this example, the color stabilization effect was compared with styrene-containing phenol compositions, especially the styrene-containing p-cresol COM 1 composition of Example 10 and comparative antioxidants such as Naugard PS-48 (or Irganox 1135), Anox 1315, Irganox 1076 (or Anox PP18) or Isonox 132 upon receipt of polyurethane foams. Comparative antioxidants did not form foams having good color stability over a long period of time at room temperature. It is also known that BHT (butyl-containing hydroxytoluene, ditret-butylparacresol), a common antioxidant, has low color stability.

The above antioxidants were mixed with polyester polyol (Fomrez 2C53), which is usually reacted with isocyanates to form polyurethanes, in amounts ranging from 8% by weight. up to 22% by weight, as shown in Table 16 below. Foams obtained from polyether polyol containing Isonox 132 (2,6-ditret-butyl-4-sec-butylphenol) showed discoloration over an extended period of time at room temperature. Polyether polyols containing various antioxidants in varying amounts were prepared by heating Fomrez 2C53, which did not contain any antioxidant, in a thermostat at 70 ° C for three hours, followed by mixing with various antioxidants, as shown below.

Table 16 Sample The mass of polyol (g) Antioxidant Mass AO (g (% wt.)) one 3960 No 0 (0%) 2 3733 Naugard ps-48 11.10 (0.298%) 3 3744 Naugard ps-48 22.03 (0.596%) four 3650 Anox 1315 13.51 (0.370%) 5 3257 Irganox 1076 13.22 (0.405%) 6 3655 COM1 8.84 (0.241%) 7 3449 COM1 16.63 (0.482%)

Samples 1-7 were sent to a testing company that reacted the polyol with TDI (toluene diisocyanate) to produce foams for color stability testing. The test results showed that foams obtained from samples 6 and 7 containing the composition of the styrene-containing phenolic compounds of the present invention passed color stability tests for a long period of time at room temperature. Sample 7 containing 0.482% of the mass. styrene-containing phenolic compounds showed the best properties, and sample 4 containing 0.241% of the mass. styrene-containing phenolic compounds showed the second best test result. The foams obtained from samples 1-5 did not pass color stability tests for a long period of time at room temperature. Similar stable foams can be expected by combining the styrene-containing phenolic compounds of the present invention with polyether polyols to form polyurethane foams.

Example 13: Obtaining low-colored phenolic stabilizers by attaching styrene to o-cresol and mixtures of o-cresol / m-cresol

2-Methyl-4,6-di (1-phenylethyl) phenol was previously obtained by the reaction of o-cresol with styrene catalyzed by an aluminum catalyst. Under the considered conditions, the conversions to the desired compound are low (for example, 75%), and the reaction product is highly colored (11 Gardner), which requires purification of 2-methyl-4,6-di (1-phenylethyl) phenol by distillation before use as an antioxidant in synthetic polymers.

This example shows that the interaction of styrene with o-cresol in the presence of trifluoromethanesulfonic acid (optionally in combination with phosphites) leads to the formation of the reaction product (conversion to 2-methyl-4,6-di (1-phenylethyl) phenol and the corresponding mono- and tri-compounds) at conversions of more than 95%, having an APHA color intensity of less than 150. The resulting composition of styrene-containing phenolic compounds (styrene-containing o-cresol) can be used as an antioxidant in synthetic polymers b of purification or distillation.

100 grams (0.925 moles; H ₂ O <256 ppm) of o-cresol and 20 μl (0.226 mmol) of trifluoromethanesulfonic acid were charged into a one-liter round-bottom flask equipped with a stirrer, thermometer, and dropping funnel. The mixture was heated at 60 ° C in a stream of nitrogen. Once the temperature stabilized, 193 grams (1.85 moles) of styrene was placed in a funnel and then added dropwise with stirring for four hours. During the addition of styrene, the temperature in the flask did not exceed 70 ° C. Stirring was continued at a temperature in the flask of 60 ° C for 1 hour after the introduction of all styrene. 100 g of water was added to the stirred reaction mixture. After 30 minutes, the reaction mixture was allowed to settle, the aqueous layer was separated, and the organic layer was dried at 80 ° C. in a 4 mm vacuum. The resulting composition of the styrene-containing mixture of o-cresol / p-cresol was analyzed as follows.

Table 17 Gas Chromatography (GC) Results (% Area) p-cresol 0.05 The sum of monostyrene-containing o-cresol + p-cresol 6.89 The sum of 2,6-distyrol-containing o-cresol + p-cresol 91.0 Tristirol-containing p-cresol 1.89 total area 99.83

APHA value = 50;

Kinematic viscosity = 1188 centistokes (30 ° C);

Mass yield = 93%.

This technique was also applied in the interaction of styrene with mixed ortho- and para-cresols, to obtain mixed 2-methyl-4,6-di (1-phenylethyl) phenol and 4-methyl-2,6-di (1-phenylethyl) phenol (as well as small amounts of the corresponding mono- and tristyrene-substituted compounds), which can also be used as an antioxidant of synthetic polymers without purification and distillation.

In a one-liter round-bottom flask equipped with a stirrer, thermometer and dropping funnel, 50 grams (0.46 moles; H ₂ O <250 ppm) of p-cresol, (50 grams, 0.46 moles; H ₂ O <250 h) were charged ppm o-cresol and 20 μl (0.226 mmol) of trifluoromethanesulfonic acid. The mixture was heated at 60 ° C in a stream of nitrogen. 193 grams (1.85 moles) of styrene was placed in a funnel and then added dropwise with stirring for four hours. During the addition of styrene, the temperature in the flask did not exceed 70 ° C. After the introduction of all styrene, stirring was continued at a temperature in the flask of 60 ° C for 1 hour. 100 g of water was added to the stirred reaction mixture. After 30 minutes, the reaction mixture was allowed to settle, the aqueous layer was separated, and the organic layer was dried at 80 ° C. in a 4 mm vacuum. The resulting composition of the styrene-containing mixture of o-cresol / p-cresol was analyzed as follows.

Table 18 Gas Chromatography (GC) Results (% Area) Amount o-cresol + p-cresol 0.05 Amount monostyrene-containing o-cresol + monostyrene-containing p-cresol 4.31 Amount 2,4-distyrene-containing o-cresol + 2,6-distyrene-containing p-cresol 91.6 The amount of tristirol-containing o-cresol + tristirol-containing p-cresol 2.76 total area 98.72

APHA value = 75;

Kinematic viscosity = 3135 centistokes (30 ° C);

Mass yield = 92%.

Example 14: Obtaining low-colored phenolic stabilizers by adding styrene to phenol

100 grams (1.06 moles; H ₂ O <250 ppm) of phenol and 20 μl (0.226 mmol) of trifluoromethanesulfonic acid were charged into a one-liter round-bottom flask equipped with a stirrer, thermometer, and dropping funnel. The mixture was heated at 60 ° C in a stream of nitrogen. Once the temperature inside the flask had stabilized, 332 grams (3.16 moles) of styrene was placed in a funnel and then added dropwise with stirring for four hours. During the addition of styrene, the temperature in the flask did not exceed 70 ° C. After the introduction of all styrene, the reaction mixture was stirred at a temperature in the flask of 60 ° C for 1 hour. 100 g of water was added to the stirred reaction mixture. After 30 minutes, the reaction mixture was allowed to settle, the aqueous layer was separated, and the organic layer was dried at 80 ° C. in a 4 mm vacuum. The resulting styrene-phenol composition was analyzed as follows.

Table 19 Gas Chromatography (GC) Results (% Area) Phenol 0.28 The amount of monostyrene-containing phenol 3.91 Amount of distyrene phenol 9.2 The amount of tristyrene phenol 81.6 The amount of tetrastyrene phenol 4.16 total area 99.15

APHA value = 50;

Kinematic viscosity = 7495 centistokes (30 ° C);

Mass yield = 94%.

Any feature considered or claimed regarding any disclosed embodiment of the invention may be combined in any combination and any one or more other features described or claimed and relating to any other disclosed embodiment or embodiments to the extent that the features the features are not necessarily technically incompatible, and all such combinations are included within the scope of the present invention. Therefore, the appended claims contain several non-limiting combinations of features within the scope of the claims of the present invention, but also intended to be covered by the scope of the claims are all possible combinations of the essence of any two or more claims, in any possible combination, provided that the combination is optional technically incompatible.

Claims (13)

1. A stabilized composition comprising a thermoplastic, thermoplastic elastomer, rubber or lubricant and a liquid composition of a styrene-containing phenolic compound in an amount of from about 0.01 to about 10% based on the total weight of the stabilized composition, wherein said phenolic compound composition contains:
(a) at least one 2,6-distirol-containing p-cresol in an amount of from about 80 to about 95% of the total gas chromatographic area;
(b) at least one monostyrene-containing p-cresol in an amount of more than 1% of the total gas chromatographic area; and
(c) at least one tristyrene-containing p-cresol in an amount of more than 1% of the total gas chromatographic area,
wherein the composition contains monostyrene-containing p-cresol and tristyrene-containing p-cresol in combination in an amount of from 5 to 20% over the total gas chromatographic area. 2. The composition according to claim 1, additionally containing a co-stabilizer, which is selected from the group consisting of phenolic compounds, phosphites, diarylamines and epoxidized vegetable oils. 3. The composition according to claim 2, where the co-stabilizer is organophosphite. 4. The composition according to claim 3, where the organophosphite is tris (nonylphenyl) phosphite. 5. The composition according to claim 1, where the co-stabilizer is a dialkyl-containing diphenylamine. 6. A polymer product made of a stabilized composition comprising a thermoplastic, thermoplastic elastomer, rubber or lubricant and a liquid composition of a styrene-containing phenolic compound in an amount of from about 0.01 to about 10% based on the total weight of the polymer product, wherein said phenolic compound composition contains :
(a) at least one 2,6-distirol-containing p-cresol in an amount of from about 80 to about 95% of the total gas chromatographic area;
(b) at least one monostyrene-containing p-cresol in an amount of more than 1% of the total gas chromatographic area; and
(c) at least one tristyrene-containing p-cresol in an amount of more than 1% of the total gas chromatographic area,
wherein the composition contains monostyrene-containing p-cresol and tristyrene-containing p-cresol in combination in an amount of from 5 to 20% over the total gas chromatographic area. 7. The polymer product according to claim 6, where the polymer is selected from the group consisting of polyolefins, PVC, polyurethanes, polyols and elastomers. 8. The polymer product according to claim 6, where the polymer is styrene-butadiene rubber. 9. The polymer product according to claim 6, where the polymer product includes a polyol or polyurethane and the composition exhibits low fogging. 10. A lubricant containing a base component with a lubricating viscosity and from about 0.01 to about 10%, based on the total weight of the lubricant, of the liquid composition of the styrene-containing phenolic compound, wherein said phenolic compound composition contains:
(a) at least one 2,6-distirol-containing p-cresol in an amount of from about 80 to about 95% of the total gas chromatographic area;
(b) at least one monostyrene-containing p-cresol in an amount of more than 1% of the total gas chromatographic area; and
(c) at least one tristyrene-containing p-cresol in an amount of more than 1% of the total gas chromatographic area,
wherein the composition contains monostyrene-containing p-cresol and tristyrene-containing p-cresol in combination in an amount of from 5 to 20% over the total gas chromatographic area. 11. The lubricant of claim 10, where the lubricant composition contains a base component in an amount of more than 90 wt.%, And a styrene-containing phenolic compound in an amount of more than 0.05%, based on the weight of the lubricant. 12. The lubricant according to claim 11, where the lubricant contains the base component of the lubricant in an amount of more than 95%, and a styrene-containing phenolic compound in an amount of from 0.1 to 5%, based on the weight of the lubricant. 13. The lubricant of claim 10, where the lubricant composition further comprises at least one antioxidant comprising one or more secondary diarylamines having the General formula (R ₄ ) _a -Ar ₁ -NH-Ar ₂ (R ₅ ) _b ,
where Ar ₁ and Ar ₂ are independent and include aromatic hydrocarbons, R ₄ and R ₅ are independent and include a hydrogen atom and hydrocarbyl groups, and a and b are independent and equal to 0-3 provided that (a + b) does not exceed 4 .