CA1047523A - Processes for preparing phenolic diesters - Google Patents
Processes for preparing phenolic diestersInfo
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- CA1047523A CA1047523A CA221,861A CA221861A CA1047523A CA 1047523 A CA1047523 A CA 1047523A CA 221861 A CA221861 A CA 221861A CA 1047523 A CA1047523 A CA 1047523A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C301/00—Esters of sulfurous acid
- C07C301/02—Esters of sulfurous acid having sulfite groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/44—Adipic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/48—Azelaic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to compounds of formula Q-O-R-O-Q wherein Q represents a substituted or unsubstituted 2-(2-hydroxybenzyl)phenyl group, and R
is a residue of a di- or tri-basic, organic or inorganic acid. compounds in accordance with the invention can be used as stabilizers for plastics materials, in particular to provide them with thermal stability and stability against ultra violet light. The low volatilities of these compounds compared with the analoguous di-phenols Q-O-H render them of particular value.
This invention relates to compounds of formula Q-O-R-O-Q wherein Q represents a substituted or unsubstituted 2-(2-hydroxybenzyl)phenyl group, and R
is a residue of a di- or tri-basic, organic or inorganic acid. compounds in accordance with the invention can be used as stabilizers for plastics materials, in particular to provide them with thermal stability and stability against ultra violet light. The low volatilities of these compounds compared with the analoguous di-phenols Q-O-H render them of particular value.
Description
This invention relates to phenolic diesters which can be used as stabilizers for plastics materials.
Numerous phenolic derivatives have been proposed hitherto as anti-oxidants and as thermal stabilizers of plastics S materials such as polyolefins. In particular, it has been proposed hitherto to use a diphenol of formula ~ OH
R3 ~ 71 ~ 3 ~I) wherein Rl and R2 are preferably hydrogen atoms, R4 is preferably a lower alkyl group, such as a methyl group, and R3 is preferably a t-butyl group.
For numerous plastics materials, such as polyolefins, these phenolic derivatives are too volatile. They have a tendency to become eliminated from p7~stics materials, through evaporation, and they can then no longer act as stabilizers.
According to the present invention there are provided compounds of formula Q - O - R - O - Q II
in which Q represents a group of formula wherein:
R5 and R6 are hydrogen or alkyl groups R7 and R8 are alkyl groups R is an acid group derived from the group consisting of thionyl chloride, phthallic acid and B~, . ~ ;, ,~
~ )47523 o o - ~ - R' - l -wherein R' is an aliphatic group having from 1 to 7 carbon atoms.
Compounds of formula II have been found to provide a particularly good stabilizing action on plastics materials while exhibiting low volatility.
Compounds of formula II can be prepared by known methods, for example by reacting an acid chloride of a polyfunctional acid with a bisphenol of formula I. The reaction can be performed using an excess of the bisphenol, under conditions whereby hydrogen chloride is eliminated as it is formed, either as a gas or by combination with a base.
The preferred compound of formula II, by virtue of its stabilizing properties with plastics materials is the diester obtained by reacting 2,2'-methylene bis-(4-methyl-6-t-butyl-phenol? with the dichloride of terephthalic acid. The product obtained is of formula ~ Ol CH3 ~-- -- C ~ C_ 0 ~3_CH3 CH 3 ~Rg R9 ~CH 3 : . '.~ ,;:J
~047S23 in which ~ represents a t-butyl group.
The compound can be prepared by heating a slight exces~ of the diphenol with the di-acid chloride of terphthalic acid in the presence of an amine which forms the c~rrespondin~ hydrochloride with hydrogen chloride.
~he reaction can be effected in the presence or absence of a solvent, and also in a medium which is a solvent for the desired product. The reaction can also be effected by the so-called interface technique, in which each reactant is in solution in a solvent which iæ immiscible with the solvent used for the other reactant. In this case, neutralization of the hydrogen chloride is preferably effected with an inorganic base.
Polye~ters of formula II have low volatility (being less volatile than the diphenol used as the starting material) and have substantial anti-oxidant properties. In addition, compounds of formula II in which R represents an aryl group can be converted into benzophenone-type compounds which absorb ultraviolet radiation. This makes them of interest in protecting plastics materials against thermal and photo-chemical degradation.
The following Examples are given by way of illustration only, and they show the preparation of the preferred compound i.e. the teraphthalate of 2,2'-methylene bis-(4-methyl 6-t-butylphenol) hereinafter referred to as HPM 12.
Example 1 Preparation of HPM 12 in a solvent 700 g (2.06 moles) of 2,2'-methylene bis-(4-methyl 6-t-butylphenol), dissolved at ambient temperature in 5000 g of alcohol-free anhydrous chloroform, were introduced into a 11~475Z3 6-liter reactor having an agitator, a condenser, a dropping funnel, a thermometer,and a tube permitting nitrogen bubbling, as required. A slight current of nitrogen was then intro-duced into the solution, and agitation started. At the end of one hour, 202 g (1 mole) of the di-chloride of terephthalic acid were quickly added. The solution was heated to 60C, and 210 g (2.08 moles) of trieth~lamine were introduced over 1 hour. A slight distillation of the chloroform occurred. After all the triethylPm;ne had been added, refluxing was maintained by heating for 5 hours, and thereafter the solution was cooled to 20C. The solution was washed four times with 3000 g of water in order to eliminate triethylamine hydrochloride. The organic phase was concentrated (2000 g of CHC13 were evaporated), cooled to 5C, and 2500 g of ethanol were added drop by drop to precipitate the product. The product was washed with 1000 g of ethanol, and dried to leave a white powder having the following properties:-- melting point - 244-247C
- hydroxyl index (found) - 147 (theory 140) - saponification index (found) - 137 (theory 1~0) - acid index (found) - 1.6 (theory 0) - elemental analysis, found:- C 79.6~/o~ H 7.90%;
calculated:- C 79.96%, H 8.2~o The weight bf product obtained was 712 g, corresponding to a yield of 88%.
Example 2 Preparation of HPM 12 without a solvent.
595 g (5 moles) of thionyl chloride were added at 20C
to 166 g (1 mole) of terephthalic acid in a 4-litre reactor ~ 0475Z3 equipped as in Example 1. Agitation was started, Pnd the temperature raised to 70C. 5 cm3 of pyridine were added very slowly, and the mixture was brought to ~OCl2 reflux for 8 hours. An abundant release of S02 and HCl occurred.
The temperature was then reduced to 70C, and the excess SOCl2 and the remaiDing hydrogen chloride were removed under vacuum until setting ~f the mixture. Agitation was then stopped.
~he addition of small amounts of anhydrous benzene before setting facilitated elimination of the SOCl2.
2000 g of anhydrous octane were then introduced into the reactor, and nitrogen bubbling and agitation were started.
When all the acid chloride - had di~solved, 680 g (2 moles) of 2,2'-methylene bis-(4-methyl-6-t-butylphenol) were quickly added. ~he temperature was raised to 80C, and 210 g (2.08 moles) of triethylamine were added over 90 minutes. A white precipitate formed duri~g the course of this introduction of triethylamine.
When the introduction was over, the temperaturo had increased to 90C, and the reaction was continued for 4 hours.
The mixture was then cooled to 20C and the precipitate filtered. The solid product was dissolved in chloroform and purified as in Example 1. 624 g (yield 7~/0) were obtained of a white product melting at 245-247C.
In the preparation described hereinbefore, the synthesis of the dichloride of terephthalic acid can be carried out using dime~hylformamide (DMF) instead of pyridine as catalyst, as follows:-166 g (1 mole) of terephthalic acid were introducedinto a 2-liter reactor having an anchor stirrer, a vertical ~0 condenser, a dropping funnel, and an immersion thermometer.
~047S23 595 g (5 moles) of cold thionyl chloride were added~ ~he mixture was agitated and heated to effect ~OCl2 reflux.
When the temperature reached 45~C, 7.3 g of DMF (0.05 mole per mole of acid function) were introduced, accelerating the temperature rise. Hydrogen chloride and sulphur oxide which were released, as well as the SOCl2 carried P1ong therewith, were neutralized at the output of the condenser by bubbling into a solution of a base.
After three hours of SOC12 reflux, all the terephthalic acid had dissolved, which indicated the end of the reaction.
EXCe8S SOC12 was distilled at atmospheric pressure, and 63%
of the excess thionyl chloride was recovered.
The chloride of the terephthalic acid obtained had a tit~e of 98.8% and it was produced in a yield of 10~/o.
By modifyi~g the conditions i~ Examples 1 and 2, it is possible to produce:-- a certain amount, generally low, of the monester of terephthalic acid. This occurs as a result of the presence of a small amount of water, the terephthalyl chloride being partly hydrolyzed to convert at least one acid chloride function into the carboxylic acid function. ~he presence of this monoester in the final product is no hindrance;
- a polymeric product. If HO-Q'-OH represents the bisphenol, and HOOC-~-COOH represents terephthalic acid, 5 the polymeric products that can be obtained are of formula:-O O O O
Il ~1 11 11 HO-Q'-O-C-~-C(O-~'-O-C-~-C)nO-i~'-OH
wherein n is an integer less than or equal to 4. Such polymers also exhibit interesting anti-oxidant and anti-ultra-violet properties, but they are generally less soluble in polyolefin~ and have anti-oxidizing activities less than those of the diesters of formula II.
Example 3 S~nthesis of the condensation product of the dichloride of adipic acid with the diphenol I(R1=R2=H; R4=CH ; R -But) _ _ 3 5 a) Preparation of the dichloride:-730 g of adipic acid (5 moles) were reacted for 8 hoursat a temperature of 60C with 1820 g of thionyl chloride (15 moles) to give, after distillation of the excess SOCl2, 910 g of the dichloride with a titre of 99.8%.
b) Synthesis of the ester, in a solvent:-640 g (2 moles) of 2,2'-methylene bis-(4-methyl 6-t~ylphenol) were dissolved in 1000 g of 1,2-dichloroethane.
183 g (1 mole) of liquid, adipyl chloride were added.
~he intro~uction of 200 g (1.08 mole) o~ trieth~lamine at 70C produced a precipitate. After washing with water and alcohol, 540 g of product were obtained:-appearance, ~i~ht-yellow coloured powder melting point 201-204C
Hydroxyl i~dex 138 ~aponification index 155 acid index 0 xample 4 S~nthesis of the condensation product of the dichloride of azelaic acid with the diphenol I (R1=R2=H;R3-CH~;R4-But) a) Preparation of the dichloride Using the same molar proportions and conditions a~ in Example 3, azelyl chloride was obtained with a titre of 99.8%.
b) Synthesis of the ester~
~047523 A precipitate was formed, as in Example 3.
Triethylamine hydrochloride was eliminated by filtration, and washing of the organic phase with water.
After distillation of the 1,2-dichloroethane, the product was crystallized from white spirit.
appearance, cream-coloured powder melting point 143-145C
hydroxyl index 160 saponification index 145 acid index traces ExamPle fi Synthesis of the condensation product of thionyl chloride with the diphenol I (R1=R2=H; R3~CH3; R4=But) 340 g of 2,2'-methylene bis-(4-methyl-6-t-butylphenol) were placed in a 2-liter reactor having an anchor stirrer, a condenser, a dropping funnel, an immersion thermometer, and an input permitting nitrOgen bubbling. The phenol was dissolved in 500 g of hot octane, aslight current of nitrogen being introduced into the solution. At the end of one hour of nitrogen bubbling, 80 g of thionyl chloride were added dropwise, the temperature being maintained at 78C. The solution was heated to 80C as long as hydrogen chloride was released. When the reaction was o~er, the medium was cooled, and the precipitate filtered, washed with octane and then dried. The product was a yield of 86% of a white powder with a melting point of 165C.
The following tests show the anti-oxidant properties of H~M 12 compared with hitherto proposed anti-oxidants.
Stabilit~
3.0 g of each substance under test were introduced ~0475Z3 and carefully spread over the entire surface of a Petri dish having a diameter of 10 cm. ~he dishes were heated in air to 200C. Weighings were effected at regular intervals, and this enabled losses by evaporation or de-composition to be followed. The results obtained aresummarised in Table I.
The results in ~able I show that ~PM 12 withstood heating under the given conditions better than the other anti-oxidants which were tested.
Anti-Oxidant ProPerties 1) On pol~rop~lene a) ~ests with pol~Pro~lene powder Mixtures were prepared of polypropylene powder (3 g) and various amounts of anti-oxidant, and the conventionally used synergistic agent, dilaurylthiodipropionate (DLTDP).
These mixtures were placed in Petri dishes and heated to different temperatures for v~rious periods.
~he results obtained were as follows:-with 0.03 mole of anti-oxidant/kg of polypropylene, and 0.01 mole DLDTP/kg of polypropylene, and heating for 36 hours to 150C, the following were obser~ed:-Polypropylene alone - dark brown agglomerate " + ~opanol CA - brown powder " + Ionox 330 - yellow powder " + Irganox 1010 - light yellow powder " + HMP 12 - white powder With 0.3% by weight of anti-oxidant and 0.1% by weight o~ DLTDP based on the polypropylene, the following were observed:-1) after heating for 168 hours at 120C, and then for 24 hours at 180C:-~47523 Polypropylene - brown film, total de-composition of polymer Prolypropylene + BB10 - brown film, decomposition of the polymer " ~ Topanol CA - light brown film, decom-position of polymer " + Irganox 1010 - brown film, partial decomposition of polymer " ~ Ionox 330 - yellow film, slight decomposition " + HPM 12 - cream film, no decomposition.
Numerous phenolic derivatives have been proposed hitherto as anti-oxidants and as thermal stabilizers of plastics S materials such as polyolefins. In particular, it has been proposed hitherto to use a diphenol of formula ~ OH
R3 ~ 71 ~ 3 ~I) wherein Rl and R2 are preferably hydrogen atoms, R4 is preferably a lower alkyl group, such as a methyl group, and R3 is preferably a t-butyl group.
For numerous plastics materials, such as polyolefins, these phenolic derivatives are too volatile. They have a tendency to become eliminated from p7~stics materials, through evaporation, and they can then no longer act as stabilizers.
According to the present invention there are provided compounds of formula Q - O - R - O - Q II
in which Q represents a group of formula wherein:
R5 and R6 are hydrogen or alkyl groups R7 and R8 are alkyl groups R is an acid group derived from the group consisting of thionyl chloride, phthallic acid and B~, . ~ ;, ,~
~ )47523 o o - ~ - R' - l -wherein R' is an aliphatic group having from 1 to 7 carbon atoms.
Compounds of formula II have been found to provide a particularly good stabilizing action on plastics materials while exhibiting low volatility.
Compounds of formula II can be prepared by known methods, for example by reacting an acid chloride of a polyfunctional acid with a bisphenol of formula I. The reaction can be performed using an excess of the bisphenol, under conditions whereby hydrogen chloride is eliminated as it is formed, either as a gas or by combination with a base.
The preferred compound of formula II, by virtue of its stabilizing properties with plastics materials is the diester obtained by reacting 2,2'-methylene bis-(4-methyl-6-t-butyl-phenol? with the dichloride of terephthalic acid. The product obtained is of formula ~ Ol CH3 ~-- -- C ~ C_ 0 ~3_CH3 CH 3 ~Rg R9 ~CH 3 : . '.~ ,;:J
~047S23 in which ~ represents a t-butyl group.
The compound can be prepared by heating a slight exces~ of the diphenol with the di-acid chloride of terphthalic acid in the presence of an amine which forms the c~rrespondin~ hydrochloride with hydrogen chloride.
~he reaction can be effected in the presence or absence of a solvent, and also in a medium which is a solvent for the desired product. The reaction can also be effected by the so-called interface technique, in which each reactant is in solution in a solvent which iæ immiscible with the solvent used for the other reactant. In this case, neutralization of the hydrogen chloride is preferably effected with an inorganic base.
Polye~ters of formula II have low volatility (being less volatile than the diphenol used as the starting material) and have substantial anti-oxidant properties. In addition, compounds of formula II in which R represents an aryl group can be converted into benzophenone-type compounds which absorb ultraviolet radiation. This makes them of interest in protecting plastics materials against thermal and photo-chemical degradation.
The following Examples are given by way of illustration only, and they show the preparation of the preferred compound i.e. the teraphthalate of 2,2'-methylene bis-(4-methyl 6-t-butylphenol) hereinafter referred to as HPM 12.
Example 1 Preparation of HPM 12 in a solvent 700 g (2.06 moles) of 2,2'-methylene bis-(4-methyl 6-t-butylphenol), dissolved at ambient temperature in 5000 g of alcohol-free anhydrous chloroform, were introduced into a 11~475Z3 6-liter reactor having an agitator, a condenser, a dropping funnel, a thermometer,and a tube permitting nitrogen bubbling, as required. A slight current of nitrogen was then intro-duced into the solution, and agitation started. At the end of one hour, 202 g (1 mole) of the di-chloride of terephthalic acid were quickly added. The solution was heated to 60C, and 210 g (2.08 moles) of trieth~lamine were introduced over 1 hour. A slight distillation of the chloroform occurred. After all the triethylPm;ne had been added, refluxing was maintained by heating for 5 hours, and thereafter the solution was cooled to 20C. The solution was washed four times with 3000 g of water in order to eliminate triethylamine hydrochloride. The organic phase was concentrated (2000 g of CHC13 were evaporated), cooled to 5C, and 2500 g of ethanol were added drop by drop to precipitate the product. The product was washed with 1000 g of ethanol, and dried to leave a white powder having the following properties:-- melting point - 244-247C
- hydroxyl index (found) - 147 (theory 140) - saponification index (found) - 137 (theory 1~0) - acid index (found) - 1.6 (theory 0) - elemental analysis, found:- C 79.6~/o~ H 7.90%;
calculated:- C 79.96%, H 8.2~o The weight bf product obtained was 712 g, corresponding to a yield of 88%.
Example 2 Preparation of HPM 12 without a solvent.
595 g (5 moles) of thionyl chloride were added at 20C
to 166 g (1 mole) of terephthalic acid in a 4-litre reactor ~ 0475Z3 equipped as in Example 1. Agitation was started, Pnd the temperature raised to 70C. 5 cm3 of pyridine were added very slowly, and the mixture was brought to ~OCl2 reflux for 8 hours. An abundant release of S02 and HCl occurred.
The temperature was then reduced to 70C, and the excess SOCl2 and the remaiDing hydrogen chloride were removed under vacuum until setting ~f the mixture. Agitation was then stopped.
~he addition of small amounts of anhydrous benzene before setting facilitated elimination of the SOCl2.
2000 g of anhydrous octane were then introduced into the reactor, and nitrogen bubbling and agitation were started.
When all the acid chloride - had di~solved, 680 g (2 moles) of 2,2'-methylene bis-(4-methyl-6-t-butylphenol) were quickly added. ~he temperature was raised to 80C, and 210 g (2.08 moles) of triethylamine were added over 90 minutes. A white precipitate formed duri~g the course of this introduction of triethylamine.
When the introduction was over, the temperaturo had increased to 90C, and the reaction was continued for 4 hours.
The mixture was then cooled to 20C and the precipitate filtered. The solid product was dissolved in chloroform and purified as in Example 1. 624 g (yield 7~/0) were obtained of a white product melting at 245-247C.
In the preparation described hereinbefore, the synthesis of the dichloride of terephthalic acid can be carried out using dime~hylformamide (DMF) instead of pyridine as catalyst, as follows:-166 g (1 mole) of terephthalic acid were introducedinto a 2-liter reactor having an anchor stirrer, a vertical ~0 condenser, a dropping funnel, and an immersion thermometer.
~047S23 595 g (5 moles) of cold thionyl chloride were added~ ~he mixture was agitated and heated to effect ~OCl2 reflux.
When the temperature reached 45~C, 7.3 g of DMF (0.05 mole per mole of acid function) were introduced, accelerating the temperature rise. Hydrogen chloride and sulphur oxide which were released, as well as the SOCl2 carried P1ong therewith, were neutralized at the output of the condenser by bubbling into a solution of a base.
After three hours of SOC12 reflux, all the terephthalic acid had dissolved, which indicated the end of the reaction.
EXCe8S SOC12 was distilled at atmospheric pressure, and 63%
of the excess thionyl chloride was recovered.
The chloride of the terephthalic acid obtained had a tit~e of 98.8% and it was produced in a yield of 10~/o.
By modifyi~g the conditions i~ Examples 1 and 2, it is possible to produce:-- a certain amount, generally low, of the monester of terephthalic acid. This occurs as a result of the presence of a small amount of water, the terephthalyl chloride being partly hydrolyzed to convert at least one acid chloride function into the carboxylic acid function. ~he presence of this monoester in the final product is no hindrance;
- a polymeric product. If HO-Q'-OH represents the bisphenol, and HOOC-~-COOH represents terephthalic acid, 5 the polymeric products that can be obtained are of formula:-O O O O
Il ~1 11 11 HO-Q'-O-C-~-C(O-~'-O-C-~-C)nO-i~'-OH
wherein n is an integer less than or equal to 4. Such polymers also exhibit interesting anti-oxidant and anti-ultra-violet properties, but they are generally less soluble in polyolefin~ and have anti-oxidizing activities less than those of the diesters of formula II.
Example 3 S~nthesis of the condensation product of the dichloride of adipic acid with the diphenol I(R1=R2=H; R4=CH ; R -But) _ _ 3 5 a) Preparation of the dichloride:-730 g of adipic acid (5 moles) were reacted for 8 hoursat a temperature of 60C with 1820 g of thionyl chloride (15 moles) to give, after distillation of the excess SOCl2, 910 g of the dichloride with a titre of 99.8%.
b) Synthesis of the ester, in a solvent:-640 g (2 moles) of 2,2'-methylene bis-(4-methyl 6-t~ylphenol) were dissolved in 1000 g of 1,2-dichloroethane.
183 g (1 mole) of liquid, adipyl chloride were added.
~he intro~uction of 200 g (1.08 mole) o~ trieth~lamine at 70C produced a precipitate. After washing with water and alcohol, 540 g of product were obtained:-appearance, ~i~ht-yellow coloured powder melting point 201-204C
Hydroxyl i~dex 138 ~aponification index 155 acid index 0 xample 4 S~nthesis of the condensation product of the dichloride of azelaic acid with the diphenol I (R1=R2=H;R3-CH~;R4-But) a) Preparation of the dichloride Using the same molar proportions and conditions a~ in Example 3, azelyl chloride was obtained with a titre of 99.8%.
b) Synthesis of the ester~
~047523 A precipitate was formed, as in Example 3.
Triethylamine hydrochloride was eliminated by filtration, and washing of the organic phase with water.
After distillation of the 1,2-dichloroethane, the product was crystallized from white spirit.
appearance, cream-coloured powder melting point 143-145C
hydroxyl index 160 saponification index 145 acid index traces ExamPle fi Synthesis of the condensation product of thionyl chloride with the diphenol I (R1=R2=H; R3~CH3; R4=But) 340 g of 2,2'-methylene bis-(4-methyl-6-t-butylphenol) were placed in a 2-liter reactor having an anchor stirrer, a condenser, a dropping funnel, an immersion thermometer, and an input permitting nitrOgen bubbling. The phenol was dissolved in 500 g of hot octane, aslight current of nitrogen being introduced into the solution. At the end of one hour of nitrogen bubbling, 80 g of thionyl chloride were added dropwise, the temperature being maintained at 78C. The solution was heated to 80C as long as hydrogen chloride was released. When the reaction was o~er, the medium was cooled, and the precipitate filtered, washed with octane and then dried. The product was a yield of 86% of a white powder with a melting point of 165C.
The following tests show the anti-oxidant properties of H~M 12 compared with hitherto proposed anti-oxidants.
Stabilit~
3.0 g of each substance under test were introduced ~0475Z3 and carefully spread over the entire surface of a Petri dish having a diameter of 10 cm. ~he dishes were heated in air to 200C. Weighings were effected at regular intervals, and this enabled losses by evaporation or de-composition to be followed. The results obtained aresummarised in Table I.
The results in ~able I show that ~PM 12 withstood heating under the given conditions better than the other anti-oxidants which were tested.
Anti-Oxidant ProPerties 1) On pol~rop~lene a) ~ests with pol~Pro~lene powder Mixtures were prepared of polypropylene powder (3 g) and various amounts of anti-oxidant, and the conventionally used synergistic agent, dilaurylthiodipropionate (DLTDP).
These mixtures were placed in Petri dishes and heated to different temperatures for v~rious periods.
~he results obtained were as follows:-with 0.03 mole of anti-oxidant/kg of polypropylene, and 0.01 mole DLDTP/kg of polypropylene, and heating for 36 hours to 150C, the following were obser~ed:-Polypropylene alone - dark brown agglomerate " + ~opanol CA - brown powder " + Ionox 330 - yellow powder " + Irganox 1010 - light yellow powder " + HMP 12 - white powder With 0.3% by weight of anti-oxidant and 0.1% by weight o~ DLTDP based on the polypropylene, the following were observed:-1) after heating for 168 hours at 120C, and then for 24 hours at 180C:-~47523 Polypropylene - brown film, total de-composition of polymer Prolypropylene + BB10 - brown film, decomposition of the polymer " ~ Topanol CA - light brown film, decom-position of polymer " + Irganox 1010 - brown film, partial decomposition of polymer " ~ Ionox 330 - yellow film, slight decomposition " + HPM 12 - cream film, no decomposition.
2) after heating at 170C for 17 hours, the polypropylene film protected with HPM 12 did not decompose;
3) after heating to 200C for 100 minutes, the poly-propylene film protected with HPM 12 remained flexible and translucent;
4) after heating at 220C for 20 minutes the poly-propylene film protected with HPM 12 retained its color and flexibilit~.
All these tests show that EPn 12 is a ~ery efficie~t antl-oxidant even at high temperatures (220C, for example).
b) Measurement b~ the "Brittle ~est"
~ he test consi~ted firstly of making polypropylene test pieces containing a selected anti-oxidant, and thereafter ageing the test pieces in a ventilated oven at high temperature. ~he time (in hours) was determined which the polymer will withstand these ageing conditions while retaining its mechanical properties sufficient to enable it to be bent.
The test pieces had a thickness of 0.3 mm, and they were circul æ (diameter 80 mm).
The following results were obtained:-- ageing temperature 140C.
3o Composition I Composition II
polypropylene 100 100 calcium stearate 0.2 0.2 D ~ T D P 0 0~15 The test pieces of Composition I did not withstand ageing for 10 hours, whereas the test pieces of Compo~ition II
withstood ageing for more than 1200 hours.
- ageing temperature 150C
Composition III Composition I~
polypropylene 100 100 calcium stearate 0.1 0.1 D S ~ D P
(dilaurylthiodipropionate) O 0.25 HPM 12 0 0.10 ~he test pieces to Composition III were completely destroyed after ageing for several hours (approximately 10) while the Compositio~ IV test pieces withstood ageing~ for more than 1700 hours.
2) On ~ol eth~lene Although polyethylene usually withstands thermal degradation better than polypropylene, anti-oxidants are required i~ its mechanical properties are to be long-lasting.
The incorporation of a phenolic anti-oxidant sometimes causes the polymer to become colored, due to reaction of residual amounts of catalyst in the polyethylene with the phenolic anti-oxidant. ~ests were conducted with ~PM 12 and a high density polyethylene exhibiting coloration phenomena with phenolic anti-oxidants.
3o _ 12 -Composition V Composition VI
Polyethylene 100 100 (high density) HPM 12 anti-oxidant 0 0.015 D. L T D P 0 0.030 The compositions were prepared in the cold in the form of a powder, placed in Petri dishes (3 g of substance per Petri dish of 90 mm diameter), and then placed in an oven.
1) Heating for 20 mins to 200C.
Composition (V) - yollow, highly reticulated product Composition (~I) - white product with retention of its mechanical properties 2) Heating for 20 mins. to 220C
Composition V - coloured, partly decomposed product Composition VI - white prcduct with retentiQn Or its mechanical properties.
Tests made with hitherto proposed anti-oxidants gave colored and degraded films. In spite of the amount of EPM 12 used being small, it was particularly efficient as an anti-oxidant.
Ultra-violet Properties The UV spectrum of HPM 12 shows a number of absorption bands, the molar absorption coefficients obtained being as follows:-I m~ 1 215 1 245 1 280 ~ r~~3-~~~ -, .
Polypropylene films containing 0.3C~o of HPM 12 and 0.1%
of DLTDP were made by heating a suitable powder mixture.
30 These films were irradiated for 50 hours with a PHI~IPS
~0~75Z3 HPR 125 ultra-violet,lamp. The distance between the lamp and the films was 30 cm.
Polypropylene film without HPM 12 became hard and brittle, On the contrary, polypropylene film containi~g HP~ 12 remained flexible and retained its mechanical propertie~, although it developed a slight yellow color.
TA~LE I
. Oven losses at 200C (%) Point After 2 hrs After 4 hrs and color IRGANOX 1010 118-120C 0.64 0.85 yellow (GEIGy) (white po~,Jder) TOPANO~ CA 178-180C 13.1 13.5 brown (ICI) (cream powder) BB 10 (SFOS) 204-207C 10.2 23.6 brown (white powder) IO~OX 330 234-236C 0.24 10.3 brown (S~F~'L) (yellow powder) HPM 12 245-248C 0.25 0.25 white (white powder) IRGA~OX 1010 But C ~CH2c2(cH2)2 ~ But 4 TOPANOL CA
CH3 But CH(CH2-CH ~ OH J
~047SZ3 But ~ OH
But . CH3 CH2 ~10 ~;~ C312 ~ But OH
But CH3 C~H7 HO ~ CH ~_ OH
But But
All these tests show that EPn 12 is a ~ery efficie~t antl-oxidant even at high temperatures (220C, for example).
b) Measurement b~ the "Brittle ~est"
~ he test consi~ted firstly of making polypropylene test pieces containing a selected anti-oxidant, and thereafter ageing the test pieces in a ventilated oven at high temperature. ~he time (in hours) was determined which the polymer will withstand these ageing conditions while retaining its mechanical properties sufficient to enable it to be bent.
The test pieces had a thickness of 0.3 mm, and they were circul æ (diameter 80 mm).
The following results were obtained:-- ageing temperature 140C.
3o Composition I Composition II
polypropylene 100 100 calcium stearate 0.2 0.2 D ~ T D P 0 0~15 The test pieces of Composition I did not withstand ageing for 10 hours, whereas the test pieces of Compo~ition II
withstood ageing for more than 1200 hours.
- ageing temperature 150C
Composition III Composition I~
polypropylene 100 100 calcium stearate 0.1 0.1 D S ~ D P
(dilaurylthiodipropionate) O 0.25 HPM 12 0 0.10 ~he test pieces to Composition III were completely destroyed after ageing for several hours (approximately 10) while the Compositio~ IV test pieces withstood ageing~ for more than 1700 hours.
2) On ~ol eth~lene Although polyethylene usually withstands thermal degradation better than polypropylene, anti-oxidants are required i~ its mechanical properties are to be long-lasting.
The incorporation of a phenolic anti-oxidant sometimes causes the polymer to become colored, due to reaction of residual amounts of catalyst in the polyethylene with the phenolic anti-oxidant. ~ests were conducted with ~PM 12 and a high density polyethylene exhibiting coloration phenomena with phenolic anti-oxidants.
3o _ 12 -Composition V Composition VI
Polyethylene 100 100 (high density) HPM 12 anti-oxidant 0 0.015 D. L T D P 0 0.030 The compositions were prepared in the cold in the form of a powder, placed in Petri dishes (3 g of substance per Petri dish of 90 mm diameter), and then placed in an oven.
1) Heating for 20 mins to 200C.
Composition (V) - yollow, highly reticulated product Composition (~I) - white product with retention of its mechanical properties 2) Heating for 20 mins. to 220C
Composition V - coloured, partly decomposed product Composition VI - white prcduct with retentiQn Or its mechanical properties.
Tests made with hitherto proposed anti-oxidants gave colored and degraded films. In spite of the amount of EPM 12 used being small, it was particularly efficient as an anti-oxidant.
Ultra-violet Properties The UV spectrum of HPM 12 shows a number of absorption bands, the molar absorption coefficients obtained being as follows:-I m~ 1 215 1 245 1 280 ~ r~~3-~~~ -, .
Polypropylene films containing 0.3C~o of HPM 12 and 0.1%
of DLTDP were made by heating a suitable powder mixture.
30 These films were irradiated for 50 hours with a PHI~IPS
~0~75Z3 HPR 125 ultra-violet,lamp. The distance between the lamp and the films was 30 cm.
Polypropylene film without HPM 12 became hard and brittle, On the contrary, polypropylene film containi~g HP~ 12 remained flexible and retained its mechanical propertie~, although it developed a slight yellow color.
TA~LE I
. Oven losses at 200C (%) Point After 2 hrs After 4 hrs and color IRGANOX 1010 118-120C 0.64 0.85 yellow (GEIGy) (white po~,Jder) TOPANO~ CA 178-180C 13.1 13.5 brown (ICI) (cream powder) BB 10 (SFOS) 204-207C 10.2 23.6 brown (white powder) IO~OX 330 234-236C 0.24 10.3 brown (S~F~'L) (yellow powder) HPM 12 245-248C 0.25 0.25 white (white powder) IRGA~OX 1010 But C ~CH2c2(cH2)2 ~ But 4 TOPANOL CA
CH3 But CH(CH2-CH ~ OH J
~047SZ3 But ~ OH
But . CH3 CH2 ~10 ~;~ C312 ~ But OH
But CH3 C~H7 HO ~ CH ~_ OH
But But
Claims (10)
1. A compound of the formula:
Wherein:
R5 and R6 are hydrogen or alkyl groups R7 and R8 are alkyl groups R is an acid group derived from the group consisting of thionyl chloride, phthallic acid and wherein R' is an aliphatic group having from 1 to 7 carbon atoms.--
Wherein:
R5 and R6 are hydrogen or alkyl groups R7 and R8 are alkyl groups R is an acid group derived from the group consisting of thionyl chloride, phthallic acid and wherein R' is an aliphatic group having from 1 to 7 carbon atoms.--
2. The compound of claim 1 wherein each R5 and R6 are hydrogen.--
3. The compound of claim 1 wherein each R7 is a t-butyl group and each R8 is a methyl group.--
4. A synthetic polymer containing a stabilizing amount of from 0.01 to 0.5% by weight of a compound having the formula:
Wherein:
R5 and R6 are hydrogen or alkyl groups R7 and R8 are alkyl groups R is an acid group derived from the group consisting of thionyl chloride, phthallic acid and wherein R' is an aliphatic group having from 1 to 7 carbon atoms.--
Wherein:
R5 and R6 are hydrogen or alkyl groups R7 and R8 are alkyl groups R is an acid group derived from the group consisting of thionyl chloride, phthallic acid and wherein R' is an aliphatic group having from 1 to 7 carbon atoms.--
5. The polymer of claim 4 wherein the polymer is a polyolefin.--
6. The compound of claim 4 wherein each R5 and R6 are hydrogen.--
7. The compound of claim 4 wherein each R7 is a t-butyl group and each R8 is a methyl group.
8. The teraphthalate of 2,2'-methylene bis-(4-methyl 6-t-butylphenol).
9. A synthetic polymer containing a stabilizing amount of from 0.01% to 0.5% by weight of teraphthalate of 2,2'-methylene bis-(4-methyl 6-t-butylphenol).
10. The polymer of claim 9 wherein the polymer is a polyolefin.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7408403A FR2264002B1 (en) | 1974-03-12 | 1974-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1047523A true CA1047523A (en) | 1979-01-30 |
Family
ID=9136200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA221,861A Expired CA1047523A (en) | 1974-03-12 | 1975-03-11 | Processes for preparing phenolic diesters |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5110854A (en) |
| BE (1) | BE826513A (en) |
| CA (1) | CA1047523A (en) |
| CH (1) | CH605579A5 (en) |
| DE (1) | DE2509552C2 (en) |
| DK (1) | DK150612C (en) |
| FR (1) | FR2264002B1 (en) |
| GB (1) | GB1453916A (en) |
| IE (1) | IE40739B1 (en) |
| IT (1) | IT1030320B (en) |
| LU (1) | LU72011A1 (en) |
| NL (1) | NL178416C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5825108B2 (en) * | 1975-09-02 | 1983-05-25 | シプロカセイ カブシキガイシヤ | How to prevent discoloration of polyurethane |
| DE2820716A1 (en) | 1977-05-23 | 1978-12-07 | Sandoz Ag | CARBONATES AND URETHANES OF 2,2'-ALKYLENE OR CYCLOALKYLENE- TO 2,4-DISUBSTITUTED PHENOL, THEIR PRODUCTION AND USE AS ANTIOXYDANTS IN POLYMERIC ORGANIC MATERIALS |
| US4427737A (en) * | 1981-04-23 | 1984-01-24 | E. R. Squibb & Sons, Inc. | Microporous adhesive tape |
| JPS5977315U (en) * | 1982-11-15 | 1984-05-25 | 株式会社ホクエイ | Transplanter groove opening device |
| FR2540504B1 (en) * | 1983-02-07 | 1986-03-07 | Solvay | PROCESS FOR THE STERILIZATION BY IRRADIATION OF POLYOLEFINIC COMPOSITIONS, POLYOLEFINIC COMPOSITIONS THUS STERILIZED AND ARTICLES MADE THEREFROM |
| DE3370319D1 (en) * | 1983-12-13 | 1987-04-23 | Sumitomo Chemical Co | Method for producing bisphenol derivatives |
| JPS62139213U (en) * | 1986-02-26 | 1987-09-02 | ||
| JPS62139212U (en) * | 1986-02-26 | 1987-09-02 | ||
| JPS62186610U (en) * | 1986-05-14 | 1987-11-27 | ||
| JPS63209A (en) * | 1986-05-25 | 1988-01-05 | 鋤柄農機株式会社 | Groove forming apparatus in deep layer fertilizer |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1089168B (en) * | 1957-06-03 | 1960-09-15 | Bayer Ag | Process for the production of anti-aging agents |
| US3038878A (en) * | 1960-07-29 | 1962-06-12 | Eastman Kodak Co | Heat-stable poly-alpha-olefin compositions |
| FR1379593A (en) * | 1963-01-21 | 1964-11-20 | Shell Int Research | New light stabilization compounds, process for their preparation and new light stable polymer compositions |
| NL130435C (en) * | 1963-08-30 | |||
| US3629322A (en) * | 1969-02-17 | 1971-12-21 | Buckman Labor Inc | Organic esters and their use as ultraviolet light absorbers and as heat stabilizers |
| US3907939A (en) * | 1969-06-16 | 1975-09-23 | Ashland Oil Inc | Phosphite esters of hindered phenols |
| JPS5111650B2 (en) * | 1972-04-05 | 1976-04-13 |
-
1974
- 1974-03-12 FR FR7408403A patent/FR2264002B1/fr not_active Expired
-
1975
- 1975-03-03 GB GB871975A patent/GB1453916A/en not_active Expired
- 1975-03-05 IE IE47875A patent/IE40739B1/en unknown
- 1975-03-05 DE DE19752509552 patent/DE2509552C2/en not_active Expired
- 1975-03-10 LU LU72011A patent/LU72011A1/xx unknown
- 1975-03-11 CA CA221,861A patent/CA1047523A/en not_active Expired
- 1975-03-11 BE BE2054196A patent/BE826513A/en not_active IP Right Cessation
- 1975-03-11 NL NL7502888A patent/NL178416C/en not_active IP Right Cessation
- 1975-03-11 IT IT6761675A patent/IT1030320B/en active
- 1975-03-12 CH CH313675A patent/CH605579A5/xx not_active IP Right Cessation
- 1975-03-12 JP JP3064375A patent/JPS5110854A/en active Granted
- 1975-03-12 DK DK100175A patent/DK150612C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2509552A1 (en) | 1975-09-18 |
| DK100175A (en) | 1975-09-13 |
| NL7502888A (en) | 1975-09-16 |
| NL178416B (en) | 1985-10-16 |
| DE2509552C2 (en) | 1984-08-09 |
| JPS5618019B2 (en) | 1981-04-25 |
| BE826513A (en) | 1975-06-30 |
| FR2264002B1 (en) | 1977-09-23 |
| CH605579A5 (en) | 1978-09-29 |
| LU72011A1 (en) | 1975-08-20 |
| DK150612C (en) | 1987-11-23 |
| GB1453916A (en) | 1976-10-27 |
| IT1030320B (en) | 1979-03-30 |
| JPS5110854A (en) | 1976-01-28 |
| IE40739L (en) | 1975-09-12 |
| NL178416C (en) | 1986-03-17 |
| IE40739B1 (en) | 1979-08-01 |
| DK150612B (en) | 1987-04-21 |
| FR2264002A1 (en) | 1975-10-10 |
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