CA1076289A - Method of preparing phenolamine resins - Google Patents
Method of preparing phenolamine resinsInfo
- Publication number
- CA1076289A CA1076289A CA236,136A CA236136A CA1076289A CA 1076289 A CA1076289 A CA 1076289A CA 236136 A CA236136 A CA 236136A CA 1076289 A CA1076289 A CA 1076289A
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- CA
- Canada
- Prior art keywords
- phenol
- carbon atoms
- alkyl radical
- resin
- resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Abstract
Abstract of the Disclosure Novel phenolamine resins which are condensation products of hexamethylene tetramine with a phenol component such as an alkylphenol with 5 to 12 carbon atoms in the alkyl radical, styrene-alkylated phenol, cumylphenol, diphenylolpropane, hyd-roxybenzoic acid. The condensation reaction is conducted is at a temperature ranging from 90 to 180°C.
The products thus prepared are efficient stabilizing agents for rubbers and vulcanizates.
The products thus prepared are efficient stabilizing agents for rubbers and vulcanizates.
Description
~o~
PHENOLAMINE RESINS AND NETHOD OF PREPARING SAME
~ he present in~ention relates to polymeric materials and, more specifically, to phenolamine resins and a method of prem paring same.
Phenolamine resins are extensively used in the production of varnishes, points, electroinsulating materials, glass-fiber plastics~
The term phenolamine resins as used herein denotes pro-ducts prepared by condensation of phenol, its substitu~ed derl-vatives and hexamethylene tetramine.
In the case of phenol derivatives, the structure of sucb resins may be represented by the following general formula~
OH OH
~ ~ C~21~UC~2 ~~ ~
where R represents methyl3 chlorine, tert.butyl3 dimethyl, while m is of from 1 to 10.
Charac~eristio feature of the phenolamine resins is the presence of phenol fragments linked by methylene amine bridges~
Noelcular weight of said resins is defined by the molar ratio between ~he phenol component and hexamethylene tetramine and by the temperature of the resin manufacture. PhenoLamine resins may be prepared without solvent7 or in a solvent medium, both under atmospheric and over-atmospheric pressure and at a temperature within the range of from 80 to 180C, preferably :. :
' :,'' ~'7~
within the range of from 120 to 150 C. Technologically convi-nient is the synthesis of phenolamine resins, since the resin is prepared in one stage.
As the phenol component for the production of phenolamine resins use is made of phenol, cresol, xylenols, p-tert.butyl phenol. To prepare phenolamine resins use is made of dimethyl-vinylethynyl-4-oxyphenylmethane, a mixture of phenol9 cresols and xylenols.
Those phenols are technologically inconvinient, since they comprise solid compounds with a high melting point such as p-tert.butylphenol or difficult-to-obtain as dimethylvinyl^
ethynyl-4-oxyphenylmethane, p-cresol.
Said phenolamine resins feature an essential disadvantage restricting their application, i.e. low solubility in aromatic aliphatic and cycloaliphatic hydrocarbons. Low solubllity of said resins~ in particular, does not make it possible to use the~ for compounding with rubbers in the stage of solutionO
It is an object of the present invention to prepare such phenolamine resins which would posses a hgh solubility in hydrocarbons, would be obtained from readily-available raw materials, would be inexpensive and feature a high efficiency during stabilization and modification of rubbers and vulcani~ ;
zates based thereon. ~-This ob~ect is accomplished by a method of preparing phenolamine res1ns of the formula:
PHENOLAMINE RESINS AND NETHOD OF PREPARING SAME
~ he present in~ention relates to polymeric materials and, more specifically, to phenolamine resins and a method of prem paring same.
Phenolamine resins are extensively used in the production of varnishes, points, electroinsulating materials, glass-fiber plastics~
The term phenolamine resins as used herein denotes pro-ducts prepared by condensation of phenol, its substitu~ed derl-vatives and hexamethylene tetramine.
In the case of phenol derivatives, the structure of sucb resins may be represented by the following general formula~
OH OH
~ ~ C~21~UC~2 ~~ ~
where R represents methyl3 chlorine, tert.butyl3 dimethyl, while m is of from 1 to 10.
Charac~eristio feature of the phenolamine resins is the presence of phenol fragments linked by methylene amine bridges~
Noelcular weight of said resins is defined by the molar ratio between ~he phenol component and hexamethylene tetramine and by the temperature of the resin manufacture. PhenoLamine resins may be prepared without solvent7 or in a solvent medium, both under atmospheric and over-atmospheric pressure and at a temperature within the range of from 80 to 180C, preferably :. :
' :,'' ~'7~
within the range of from 120 to 150 C. Technologically convi-nient is the synthesis of phenolamine resins, since the resin is prepared in one stage.
As the phenol component for the production of phenolamine resins use is made of phenol, cresol, xylenols, p-tert.butyl phenol. To prepare phenolamine resins use is made of dimethyl-vinylethynyl-4-oxyphenylmethane, a mixture of phenol9 cresols and xylenols.
Those phenols are technologically inconvinient, since they comprise solid compounds with a high melting point such as p-tert.butylphenol or difficult-to-obtain as dimethylvinyl^
ethynyl-4-oxyphenylmethane, p-cresol.
Said phenolamine resins feature an essential disadvantage restricting their application, i.e. low solubility in aromatic aliphatic and cycloaliphatic hydrocarbons. Low solubllity of said resins~ in particular, does not make it possible to use the~ for compounding with rubbers in the stage of solutionO
It is an object of the present invention to prepare such phenolamine resins which would posses a hgh solubility in hydrocarbons, would be obtained from readily-available raw materials, would be inexpensive and feature a high efficiency during stabilization and modification of rubbers and vulcani~ ;
zates based thereon. ~-This ob~ect is accomplished by a method of preparing phenolamine res1ns of the formula:
-2 . - ,- , : ~ . .... ; . .. ;:
pH QH
~ CH2 - NH C~2 Xn R R m OH
where X i~ hydrogen or -ÇH2 ~ NH - CH2 ~ COOH
when x is hydrogen, R represents an alkyl radical with 5 to 12 carbon atoms, phenylethyl, cumyl, carboxy, OH
when X is -CH2 - NH - CH2 ~ - COOH
R represent~ an alkyl radical with 1 to 12 carbon atoms, phenyl-ethyl, cumyl, hydroxyarylalkyl, or carboxy, n and m are o~ from 1 to 20, which method, in accordance with the present invention, involve~
condensation of hexamethylene tetramine with a phenol component which i~ repre~ented by alkylphenols with 5 to 12 carbon atoms in the alkyl radicals, styrene-alkylated phenol, cumylphenol/
diphenylolpropane, hydroxybenzoic acid, and mixtures thereof.
Owing ~o the use of a substituted phenol with a long side chain as a phenol component selected from the series of hexylphenol, octylphenol, nonylphenol, dodecylphenol, styrene-alkylated phenol, cumylphenol or mixture~ thereof with other phenol derivatives, corresponding phenolamine re~in~ feature a high solubility in organic solvents. Thiq property of the re~in~
broadens tbe rango of their application in industry.
" ';: '
pH QH
~ CH2 - NH C~2 Xn R R m OH
where X i~ hydrogen or -ÇH2 ~ NH - CH2 ~ COOH
when x is hydrogen, R represents an alkyl radical with 5 to 12 carbon atoms, phenylethyl, cumyl, carboxy, OH
when X is -CH2 - NH - CH2 ~ - COOH
R represent~ an alkyl radical with 1 to 12 carbon atoms, phenyl-ethyl, cumyl, hydroxyarylalkyl, or carboxy, n and m are o~ from 1 to 20, which method, in accordance with the present invention, involve~
condensation of hexamethylene tetramine with a phenol component which i~ repre~ented by alkylphenols with 5 to 12 carbon atoms in the alkyl radicals, styrene-alkylated phenol, cumylphenol/
diphenylolpropane, hydroxybenzoic acid, and mixtures thereof.
Owing ~o the use of a substituted phenol with a long side chain as a phenol component selected from the series of hexylphenol, octylphenol, nonylphenol, dodecylphenol, styrene-alkylated phenol, cumylphenol or mixture~ thereof with other phenol derivatives, corresponding phenolamine re~in~ feature a high solubility in organic solvents. Thiq property of the re~in~
broadens tbe rango of their application in industry.
" ';: '
- 3 :
¢-7, ~076~
Shown in ~able 1 are data illustrating solubility of the phenolamine resin prepared in accordance with the present in-vPn~ion on the basis of octylphenol (resin A) in comparison with the prior art resins based on dimethylvinylethynyl-4-oxy-phenylmethane (resin s), p~ert.bu~ylphenol (resin C), p~cre-sol (resin D).
Table 1 Solubility of resins A, B9 C and D at 20C
g per 100 ml of a solvent No. S o 1 v e n t resins A B C D
1~ Hexane 80 1 1insoluble 2. Hexane~cyclohexane, 15:85 85 1 1.5 insoluble 3. Toluene ~3 5 20 10 _ .. _ _ _ _ .. _ _ -- -- -- -- -- -- -- :
High solubility of the resins according to the present ~;
in~ention enables their extensive use in various ind~stries.
When as the phenol component use is made of a hydroxy-benzoic acid such as salicylic acid or para-hydroxybenzoic acid9 phenolamine resins acquire a property to be soluble in alkalis. This property also brosdens the application range of phenolaminelresins.
In accordance with the present invention, ~he method of p~eparing said resins is effected by condensation of hexamet-hylene te~ramine with a phenol component which is represented by an alkylphenol with a molecular weight of 160 ~o 350 and 5 to 12 carbon atoms in the alkyl radical such as styrene~
-4_ ' ~, ::
7~
-alkylated phenol~ cumylphenol, diphenylolpropane, hydroxyben~
zoic aeid. Hexamethylene tetramine and the phenol component are taken in a molar ra~io of from 0.02:1 to 1:1 and the reac-tion is conducted at a temperature ranging from 90 to 180 C.
Said resins f2ature an advantage residing in their non-toxi~lty, availability of raw materials; the method of produc-ing such resins is readily commercially implemènted without the forma~ion of ha~mful waste waters. Alkylphenols with S to 12 carbon atoms as well as styrene-alkylated phenol, diphenyl-olpropane, hydroxybenzoic acids are available raw materials, since they are obtained on a commercial scale in all indust-rially developed countries.
It has been found that said phenolamine resins have a highly pr~nounced st~bilizing.~effec~ against thermal agelng of rubbers and vulcanizates based thereon and a good compati-bility with rubbers which is illustrated in Examples given hereinbelow. The use of the res.ins according to the present invention makes it possible to exclude such a toxic antioxi~
dant as N-phenyl-2~naphthylamine (Neozone-D)*, to improve sani- .
tary conditions of labour simultaneously enhancing quality of rubbers and vulcanizatesO
For better understanding of the present invention some speci~ic Example 1 through 15 illustrating the method of pre- ~:
paring phenolamine resins and Example 16 - 19 illustrating use thereof are given hereinbelow~
* TFademark ~.:
: .
-6~
Example 1 A mixture containing 97 g (0.5 g-mol~ of octylphenol with the molecular weight of 194 and 14.Q g (Ool g~mol) of hexamet-hylene tetramine are heated in a reaction flask under stirring to a te~perature of 140 - 145C. Condensation reaction which starts a~ this temperature is accompanied by self-heating of the reaction mixture to 165C and vigorous evolution of am~o-nia. On completion of the reaction (20 - 30 minutes) e~idenced by ~torage of the evolution of ammonia~ the reaction mass is poured into a porcelain cup. ~he resins is rapidly cooled and comprises a solid brittle amber-coloured product. After disin-tegration it is in the form of a light-yellow powder with a drop point of 94C~ The resin yield is 107 g. The resin is rea~
dily soluble in ben~ene, toluene, hexane, cyclohexane. Chara-cteristics of the resin are given in Table 2 hereinbelow. ;
Table 2 Resin Characteristics No. P a r a m e ~ e r V a 1 u e l. Appearance light-yellow powder 2. Molecular weight 728 3. Ubbelohde drop point~ C 94 -
¢-7, ~076~
Shown in ~able 1 are data illustrating solubility of the phenolamine resin prepared in accordance with the present in-vPn~ion on the basis of octylphenol (resin A) in comparison with the prior art resins based on dimethylvinylethynyl-4-oxy-phenylmethane (resin s), p~ert.bu~ylphenol (resin C), p~cre-sol (resin D).
Table 1 Solubility of resins A, B9 C and D at 20C
g per 100 ml of a solvent No. S o 1 v e n t resins A B C D
1~ Hexane 80 1 1insoluble 2. Hexane~cyclohexane, 15:85 85 1 1.5 insoluble 3. Toluene ~3 5 20 10 _ .. _ _ _ _ .. _ _ -- -- -- -- -- -- -- :
High solubility of the resins according to the present ~;
in~ention enables their extensive use in various ind~stries.
When as the phenol component use is made of a hydroxy-benzoic acid such as salicylic acid or para-hydroxybenzoic acid9 phenolamine resins acquire a property to be soluble in alkalis. This property also brosdens the application range of phenolaminelresins.
In accordance with the present invention, ~he method of p~eparing said resins is effected by condensation of hexamet-hylene te~ramine with a phenol component which is represented by an alkylphenol with a molecular weight of 160 ~o 350 and 5 to 12 carbon atoms in the alkyl radical such as styrene~
-4_ ' ~, ::
7~
-alkylated phenol~ cumylphenol, diphenylolpropane, hydroxyben~
zoic aeid. Hexamethylene tetramine and the phenol component are taken in a molar ra~io of from 0.02:1 to 1:1 and the reac-tion is conducted at a temperature ranging from 90 to 180 C.
Said resins f2ature an advantage residing in their non-toxi~lty, availability of raw materials; the method of produc-ing such resins is readily commercially implemènted without the forma~ion of ha~mful waste waters. Alkylphenols with S to 12 carbon atoms as well as styrene-alkylated phenol, diphenyl-olpropane, hydroxybenzoic acids are available raw materials, since they are obtained on a commercial scale in all indust-rially developed countries.
It has been found that said phenolamine resins have a highly pr~nounced st~bilizing.~effec~ against thermal agelng of rubbers and vulcanizates based thereon and a good compati-bility with rubbers which is illustrated in Examples given hereinbelow. The use of the res.ins according to the present invention makes it possible to exclude such a toxic antioxi~
dant as N-phenyl-2~naphthylamine (Neozone-D)*, to improve sani- .
tary conditions of labour simultaneously enhancing quality of rubbers and vulcanizatesO
For better understanding of the present invention some speci~ic Example 1 through 15 illustrating the method of pre- ~:
paring phenolamine resins and Example 16 - 19 illustrating use thereof are given hereinbelow~
* TFademark ~.:
: .
-6~
Example 1 A mixture containing 97 g (0.5 g-mol~ of octylphenol with the molecular weight of 194 and 14.Q g (Ool g~mol) of hexamet-hylene tetramine are heated in a reaction flask under stirring to a te~perature of 140 - 145C. Condensation reaction which starts a~ this temperature is accompanied by self-heating of the reaction mixture to 165C and vigorous evolution of am~o-nia. On completion of the reaction (20 - 30 minutes) e~idenced by ~torage of the evolution of ammonia~ the reaction mass is poured into a porcelain cup. ~he resins is rapidly cooled and comprises a solid brittle amber-coloured product. After disin-tegration it is in the form of a light-yellow powder with a drop point of 94C~ The resin yield is 107 g. The resin is rea~
dily soluble in ben~ene, toluene, hexane, cyclohexane. Chara-cteristics of the resin are given in Table 2 hereinbelow. ;
Table 2 Resin Characteristics No. P a r a m e ~ e r V a 1 u e l. Appearance light-yellow powder 2. Molecular weight 728 3. Ubbelohde drop point~ C 94 -
4. Dumas nitrogen content, Z 6.5
5. Solubility, g per 100 ml of toluene 83 he~ane 80 mixture hexane-cyclohexane (15:85) 85 _ O _ _ ~
-6- ~
;~v~
Taken for the reaction are 194 g (1.0 g-mol) of octylphe-nol (with the characeeristic of ExamplP 1~ and 23.4 g (00167 g-mol) of hexamethylene tetramine. Condensa~ion without sol-vent is conducted as in Example 1. Condensa~ion time, a~ a temperature of f~om 140 to 165C, is 30 to 35 minutes. Chara-cteristics of the thus-prepared resin are given in Table 3 hereinbelow.
Table 3 Resin Char~cteristics No. P a r a m e t e r V a 1 u e .. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 1. Appearance light-yellow powder 2. ~olecular weight 600 3. Ubbelohde drop point, C 88.5 4. Dumas nitrogen content, % 6.7 5~ Solubility~ g per 100 ml of toluene 81 hexane 67 mixture h~xane~cyclohexane (15:85)75 Example 3 Taken for the reaction are 194 g (1.0 g-mol) o~ octylphe-nol (with the characteristic as in Example 1) and 46.6 g (0~333 g-mol) of hex~methylene tetramine. Condensation is con-ducted as in Example 1. Condensation temperature is within the range of from 150 to 165C; reaction time is 20 ~ 25 minutes.
Characteristics of the thus-prepared resin ls given in Table 4.
'
;~v~
Taken for the reaction are 194 g (1.0 g-mol) of octylphe-nol (with the characeeristic of ExamplP 1~ and 23.4 g (00167 g-mol) of hexamethylene tetramine. Condensa~ion without sol-vent is conducted as in Example 1. Condensa~ion time, a~ a temperature of f~om 140 to 165C, is 30 to 35 minutes. Chara-cteristics of the thus-prepared resin are given in Table 3 hereinbelow.
Table 3 Resin Char~cteristics No. P a r a m e t e r V a 1 u e .. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 1. Appearance light-yellow powder 2. ~olecular weight 600 3. Ubbelohde drop point, C 88.5 4. Dumas nitrogen content, % 6.7 5~ Solubility~ g per 100 ml of toluene 81 hexane 67 mixture h~xane~cyclohexane (15:85)75 Example 3 Taken for the reaction are 194 g (1.0 g-mol) o~ octylphe-nol (with the characteristic as in Example 1) and 46.6 g (0~333 g-mol) of hex~methylene tetramine. Condensation is con-ducted as in Example 1. Condensation temperature is within the range of from 150 to 165C; reaction time is 20 ~ 25 minutes.
Characteristics of the thus-prepared resin ls given in Table 4.
'
-7- ~
.
~7~;Z~ -Table 4 Resin Characteristics _ No. P a r a m e t e r s V a 1 u e 1. Appearance light-yellow powder 2. Molecular weigh~ 1084 3O Ubbelohde drop point, C 112~2 4. Du~as nitrogen content~ % 6089 5. Solubility~ g per 100 ml of toluene 77 hexane 61 mix~ure hexane-cyclohexane 515:85) 72 , :
~e~ , Condensation of octylphenol with hexamethylene tetramine .`
(l~MTA~ is conducted as in Examples 1, 2 and 3 at a molar ratio of the reagents of 1:1~ 1:0.13; 1:0.1; 1:0.05; 1:0,02 at a tem- :
perature within the range of from 125 to 160C. Characteristics :;
of the thus-prepared aminophenol resins are given in Table 5.
Table 5 :. :
Resin Characteristics .. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ,. _ _ _ _ _ __ No. Ratio alkylphenols:HMTA Ubbelohde drop point, C
1. 1:1 160 ~ :
2. 1~0~13 78.7 3. 1:0.1 70 4. 1:0.05 viscous liquid ::~
5. 1:0.02 viscous liquid .:
_ _ - ., '~ ,,,
.
~7~;Z~ -Table 4 Resin Characteristics _ No. P a r a m e t e r s V a 1 u e 1. Appearance light-yellow powder 2. Molecular weigh~ 1084 3O Ubbelohde drop point, C 112~2 4. Du~as nitrogen content~ % 6089 5. Solubility~ g per 100 ml of toluene 77 hexane 61 mix~ure hexane-cyclohexane 515:85) 72 , :
~e~ , Condensation of octylphenol with hexamethylene tetramine .`
(l~MTA~ is conducted as in Examples 1, 2 and 3 at a molar ratio of the reagents of 1:1~ 1:0.13; 1:0.1; 1:0.05; 1:0,02 at a tem- :
perature within the range of from 125 to 160C. Characteristics :;
of the thus-prepared aminophenol resins are given in Table 5.
Table 5 :. :
Resin Characteristics .. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ,. _ _ _ _ _ __ No. Ratio alkylphenols:HMTA Ubbelohde drop point, C
1. 1:1 160 ~ :
2. 1~0~13 78.7 3. 1:0.1 70 4. 1:0.05 viscous liquid ::~
5. 1:0.02 viscous liquid .:
_ _ - ., '~ ,,,
-8 .~. ,. ~ . .
7~2~3 Example 5 A mixture containing 17.2 g (0.1 g-mol) of hexylphenol wi~h the molecular weight of 170 and 7 g (0.05 g-mol) of hexa-methylene tetramine are heated in a flask to a temperature of from 140 to 145C under stirring. On completion of ammonia liberation (30 minutes) the reaction mass is poured into a por-celain cup. The resln is rapidly cooled and becomes a solid brlttle amber-coloured product. After di~integration it compri- `~
ses a light-yellow powder with the drop point of 105~C. The `
resln is readily soluble in ben7ene, toluene, hexane, cyclohe-xane. The resin characteristics are given in Table 6.
Table 6 Resin Characteristics NoO P a r a m e t e r s Value ~-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ _ _ _ _ _ _ _ _ _ _ .. _ _ _ 1. Molecular weight 680 2. Ubbelohde drop point, C 105 3. Dumas nitrogen conten~, % 6.2 4, Solubility~ g per 100 ml of ~oluene 72 ,: .
A mixture of 10 g of nonylphenol with the molecular weight of 227 and 1.5 g of hexamethylene tetramlne is heated to 160~C
maintained at 160 - 170C for 2~ minutes and poured lnto a porcelain cup to form a light-yellow melt after cooling; the resin drop point is 118C~ molecular weight 1,400.
~'7f~
Example 7 A mixture of 25 g of dodecylphenol with the molecular weight of 290 and 4 g of hexamethylene tetramine are heated at 150 - 170C for one hour, After cooling~ a melt is obkained having dark-brown colour and drop point of 60C.
Example 8 A mixeure containing 37 g (0~175 g-mol) of cumylphenol (alkylation product of phenol with alpha-methylstyrene) with melting point of 68 - 71C and 4.9 g (00035 g-mol) of hexa~et-hylene tetramine is heated to 135C under stirring. Condensa~
tio~ reaction starting at this temperature is acco~panied by self-heating of the reaction mixture to 150C and vigorous liberation of ammonia. On completion of the reaction evidenced by ~he stoppage of ammonia evolution, the reaction m~xture is poured into a porcelain cupO Cooled resin comprises a solid brittle amber-coloured product. After dislntegration the re~ ~ -sin ls in the fo~m of a light~yellow powder with the drop point of 101C. The yield of resin is 40 gQ The resin is well-soluble in cyclohexane. Characteristics of the resin are given in Table 7 Table 7 Resin Characteristics _ _ _ _ _ _ _ _ _ _ _ Y _ _ _ _ _ _ _ _ _ _ ~ _ _ _ _ _ _ _ _ NoO P a r a m e t e r s Value l. Appearance light-yellow powder 2. Nolecular weight 880 3. Ubbelohde drop point, C lOl 4O Dumas nitrogen conten~, % 4.5 5 Solubility in cyclohexane, g/100 mlover 11 ~10- .
~0~6Z~
Example 9 A mixture of 42 g (0.212 g-mol) of an alkylation product of phenol wieh styrene with a boiling point of from 140 to 150c and molecular weight of 198 and 4.94 g (0.035 g-mol) o~
hexamethylene tetramine in a reaction flask are heated at 130C for 50 minutes. The condensation reaction is accompanied by vigorous liberation of ammonia. After cooling the thus-pre~
pared resin comprises a very viscous liquid of a golden-yellow colour. Moelcular weight of the resin is 5509 nitrogen content 4~ 1%o Exam~le 10 A mixture of 20 g of diphenylolpropane (condensation pro-duct of phenol and aoetone) and 4 g of hexamethylene tetramine are heated at 160C for 30 minutes. Upon cooling a resin is obtained in the form of a brlttle amber~coloured melt with the drop point of 158C.
Example 11 Into a flask provided with a stirrer 23.6 g (0.18 g-mol) of salicyllc acid~ 4 g (0.029 g-mol) of hexamethylene tetrami-ne are charged and heated to 150C. Ammonia evolution is ob-served d~ring the reaction. After 20 minutes the flask con-tents is poured into a porcelain cup~ The reaction mixture is solidified with the ~orma~ion of an amber-coloured mass. ~he thus-prepared product has a drop point of 129.5C and is in-soluble in benzene and toluene~ The resin is soluble in an aqueous solution of sodium hydroxide.
' ~ 62~
Example 12 Into a flask there are charged 10 g (0.072 g-mol~ of sa~
licylic acid, 75 g (0.34 g-mol) of octylphenol and 15 g (0.107 g-mol) of hexamethyle~e tetramineO The reaction mass is heated and maintained at L45C for 120 minutesc The result-ing product ~omprises a melt of amber colour with the drop point of 141C~ Shown in Table 8 are characteristics of carbo~
xyl-containlng phe~olamine resins depending on the content of :~
salicylic acid in the reaction mixture. Most of the resins thus prepared are soluble in an aqueous solution of sodium hydroxyde. . .
Table ô
Charac~eristics of carboxyl-containing phenolamlne resins depending on the content of salicylic acid in the starting :::
mixture No.Salicylic acid Drop Molecular Solubility content~ % point, weight~ in toluene, C(cryoscopic) %
_ 1 0 150 1~200 60 ~ -2 5 139 1~246 3 10 141 1,560 8 131 1.630 6 33 121 - - .
7 50 114 - poor soluble ô 85 129 - insoluble _ _ O _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .0 _ _ _ _ .. _ .. _ _ _ _ ~ , : :
~ .
Into a reaction flask provided with a thermometer and stirrer 60 g (0.4 g~mol) of p-tert.butylphenol, lO g (0.071 ~12_ '' ' ' ~;[)7~Z~
g-mol) of hexamethylene tetramine and 7.8 g (0.056 g-mol) of salicylic acid are charged.
Tha reaction mixture is heated to the temperature of 150C~ The reaction is accompanied by vigorous evolution of ammonia. The mixture is main~ained at 150C for lr5 hours and then is poured, still in a hot conditlon, lnto a cup and the reaction mass is svlidified in the for~ of a solid brittle amber-coloured resin. Drop point is 140C~ ~
~ ,. ':
:
Into a reaction flask provided with a stirrer and thermo-meter 90 g (0.45 g-mol~ of an alkylation product of phenol with styrene (a mixture of phenylethylphenols)~ 15 g (0.107 g-mol) of hexamethylene tetramine and 11~7 g (0.08 g-mol) of salicylic acid are charged~ The mixture is heated on an oil bath to the temperature of 150C. Within the first five minutes of the reaction the reaction mixture is self-heated and ammonia evo-lution is observed. The mixture is maintained for 1.5 hours under stirring and then poured, still in a hot condition, into a cup. The resulting product is solidified to give a solid bri~tle darkamber resin wi~h the drop point of 121C.
Ex ~ 15 A mix~ure oP 78.7 g of octylphenol with the molecular weight of 220~ 7 g of para-hydrobenzoic acid and 14.3 g of hexame~hylene tetramine are heated at 130C for 1 hour. A light gellow melt is poured into a porcelain cup; the resin drop point is 93C.
:~, '.'.
: ' .':
" :' ~13-': '"
~0~t;2~
Example 16 To 16 1 of commercial latex of butadiene alpha-methylsty-rene rubber (analogue of rubber-1712) with the solids content of 20% there are added 7.5 g of the condensation product of octylphenol with hexamethylene tetramine prepared as in Example 1 and 336 g of naphthenoaromatic oil. Separation of rubber is effected by a conventional method using sodium chloride and sulphuric acid.
In a si~ilar manner control samples of rubber with the commercially employed antioxidant system (Neozone D + diphenyl-p-phenylene di~mine (DPPD)~ Wingstey 200 produced by Goodyear (p-phenylene diamine derivative) and phenol-formaldehyde resin are prepared.
Rubber stabillty is evaluated by retainin8 Mooney visco-sity after rolling at 140C for 20 minutes~ Treated by rolling are ~00 g of rubber; clearance between rolls is 1 mm~ roll di-mensions 320 x 160 mm, friction ratio 1:1.2~, Data obtained for different proportions of the antioxidant are shown in Table 9 hereinbelow.
Table 9 Stability of 1712 Type Resin under Contains of Thermomechanical Treatment on Rolls n~
Percen-~ Retained Moo-No. Antioxidant t ney viscosity age after rolling, . .
_ 1. 2 3 4 - :
1. Condensation product of octyl- ~. 0.5 77 : ::
phenol wlth hexamethylene tetramine l.0 76 .
; " .
-14~ ;:
~lO7~2~
2~ Neozone D + 1.2 31 DPPD 0.3 3. Wingstey-200 0,5 33 1.0 47 4. Phenol~formaldehyde (novolac) resin 1.0 47 As it is seen from Table 9, phenolamine resin prepared from octylphenol and hexamethylene te~ramine is considerably superior to phenol-formaldehyde resin and commercial an~ioxi-dants on its stabilizing ~éffectiveness.
ExAamp~le 17, To 200 ~ of but~diene-alpha-methyls~yrene rubber iilled with 15b of an aromatic oil containing 1.2% of Neozone D there are added~ during the rolling operation~ 1 g of a condensation product of nonyl~phenol with hexamethylene tetramine prepared as in Example 6, Samples of the initial rubber with th~ phenol~
amine resin are maintained at 140C for 30 minutes in the air.
Shown in Table 10 hereinbelow are data illustrating initial plasticity and that a~ter ageing (by the Walles method~ and lndex of retained plasticity expressed in per cent~
As i~ is seen fro~ Table 10~ in the presence of the phe~
nolamine resin of the present invention the test rubber retains lts properties practically unchanged~ while the rubber with Neozone D is deeply destructed.
' . ' ~ 7~i2~
Table 10 Retained Walles plasticity of a rubber with a condensa-tion product of nonylphenol with hexamethyle~e tetramine Walles plasti~ Retained plasti, ci~y city index, %
No. Antioxidant ini- after tial ageing .
_ _ ...._ _ _ _ _ ~ . ~ _ _ _ _ _ _ _ _ , _ ._ _ _ _ _ _ ,_ ~ _ 1. Neo~one D 0.23 0.05 27 2~ Condensation product of nonylphenol with hexamethylene tetramine 0022 O.Z0 95 ~E~
Tv a butadiene-styrene rubber filled with 15% of a nap-hthenoaromatic oil is added, during the rolling operation, a phenolamine resin prepared by condensation of hexamethylene tetramine with cumylphenol as in Example 8 hereinabove. Con-' trol samples are filled with a phenol-formaldehyde novolac resin and Neo~one D.
Shown in Table 11 hereinbelow are data illustra~ing al-terna~ion of physico-mechanical properties of a rubber during its ~echanical processing on rolls at the temperature of 140C
for 20 minutes~
The data of Table 11 reveal that the incorporation of the phenolamine resin according ~o the present invent:ion into a rubber makes it possible to substantially increase its sta~
b~ y to a level of retention Defo-hardness as high as ~4C~o ~ " .
.' " ' , .,:. , ~, -16- : .
~6~3 after ageing. Retained Defo-hardness of the rubber under the conditions shown in Table 11 in the presence of Neozone D and a phenol-fo~maldehyde resin is 29%.
Table 11 Rubber Stability under Condition of Thermomechanical Treatment Retained Percen~
No. Antioxidant tage Defo-hard- Reco-ness~ % very,%
.. ~
1. ~eozone D 1~5 29 29 2. Phenol-formaldehyde resin 0.3 29 26 3. Condensation product of cumylphenol with hexamethyl-ene tetramine 0.1 78 88 4~ Ditto 0.3 94 lO0 5. Ditto 0.5 91 lO0 To lO0 g of a butadiene-styrene rubber filled with 15%
of a naphtheno~aromatic oil 0.30 g of a resin prepared by con-densation of hexamethylene tetramine with a mixture of octyl- ~ :
phenol and salicylic acid as ini Exa~ple 11 is added on rolls.
Thermal ageing is effected at 140C for 30 minutes; retai~ :
ned pliasticity index is 90%; f or a control sample containing Neozone ~ in the amoun~ of 1.2% i~ is equal to 45Z~
":'' ~.
' .:
. : ' -'',' : 17 '. ' ' ' .
7~2~3 Example 5 A mixture containing 17.2 g (0.1 g-mol) of hexylphenol wi~h the molecular weight of 170 and 7 g (0.05 g-mol) of hexa-methylene tetramine are heated in a flask to a temperature of from 140 to 145C under stirring. On completion of ammonia liberation (30 minutes) the reaction mass is poured into a por-celain cup. The resln is rapidly cooled and becomes a solid brlttle amber-coloured product. After di~integration it compri- `~
ses a light-yellow powder with the drop point of 105~C. The `
resln is readily soluble in ben7ene, toluene, hexane, cyclohe-xane. The resin characteristics are given in Table 6.
Table 6 Resin Characteristics NoO P a r a m e t e r s Value ~-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ _ _ _ _ _ _ _ _ _ _ .. _ _ _ 1. Molecular weight 680 2. Ubbelohde drop point, C 105 3. Dumas nitrogen conten~, % 6.2 4, Solubility~ g per 100 ml of ~oluene 72 ,: .
A mixture of 10 g of nonylphenol with the molecular weight of 227 and 1.5 g of hexamethylene tetramlne is heated to 160~C
maintained at 160 - 170C for 2~ minutes and poured lnto a porcelain cup to form a light-yellow melt after cooling; the resin drop point is 118C~ molecular weight 1,400.
~'7f~
Example 7 A mixture of 25 g of dodecylphenol with the molecular weight of 290 and 4 g of hexamethylene tetramine are heated at 150 - 170C for one hour, After cooling~ a melt is obkained having dark-brown colour and drop point of 60C.
Example 8 A mixeure containing 37 g (0~175 g-mol) of cumylphenol (alkylation product of phenol with alpha-methylstyrene) with melting point of 68 - 71C and 4.9 g (00035 g-mol) of hexa~et-hylene tetramine is heated to 135C under stirring. Condensa~
tio~ reaction starting at this temperature is acco~panied by self-heating of the reaction mixture to 150C and vigorous liberation of ammonia. On completion of the reaction evidenced by ~he stoppage of ammonia evolution, the reaction m~xture is poured into a porcelain cupO Cooled resin comprises a solid brittle amber-coloured product. After dislntegration the re~ ~ -sin ls in the fo~m of a light~yellow powder with the drop point of 101C. The yield of resin is 40 gQ The resin is well-soluble in cyclohexane. Characteristics of the resin are given in Table 7 Table 7 Resin Characteristics _ _ _ _ _ _ _ _ _ _ _ Y _ _ _ _ _ _ _ _ _ _ ~ _ _ _ _ _ _ _ _ NoO P a r a m e t e r s Value l. Appearance light-yellow powder 2. Nolecular weight 880 3. Ubbelohde drop point, C lOl 4O Dumas nitrogen conten~, % 4.5 5 Solubility in cyclohexane, g/100 mlover 11 ~10- .
~0~6Z~
Example 9 A mixture of 42 g (0.212 g-mol) of an alkylation product of phenol wieh styrene with a boiling point of from 140 to 150c and molecular weight of 198 and 4.94 g (0.035 g-mol) o~
hexamethylene tetramine in a reaction flask are heated at 130C for 50 minutes. The condensation reaction is accompanied by vigorous liberation of ammonia. After cooling the thus-pre~
pared resin comprises a very viscous liquid of a golden-yellow colour. Moelcular weight of the resin is 5509 nitrogen content 4~ 1%o Exam~le 10 A mixture of 20 g of diphenylolpropane (condensation pro-duct of phenol and aoetone) and 4 g of hexamethylene tetramine are heated at 160C for 30 minutes. Upon cooling a resin is obtained in the form of a brlttle amber~coloured melt with the drop point of 158C.
Example 11 Into a flask provided with a stirrer 23.6 g (0.18 g-mol) of salicyllc acid~ 4 g (0.029 g-mol) of hexamethylene tetrami-ne are charged and heated to 150C. Ammonia evolution is ob-served d~ring the reaction. After 20 minutes the flask con-tents is poured into a porcelain cup~ The reaction mixture is solidified with the ~orma~ion of an amber-coloured mass. ~he thus-prepared product has a drop point of 129.5C and is in-soluble in benzene and toluene~ The resin is soluble in an aqueous solution of sodium hydroxide.
' ~ 62~
Example 12 Into a flask there are charged 10 g (0.072 g-mol~ of sa~
licylic acid, 75 g (0.34 g-mol) of octylphenol and 15 g (0.107 g-mol) of hexamethyle~e tetramineO The reaction mass is heated and maintained at L45C for 120 minutesc The result-ing product ~omprises a melt of amber colour with the drop point of 141C~ Shown in Table 8 are characteristics of carbo~
xyl-containlng phe~olamine resins depending on the content of :~
salicylic acid in the reaction mixture. Most of the resins thus prepared are soluble in an aqueous solution of sodium hydroxyde. . .
Table ô
Charac~eristics of carboxyl-containing phenolamlne resins depending on the content of salicylic acid in the starting :::
mixture No.Salicylic acid Drop Molecular Solubility content~ % point, weight~ in toluene, C(cryoscopic) %
_ 1 0 150 1~200 60 ~ -2 5 139 1~246 3 10 141 1,560 8 131 1.630 6 33 121 - - .
7 50 114 - poor soluble ô 85 129 - insoluble _ _ O _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .0 _ _ _ _ .. _ .. _ _ _ _ ~ , : :
~ .
Into a reaction flask provided with a thermometer and stirrer 60 g (0.4 g~mol) of p-tert.butylphenol, lO g (0.071 ~12_ '' ' ' ~;[)7~Z~
g-mol) of hexamethylene tetramine and 7.8 g (0.056 g-mol) of salicylic acid are charged.
Tha reaction mixture is heated to the temperature of 150C~ The reaction is accompanied by vigorous evolution of ammonia. The mixture is main~ained at 150C for lr5 hours and then is poured, still in a hot conditlon, lnto a cup and the reaction mass is svlidified in the for~ of a solid brittle amber-coloured resin. Drop point is 140C~ ~
~ ,. ':
:
Into a reaction flask provided with a stirrer and thermo-meter 90 g (0.45 g-mol~ of an alkylation product of phenol with styrene (a mixture of phenylethylphenols)~ 15 g (0.107 g-mol) of hexamethylene tetramine and 11~7 g (0.08 g-mol) of salicylic acid are charged~ The mixture is heated on an oil bath to the temperature of 150C. Within the first five minutes of the reaction the reaction mixture is self-heated and ammonia evo-lution is observed. The mixture is maintained for 1.5 hours under stirring and then poured, still in a hot condition, into a cup. The resulting product is solidified to give a solid bri~tle darkamber resin wi~h the drop point of 121C.
Ex ~ 15 A mix~ure oP 78.7 g of octylphenol with the molecular weight of 220~ 7 g of para-hydrobenzoic acid and 14.3 g of hexame~hylene tetramine are heated at 130C for 1 hour. A light gellow melt is poured into a porcelain cup; the resin drop point is 93C.
:~, '.'.
: ' .':
" :' ~13-': '"
~0~t;2~
Example 16 To 16 1 of commercial latex of butadiene alpha-methylsty-rene rubber (analogue of rubber-1712) with the solids content of 20% there are added 7.5 g of the condensation product of octylphenol with hexamethylene tetramine prepared as in Example 1 and 336 g of naphthenoaromatic oil. Separation of rubber is effected by a conventional method using sodium chloride and sulphuric acid.
In a si~ilar manner control samples of rubber with the commercially employed antioxidant system (Neozone D + diphenyl-p-phenylene di~mine (DPPD)~ Wingstey 200 produced by Goodyear (p-phenylene diamine derivative) and phenol-formaldehyde resin are prepared.
Rubber stabillty is evaluated by retainin8 Mooney visco-sity after rolling at 140C for 20 minutes~ Treated by rolling are ~00 g of rubber; clearance between rolls is 1 mm~ roll di-mensions 320 x 160 mm, friction ratio 1:1.2~, Data obtained for different proportions of the antioxidant are shown in Table 9 hereinbelow.
Table 9 Stability of 1712 Type Resin under Contains of Thermomechanical Treatment on Rolls n~
Percen-~ Retained Moo-No. Antioxidant t ney viscosity age after rolling, . .
_ 1. 2 3 4 - :
1. Condensation product of octyl- ~. 0.5 77 : ::
phenol wlth hexamethylene tetramine l.0 76 .
; " .
-14~ ;:
~lO7~2~
2~ Neozone D + 1.2 31 DPPD 0.3 3. Wingstey-200 0,5 33 1.0 47 4. Phenol~formaldehyde (novolac) resin 1.0 47 As it is seen from Table 9, phenolamine resin prepared from octylphenol and hexamethylene te~ramine is considerably superior to phenol-formaldehyde resin and commercial an~ioxi-dants on its stabilizing ~éffectiveness.
ExAamp~le 17, To 200 ~ of but~diene-alpha-methyls~yrene rubber iilled with 15b of an aromatic oil containing 1.2% of Neozone D there are added~ during the rolling operation~ 1 g of a condensation product of nonyl~phenol with hexamethylene tetramine prepared as in Example 6, Samples of the initial rubber with th~ phenol~
amine resin are maintained at 140C for 30 minutes in the air.
Shown in Table 10 hereinbelow are data illustrating initial plasticity and that a~ter ageing (by the Walles method~ and lndex of retained plasticity expressed in per cent~
As i~ is seen fro~ Table 10~ in the presence of the phe~
nolamine resin of the present invention the test rubber retains lts properties practically unchanged~ while the rubber with Neozone D is deeply destructed.
' . ' ~ 7~i2~
Table 10 Retained Walles plasticity of a rubber with a condensa-tion product of nonylphenol with hexamethyle~e tetramine Walles plasti~ Retained plasti, ci~y city index, %
No. Antioxidant ini- after tial ageing .
_ _ ...._ _ _ _ _ ~ . ~ _ _ _ _ _ _ _ _ , _ ._ _ _ _ _ _ ,_ ~ _ 1. Neo~one D 0.23 0.05 27 2~ Condensation product of nonylphenol with hexamethylene tetramine 0022 O.Z0 95 ~E~
Tv a butadiene-styrene rubber filled with 15% of a nap-hthenoaromatic oil is added, during the rolling operation, a phenolamine resin prepared by condensation of hexamethylene tetramine with cumylphenol as in Example 8 hereinabove. Con-' trol samples are filled with a phenol-formaldehyde novolac resin and Neo~one D.
Shown in Table 11 hereinbelow are data illustra~ing al-terna~ion of physico-mechanical properties of a rubber during its ~echanical processing on rolls at the temperature of 140C
for 20 minutes~
The data of Table 11 reveal that the incorporation of the phenolamine resin according ~o the present invent:ion into a rubber makes it possible to substantially increase its sta~
b~ y to a level of retention Defo-hardness as high as ~4C~o ~ " .
.' " ' , .,:. , ~, -16- : .
~6~3 after ageing. Retained Defo-hardness of the rubber under the conditions shown in Table 11 in the presence of Neozone D and a phenol-fo~maldehyde resin is 29%.
Table 11 Rubber Stability under Condition of Thermomechanical Treatment Retained Percen~
No. Antioxidant tage Defo-hard- Reco-ness~ % very,%
.. ~
1. ~eozone D 1~5 29 29 2. Phenol-formaldehyde resin 0.3 29 26 3. Condensation product of cumylphenol with hexamethyl-ene tetramine 0.1 78 88 4~ Ditto 0.3 94 lO0 5. Ditto 0.5 91 lO0 To lO0 g of a butadiene-styrene rubber filled with 15%
of a naphtheno~aromatic oil 0.30 g of a resin prepared by con-densation of hexamethylene tetramine with a mixture of octyl- ~ :
phenol and salicylic acid as ini Exa~ple 11 is added on rolls.
Thermal ageing is effected at 140C for 30 minutes; retai~ :
ned pliasticity index is 90%; f or a control sample containing Neozone ~ in the amoun~ of 1.2% i~ is equal to 45Z~
":'' ~.
' .:
. : ' -'',' : 17 '. ' ' ' .
Claims (4)
1. Phenolamine resins containing a fragment of a substi-tuted phenol and methylene amine bridges of the formula:
where X is hydrogen or m and n are from 1 to 20, when X is H, R represents an alkyl radical with 5 to 12 carbon atoms, phenyl-ethyl, cumyl, hydroxyarylalkyl carboxy, when X is R represents an alkyl radical with 1 to 12 carbon atoms, phenylethyl, cumyl, hydroxyarylalkyl, or carboxy com-prising a product of condensation of hexamethylene tetramine with a phenol component selected from the group consisting of an alkylphenol with 5 to 12 carbon atoms in the alkyl radical, styrene-alkylated phenol, cumylphenol, diphenylolpropane, hydroxybenzoic acid and mixtures thereof.
where X is hydrogen or m and n are from 1 to 20, when X is H, R represents an alkyl radical with 5 to 12 carbon atoms, phenyl-ethyl, cumyl, hydroxyarylalkyl carboxy, when X is R represents an alkyl radical with 1 to 12 carbon atoms, phenylethyl, cumyl, hydroxyarylalkyl, or carboxy com-prising a product of condensation of hexamethylene tetramine with a phenol component selected from the group consisting of an alkylphenol with 5 to 12 carbon atoms in the alkyl radical, styrene-alkylated phenol, cumylphenol, diphenylolpropane, hydroxybenzoic acid and mixtures thereof.
2. Phenolamine resins as claimed in claim 1 of the formula:
where R is an alkyl radical with 1 to 12 carbon atoms, phenyl-ethyl, cumyl; m and n are of from 1 to 20, comprising condensa-tion products of hexamethylene tetramine with a mixture of salicylic acid and an alkylphenol with 1 to 12 carbon atoms in the alkyl radical or styrene-alkylated phenol or cumylphenol.
where R is an alkyl radical with 1 to 12 carbon atoms, phenyl-ethyl, cumyl; m and n are of from 1 to 20, comprising condensa-tion products of hexamethylene tetramine with a mixture of salicylic acid and an alkylphenol with 1 to 12 carbon atoms in the alkyl radical or styrene-alkylated phenol or cumylphenol.
3. A method of preparing phenolamine resins as claimed in Claim 1 comprising condensation of hexamethylene tetramine with a phenol component representing an alkylphenol with 5 to 12 carbon atoms in the alkyl radical and a molecular weight of from 160 to 350, styrene-alkylated phenol, cumylphenol, diphenylol-propane, hydroxybenzoic acids or mixtures thereof taken in a molar ratio of from 0.02:1 to 1:1 at a temperature within the range of from 90 to 180°C.
4. A method as claimed in Claim 3, wherein said con-densation is effected with hexamethylene tetramine and a phenol component representing a mixture of salicyclic acid and an alkyl-phenol with 1 to 12 carbon atoms in the alkyl radical taken in a molar ratio of from 0.02:1 to 1:1 at a temperature within the range of from 90 to 180°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU2081749A SU550405A1 (en) | 1974-12-09 | 1974-12-09 | The method of obtaining phenolamine resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076289A true CA1076289A (en) | 1980-04-22 |
Family
ID=20602782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,136A Expired CA1076289A (en) | 1974-12-09 | 1975-09-23 | Method of preparing phenolamine resins |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5270000A (en) |
| CA (1) | CA1076289A (en) |
| CS (1) | CS184981B1 (en) |
| DE (1) | DE2543649B2 (en) |
| FR (1) | FR2294204A1 (en) |
| RO (1) | RO71676A (en) |
| SU (1) | SU550405A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8841485B2 (en) | 2010-07-27 | 2014-09-23 | Sumitomo Bakelite Co., Ltd. | Liquid phenol resin and method of preparing the same |
| US9657139B2 (en) | 2011-01-14 | 2017-05-23 | Sumitomo Bakelite Co., Ltd. | Liquid resol-type phenolic resin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103596789B (en) | 2011-04-04 | 2016-10-26 | 舍弗勒技术股份两合公司 | For transmitting the device of torque |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3228899A (en) * | 1961-07-10 | 1966-01-11 | Monsanto Co | Phenolic resins from styrene, phenol and a vegetable drying oil |
| US3321434A (en) * | 1966-06-16 | 1967-05-23 | Minnesota Mining & Mfg | Saturation of porous material with solution of phenolic compound and hexamethylenetetramine in solvent containing acetic acid, propionic acid or mixtures thereof |
| CH579602A5 (en) * | 1972-06-21 | 1976-09-15 | Hoechst Ag |
-
1974
- 1974-12-09 SU SU2081749A patent/SU550405A1/en active
-
1975
- 1975-09-23 CA CA236,136A patent/CA1076289A/en not_active Expired
- 1975-09-30 DE DE2543649A patent/DE2543649B2/en not_active Withdrawn
- 1975-09-30 RO RO7583486A patent/RO71676A/en unknown
- 1975-10-08 FR FR7530821A patent/FR2294204A1/en active Granted
- 1975-10-14 CS CS7500006930A patent/CS184981B1/en unknown
- 1975-12-08 JP JP50145184A patent/JPS5270000A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8841485B2 (en) | 2010-07-27 | 2014-09-23 | Sumitomo Bakelite Co., Ltd. | Liquid phenol resin and method of preparing the same |
| US9657139B2 (en) | 2011-01-14 | 2017-05-23 | Sumitomo Bakelite Co., Ltd. | Liquid resol-type phenolic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2543649A1 (en) | 1976-06-10 |
| JPS5270000A (en) | 1977-06-10 |
| CS184981B1 (en) | 1978-09-15 |
| SU550405A1 (en) | 1977-03-15 |
| DE2543649B2 (en) | 1981-02-26 |
| FR2294204B1 (en) | 1981-09-18 |
| RO71676A (en) | 1982-09-09 |
| FR2294204A1 (en) | 1976-07-09 |
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