CA2024121A1 - Process for the production of rubbers - Google Patents
Process for the production of rubbersInfo
- Publication number
- CA2024121A1 CA2024121A1 CA 2024121 CA2024121A CA2024121A1 CA 2024121 A1 CA2024121 A1 CA 2024121A1 CA 2024121 CA2024121 CA 2024121 CA 2024121 A CA2024121 A CA 2024121A CA 2024121 A1 CA2024121 A1 CA 2024121A1
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- Prior art keywords
- rubbers
- weight
- phenol
- acid
- phenols
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A PROCESS FOR THE PRODUCTION OF RUBBERS
A b s t r a c t The invention relates to a process for the production of rubbers containing phenolic OH groups and to the rubbers obtainable by the process according to the invention.
A b s t r a c t The invention relates to a process for the production of rubbers containing phenolic OH groups and to the rubbers obtainable by the process according to the invention.
Description
202~121 '..
A PROCESS FOR THE PRODUCTION OF RUBBERS
This invention relates to a process for the production of a rubber containing 5 to 60 and preferably 5 to 40 phenolic OH groups, characterized in that rubbers contain-lng 3 to 250 and preferably 3 to 10 double bonds per 1,000 S carbon atoms in the rubber are reacted in bulk with phen-018, optionally in the presence of a catalyst, for 1 minute to 30 ~inutes at temperatures of 50 to 150-C and preferably at temperatures of 70 to 130-C. The reaction product is --cooled and granulated in the usual way.
The invention also relates to the rubbers obtainable by the process according to the invention. ~ ~
' ' ';.`; ., , ,:
prior Art ~ -,. . , .. .. -lS Hydrocarbon polymers bearing hydroxyphenyl-terminated hydrocarbon chains in the end position or as grafted-on side chains are known from JA 63/268 703. They are pro-duced, ~or example, from hydrogenated polybutadiene con-taining alcoholic OH groups and methyl salicylate in the presence of p-toluenesulfonic acid. However, the terminal bydroxyphenyl groups may also be introduced during the synthesis of the hydrocarbon chains by anionic polymeriza-tion of dienes with incorporation of p-hydroxystyrene of which the hydroxy group is temporarily masked.
JA 52/009 098 (only available as an abstract) de-scribes reaction products of rubbers with phenols in the `~ presence of Friedel-Crafts catalysts which are reacted to polyp~enylene oxides by oxidative coupling.
Hydrocarbon resin~polyphenylene ether comb polymers are known from DE-OS 3 509 093 and from EP-A O 195 199.
These comb polymers are produced by reaction of hydrocarbon resins, i.e. rubbers, with phenols in the presence of an acid (see page 8 of DE-OS 3 509 093).
Le A 26 793 ~. 2 ~ ~ 4 ~ 2 ~
; ,.-It can be seen from Example 1 of DE-OS 3 509 093 that the reaction takes place in solution.
However, acid-catalyzed reactions such as these in solution have the disadvantage that the phenols are poly-alkylated in the ring by the unsaturated groups of the hydrocarbon resins.
$o avoid this, special phenol s which can only be alkylated once on account of their particular substitution are used in accordance with DE-OS 3 509 093 and ~P-A O 195 199 (cf. the phenols (IV) on page 8 and in claim 1 of DE-OS 3 509 093)-Corresponding reaction products of hydrocarbon resins with phenols are known from EP-A O 236 554. In this case, too, the reaction i6 only described in solution. It was ~ -again found (cf. the "Makromol. Chem. 24, 205 ç~ ~ç~
~1972), more particularly page 212, cited on page 3 of EP-A-O 236 554) that polyalkylation occurs and leads to -crosslinking of the products. It has now surprisingly been found that ~ven polyalkylatable pbenols, i.e. phenols unsubstituted in at least two ortho and/or para positions, can be attached to rubbers without crosslinking.
S~uitable phenols for the process according to the invention are, preferably, phenols corre~ponding to formula (I) R2~__~RI
~)H (I) ;;
in which R" R2 and R3, independently of one another, may be the same or different and represent H, Cll2 alkyl, cyclohexyl, phenyl, C~.l2 alkoxy, C~ alkyl phenyl, phen-Cl.6-alkyl, fluorine or chlorine. In addition, Rl and Rz may form a cycloaliphatic or aromat~c, fused 6-membered ring.
Other preferred phenols for the proces6 according to .
Le A 26 793 2 ;
202412t .. . .
the invention are phenols corresponding to formula (II) ~ R 1 Y¦ ~ H~
l ~3 m in which R~ to R~ are as defined for formula (I), m - 1 or 2 and Y i8 a raaical-reactive group In the context of the invention, the radical-reactive group Y 1~ preferably an alkenyl group, an HS group, an alkylmercaptan ~roup or a poly~ulflde bridge containing in particular 2 to 8 S atoms Suitable phenols corresponding to formula (I) are, for example, phenol chlorophenola, such as 2-chlorophenol, 3~
ohlorophenol, 4-chlorophenolf 2,5-dichlorophenol alkyl-ph-nols, ~uch as technical cresol, 2-methylphenol, 3-~othylph-nol, 4-methylph-nol, 2,3-dimethylphenol, 3,4-dim thylphenol, 3,5-di~ethylphenol, 2,5-dimethylphenol, ;
ao ; 2,3,S-trimethylphenol, 2-ethylphenol, 2-isopropylphenol, 3-ethyl-S-methylph-nol, 2-soc -butylphenol, 2-tert -butyl-phenol~ 4-t-rt -butylph-nol, 2-lsopropyl-S-methylphenol, 3- ~ ~
lsopropyl-5-methylphenol~4-tert~-pentylphenol~4-~ 3~3- ; ~ ;-tetramethylbutyl)-phenol, nonylphenol, dodecylphenol 4-25 ~ cyolohexylphenol, 2-oyclohexylphenol,; 2-phenylphenol, 4- ;;;
phenylphenol, 3-phenylphenol; 5,6,7,8-tetrahydro-1-naph-thol, 1,1,3,3-tetramethyl-5-indanol, l-naphthol, l-anthrol;
benzylphenol; 3-methoxyphenol, 2-methoxyphenol, 2-ethoxy-' iphenol, 2-isopropoxyphenol and 4-methoxyphenol ; ~ 30Suitable phenolsi corresponding to formula (II) are, `;i -for example, 4-moraaptouhenol, 4-methylmercaptophenol; bis- - i~ ;
;~ (4-hydroxyphonyl)-dlsulfido, bl~i-(4-hydroxyphenylj-trisul- ;; i fide, bisi-~4-hydroxy-3-methylphenyl)-disulfide, 4-vinyl- ` i phonol, 2-methyl-4-vinylphonol, 3-methyl-4-vinylphenol, 4- ` ;
;~ ~3Sisoproponylphenol, 2-methyl-4-i~opropenylphenol and 4-(1-Le A 26 793 3 , .:. .,;~ . .. .
' "i'~,.,','-'' :.,"
: ` 20~2~
' - .
buten-2-yl)-phenol.
Preferred phenols corresponding to formulae (I) and (II) are phenol, 2-methylphenol, 3-methylphenol, 4-methyl-phenol, naphthol, 4-isopropenylphenol and bis-(4-hydroxy-phenyl)-disulfide. ~ ;
Phenol is particularly preferred.
Catalysts suitable for the reaction with the phenols corresponding to formula (I) are protonic acids, such as for example sulfuric acid, phosphoric acid, phosphorous acid, hydrogen halides, perchloric acid or strong organic acids, such as alkyl or aryl sulfonic acid, such as me-thanesulfonic acid, 2-chloroethanesulfonic acid, trifluoro- -methanesulfonic acid, perfluorobutane-1-sulfonic acid, benzenesulfonic acid~, toluenesulfonic acid, naphthalenesul-lS fonic acid, 1,3-benzenedisulfonic acid and benzylsulfonic acld; formic acid, acetic acid, trichloroacetic acid or ~ewis acids, ouch as for example boron trifluoride, alumin-ium chloride, zinc chloride, iron(III) chloride, tin tetrachloride, titanium(IV) chloride or mixtures of the catalysts mentioned.
Catalysts suitable for the reaction with the phenols corresponding to formula (II) are azo compounds, such as for example azo-bis-isobutyronitrile, 2,2'-azo-bis-(2,4-dimethylvaleronitrile),(l-phenylethyl)-azodiphenylmethane, dimethyl-2,2'-azo-bis-isobutyrate, l,l'-azo-bis-(l-cyclo-hexanecarbonitrile),2,2'-azo-bis-(2,4,4-trimethylpentane), 2,2'-azo-bis-(2-methylpropane), or organic peroxides, such as for example diacyl peroxides, such as dilauroyl per~
oxide, diacetyl peroxide, dibenzoyl peroxide; peroxydicar-bonates, such as diacetyl peroxydicarbonate; alkyl per-esters, such as tert.-butyl per-2-ethyl hexanoate, tert.-butyl perisononanoate, tert.-butyl perbenzoate; dialkyl peroxides, such as dicumyl peroxide, di-tert.-butyl per-oxide, di-(tert.-butylperoxyisopropyl)-benzene; alkyl hydroperoxides, such as cumenehydroperoxide, tert.-butyl Le A 26 793 4 ~- 2~%~21 :
.
bydroperoxide or perketals and ketone peroxides, such as 2,2-bis-(tert.-butylperoxy)-butane and methylethyl ketone peroxide.
Preferred catalysts for phenols corresponding to formula (I) are alkyl and aryl sulfonic acids, methanesul-fonic acid being particularly preferred.
The quantity of catalyst used depends on the type and quantity of phenol, the reactivity of the rubber used and the desired phenol content of the end product and is from 0 to 0.2 mol and preferably from 0.05 to 0.1 mol per mol phenol. There is no need for the catalyst if the phenol used ha~ suffiaient acid strength. The reaction with the reactive phenols is generally carried out in the absence of catalysts by thermal activation of the reactive substit-uent~.
a large number of rubbers may be provided with hydrox-yphenyl groups by the described process.
Natural or ~ynthetic rubbers having an Mn of greater than 40,000 and preferably in the range from 40,000 to 200,000, or mixtures thereof, may be used for the process aocord~ng to the invent~on. Homopolymers of a diene, copolymers o~ at least two con~ugated dienes, copolymers of at least one con~ugated diene and at least one other olefinic monomer, polymers obtained by ring-opening poly-merization of a cycloolefin, copolymers of a cyclic, uncon-~ugated diene and at least one other olefinic monomer, polymers obtained by partial hydrogenation of the above-mentioned polymers, or mixtures thereof, may be used. More particularly, suitable rubbers are natural rubber, syn-thetic rubbers, such as polybutadiene, styrene/butadiene rubbers, acrylonitrile/butadiene rubbers, partly hydrogen-ated acrylonitrile/butadiene rubbers, polychloroprene, isoprene/isobutylene rubbers, halogenated copolymers of isoprene and isobutylene, ethylene/propylene/diene rubber~
propylene oxide/allyl glycidyl ether copolymers, polyocten-, .~ .:
Le A 26 793 ~ ~ ~`'~
202~.t21 ; ~:
' : , : ' : -ylene and polynonbornene.
It is preferred to use polymers in the form of a terpolymer of 20 to 60% by weight propene, 40 to 80% by weight ethene and 1.5 to 13% by weight of a C~ 2~ diene, 5preferably a 5-alkylidene-2-norbornene, in which the al~cylidene group contains 2 to 5 carbon atoms, having a molecular weight Mn of greater than 40,000.
Copolymers of 55 to 85S by weight butadiene and 15 to ;
45% by weight acrylonitrile, in which 90 to 999~ of the 10double bonds present have been saturated by hydrogenation, are also preferred. Within this group, copolymers of 55 to 70% by weight butadiene and 30 to 45% by weight acrylo-nitrile, in which 93 to 97% of the double bonds present have been saturated by hydrogenation, are particularly lSpr-f-rred.
Particularly suitable rubbers according to the inven- ~;
tion are rubbers having Mooney viscosities of at least 30 and pr-fe,rably 30 to 150 (as measured in accordance with DIN 53 523 (Part 1-3); ASTM-D 1646-74 at 100-C) in addition 20to the required Mn of at least 40,000 and preferably 40,000 to 200,000.
F~r the process according to the invention, the ratio of phenols to rubbers ahould be gauged in such a way that 1 to 5 phenolic OH is used in the reaction mixture for 25every phenolic OH group in the reaction product.
The process according to the invention is carried out in the absence of a solvent by intensive mixing of the components. Mixing is carried out in a mixing unit of the -kind typically used in the processing of rubber or plas-30tics, including for example reaction screws, extruders or knoaders. The reaction time is between 1 and 30 minutes.
After the reaction, excess phenol, if any, may be removed in a vacuum stage, by stripping with steam or by extraction with a solvent.
35The mixing temperature is between 50 and 150-C and Le A 26 793 6 -r~ 202~1:121 I
preferably between 70 and 130-C. The reaction product i8 cooled and may then be granulated or compacted in known manner.
The following substances known EÇL se may be used as S additional additives during or after the reaction according to the invention: stabilizers, such as antiagers, anti-fatigue agents and anti-ozonants, plasticizers, fillers, pigments, factices, release agents or powdering agents and the vulcanization auxiliaries typically used in the rubber industry.
The rubbers obtainable by the process according to the -~
invention may be vulcanized to moldings of any kind by standard methods of vulcanization.
The moldings obtained, for example in the form of lS s-als, may be industrially used in the same way as normal rubber articles. ~
However, the rubbers obtainable in accordance with the ~ -lnv-ntion may al-o be used without preliminary vulcaniza-tion as a mixing component in other rubbers, for example to improve their tackiness. - ;; v , ,; , :: .
' ~ ,;,.; ",:,.. ' ;'.,. ;:, ~3xamDle-s " ,': ' " i, :,.~ '`: ' :"
Exam~le 1 ; 25 ~ In a twin-screw extruder equipped in its end zone with i ~`
;~ a vacuum evaporation unit to remove the excess phenol, an EPDM resin (copolymer consisting of 50% by weight ethylene, ~ -41% by weight propylene and 9% by weight 5-ethylidene- -bicyclo-(2.2.1)-hept-2-ene, Mooney viscosity ML (1+4) at ~1 ;~ ~ lOO'C - gO, Mn approx. 95,000) i5 mixed with 9% by weight ~ -of a mixture o~ phenol and methanesulfonic acid (99:1) at a cylinder temperature of 90-C. The exit temperature is -~
approx. 120'C and the average residence time to the vacuum `~
stage approx. 12 minutes. The issuing strand is passed ; ;~
- - ,-: . " , Le A 26 793 7 : ~
~ 2024121 through a water bath, air-dried and then granulated with addition of 1% by weight talcum. According to IR measure-ments, the bound phenol content is 2.8 to 3.2% by weight.
The free-flowing granules dissolve without gel formation and can be sheeted out.
EX~1Ç 2 An EPDM resin (copolymer consisting of 68% by weight ethylene, 27% by weight propylene and 5% by weight 5-ethylidenebicyclo-(2.2.1)-hept-2-ene, Mooney viscosity ML
(114) at lOO-C - 85, Mn approx. so,ooO) is treated as in Example 1. In~tead of talcum, however, bisphenol A poly-¢arbonate powder i8 used for powdering. According to IR
measuremQnts, the bound phenol content is 1.9 to 2.5% by woight. The product dissolves without gel formation and can be sheeted out.
~' '.
Example 2 is repeated without the addition of powder-lng agents. The granules remain free-flowinq through rapid cooling to approx. 20-C.
ExamDle 4 10% by weight bisphenol A polycarbonate powder is added to the EPDM resin of Example 1 during introduction into the screws. The granules obtained remain free-flowing without powdering.
~xample 5 800 g of the EPDM resin of Example 1 are masticated in a 1.3 liter Pomini kne~der at a ~acket temperature of 60~C
and at a rotational speed of 40 l/minute. After 1 minute, 72 g phenol, 7.2 g methanesulfonic acid and another 100 g EPDM resin are added and mixed for another 8 minutes. The melt temperature rises to 90 - lOO'C. The product i9 Le A 26 793 8 ~ 20241~
. ....
ejected into a water bath. After removal of the excess phenol by extraction with toluene/methanol, the bound phenol content is 3.2% by weight, as determined by IR
6pectroscopy. The product dissolves without gel formation S and ean be sheeted out.
Exam, D~6 A total of 900 g of an HNBR resin (copolymer of 43% by weight aerylonitrile and 57% by weight butadiene, Nooney viseosity ML (1+4) at lOO-C - 75, Nn approx. 70,000, r-dueed by hydrogenation to 4~ of the original double bond eontent) are treated as in Example 4. The bound phenol eontent is 3.8~ by weight, a- determined by IR spectro~
~eopy. The produet di~-olves without gel formation and ean lS b- ~heeted out.
`.:,: " ' ExamDle 7 2.12 g b1--(4-hydroxyphenyl)-di-ulfide are added to, and mixed for 10 minutes with, 45 g of the EPDM resin of Exampl- 1 in a 70 ml kn-ader at a ~aeket temperature of 120-C and at a rotational speed of S0 l/min. The erude produot i~ xtraeted with tolu-ne/ethanol: the ¢ontent of phenolie group- i- 2.8% by weight, as determined by IR-speetroseopy.
ExamDle 8 2.3 g isopropenyl phenol are added to, and mixed for 0 minutes with, 45 g of the EPDM resin of Examplell inla '`` 70 ml kneader at a jacket temperature of 120-C and at a rotational speed of S0 l/min. The crude product is ex-traeted with toluene/ethanol; the content of phenolic group- ls 1.7% by weight, a- determined by IR-spectroscopy.
Le A 26 793 9
A PROCESS FOR THE PRODUCTION OF RUBBERS
This invention relates to a process for the production of a rubber containing 5 to 60 and preferably 5 to 40 phenolic OH groups, characterized in that rubbers contain-lng 3 to 250 and preferably 3 to 10 double bonds per 1,000 S carbon atoms in the rubber are reacted in bulk with phen-018, optionally in the presence of a catalyst, for 1 minute to 30 ~inutes at temperatures of 50 to 150-C and preferably at temperatures of 70 to 130-C. The reaction product is --cooled and granulated in the usual way.
The invention also relates to the rubbers obtainable by the process according to the invention. ~ ~
' ' ';.`; ., , ,:
prior Art ~ -,. . , .. .. -lS Hydrocarbon polymers bearing hydroxyphenyl-terminated hydrocarbon chains in the end position or as grafted-on side chains are known from JA 63/268 703. They are pro-duced, ~or example, from hydrogenated polybutadiene con-taining alcoholic OH groups and methyl salicylate in the presence of p-toluenesulfonic acid. However, the terminal bydroxyphenyl groups may also be introduced during the synthesis of the hydrocarbon chains by anionic polymeriza-tion of dienes with incorporation of p-hydroxystyrene of which the hydroxy group is temporarily masked.
JA 52/009 098 (only available as an abstract) de-scribes reaction products of rubbers with phenols in the `~ presence of Friedel-Crafts catalysts which are reacted to polyp~enylene oxides by oxidative coupling.
Hydrocarbon resin~polyphenylene ether comb polymers are known from DE-OS 3 509 093 and from EP-A O 195 199.
These comb polymers are produced by reaction of hydrocarbon resins, i.e. rubbers, with phenols in the presence of an acid (see page 8 of DE-OS 3 509 093).
Le A 26 793 ~. 2 ~ ~ 4 ~ 2 ~
; ,.-It can be seen from Example 1 of DE-OS 3 509 093 that the reaction takes place in solution.
However, acid-catalyzed reactions such as these in solution have the disadvantage that the phenols are poly-alkylated in the ring by the unsaturated groups of the hydrocarbon resins.
$o avoid this, special phenol s which can only be alkylated once on account of their particular substitution are used in accordance with DE-OS 3 509 093 and ~P-A O 195 199 (cf. the phenols (IV) on page 8 and in claim 1 of DE-OS 3 509 093)-Corresponding reaction products of hydrocarbon resins with phenols are known from EP-A O 236 554. In this case, too, the reaction i6 only described in solution. It was ~ -again found (cf. the "Makromol. Chem. 24, 205 ç~ ~ç~
~1972), more particularly page 212, cited on page 3 of EP-A-O 236 554) that polyalkylation occurs and leads to -crosslinking of the products. It has now surprisingly been found that ~ven polyalkylatable pbenols, i.e. phenols unsubstituted in at least two ortho and/or para positions, can be attached to rubbers without crosslinking.
S~uitable phenols for the process according to the invention are, preferably, phenols corre~ponding to formula (I) R2~__~RI
~)H (I) ;;
in which R" R2 and R3, independently of one another, may be the same or different and represent H, Cll2 alkyl, cyclohexyl, phenyl, C~.l2 alkoxy, C~ alkyl phenyl, phen-Cl.6-alkyl, fluorine or chlorine. In addition, Rl and Rz may form a cycloaliphatic or aromat~c, fused 6-membered ring.
Other preferred phenols for the proces6 according to .
Le A 26 793 2 ;
202412t .. . .
the invention are phenols corresponding to formula (II) ~ R 1 Y¦ ~ H~
l ~3 m in which R~ to R~ are as defined for formula (I), m - 1 or 2 and Y i8 a raaical-reactive group In the context of the invention, the radical-reactive group Y 1~ preferably an alkenyl group, an HS group, an alkylmercaptan ~roup or a poly~ulflde bridge containing in particular 2 to 8 S atoms Suitable phenols corresponding to formula (I) are, for example, phenol chlorophenola, such as 2-chlorophenol, 3~
ohlorophenol, 4-chlorophenolf 2,5-dichlorophenol alkyl-ph-nols, ~uch as technical cresol, 2-methylphenol, 3-~othylph-nol, 4-methylph-nol, 2,3-dimethylphenol, 3,4-dim thylphenol, 3,5-di~ethylphenol, 2,5-dimethylphenol, ;
ao ; 2,3,S-trimethylphenol, 2-ethylphenol, 2-isopropylphenol, 3-ethyl-S-methylph-nol, 2-soc -butylphenol, 2-tert -butyl-phenol~ 4-t-rt -butylph-nol, 2-lsopropyl-S-methylphenol, 3- ~ ~
lsopropyl-5-methylphenol~4-tert~-pentylphenol~4-~ 3~3- ; ~ ;-tetramethylbutyl)-phenol, nonylphenol, dodecylphenol 4-25 ~ cyolohexylphenol, 2-oyclohexylphenol,; 2-phenylphenol, 4- ;;;
phenylphenol, 3-phenylphenol; 5,6,7,8-tetrahydro-1-naph-thol, 1,1,3,3-tetramethyl-5-indanol, l-naphthol, l-anthrol;
benzylphenol; 3-methoxyphenol, 2-methoxyphenol, 2-ethoxy-' iphenol, 2-isopropoxyphenol and 4-methoxyphenol ; ~ 30Suitable phenolsi corresponding to formula (II) are, `;i -for example, 4-moraaptouhenol, 4-methylmercaptophenol; bis- - i~ ;
;~ (4-hydroxyphonyl)-dlsulfido, bl~i-(4-hydroxyphenylj-trisul- ;; i fide, bisi-~4-hydroxy-3-methylphenyl)-disulfide, 4-vinyl- ` i phonol, 2-methyl-4-vinylphonol, 3-methyl-4-vinylphenol, 4- ` ;
;~ ~3Sisoproponylphenol, 2-methyl-4-i~opropenylphenol and 4-(1-Le A 26 793 3 , .:. .,;~ . .. .
' "i'~,.,','-'' :.,"
: ` 20~2~
' - .
buten-2-yl)-phenol.
Preferred phenols corresponding to formulae (I) and (II) are phenol, 2-methylphenol, 3-methylphenol, 4-methyl-phenol, naphthol, 4-isopropenylphenol and bis-(4-hydroxy-phenyl)-disulfide. ~ ;
Phenol is particularly preferred.
Catalysts suitable for the reaction with the phenols corresponding to formula (I) are protonic acids, such as for example sulfuric acid, phosphoric acid, phosphorous acid, hydrogen halides, perchloric acid or strong organic acids, such as alkyl or aryl sulfonic acid, such as me-thanesulfonic acid, 2-chloroethanesulfonic acid, trifluoro- -methanesulfonic acid, perfluorobutane-1-sulfonic acid, benzenesulfonic acid~, toluenesulfonic acid, naphthalenesul-lS fonic acid, 1,3-benzenedisulfonic acid and benzylsulfonic acld; formic acid, acetic acid, trichloroacetic acid or ~ewis acids, ouch as for example boron trifluoride, alumin-ium chloride, zinc chloride, iron(III) chloride, tin tetrachloride, titanium(IV) chloride or mixtures of the catalysts mentioned.
Catalysts suitable for the reaction with the phenols corresponding to formula (II) are azo compounds, such as for example azo-bis-isobutyronitrile, 2,2'-azo-bis-(2,4-dimethylvaleronitrile),(l-phenylethyl)-azodiphenylmethane, dimethyl-2,2'-azo-bis-isobutyrate, l,l'-azo-bis-(l-cyclo-hexanecarbonitrile),2,2'-azo-bis-(2,4,4-trimethylpentane), 2,2'-azo-bis-(2-methylpropane), or organic peroxides, such as for example diacyl peroxides, such as dilauroyl per~
oxide, diacetyl peroxide, dibenzoyl peroxide; peroxydicar-bonates, such as diacetyl peroxydicarbonate; alkyl per-esters, such as tert.-butyl per-2-ethyl hexanoate, tert.-butyl perisononanoate, tert.-butyl perbenzoate; dialkyl peroxides, such as dicumyl peroxide, di-tert.-butyl per-oxide, di-(tert.-butylperoxyisopropyl)-benzene; alkyl hydroperoxides, such as cumenehydroperoxide, tert.-butyl Le A 26 793 4 ~- 2~%~21 :
.
bydroperoxide or perketals and ketone peroxides, such as 2,2-bis-(tert.-butylperoxy)-butane and methylethyl ketone peroxide.
Preferred catalysts for phenols corresponding to formula (I) are alkyl and aryl sulfonic acids, methanesul-fonic acid being particularly preferred.
The quantity of catalyst used depends on the type and quantity of phenol, the reactivity of the rubber used and the desired phenol content of the end product and is from 0 to 0.2 mol and preferably from 0.05 to 0.1 mol per mol phenol. There is no need for the catalyst if the phenol used ha~ suffiaient acid strength. The reaction with the reactive phenols is generally carried out in the absence of catalysts by thermal activation of the reactive substit-uent~.
a large number of rubbers may be provided with hydrox-yphenyl groups by the described process.
Natural or ~ynthetic rubbers having an Mn of greater than 40,000 and preferably in the range from 40,000 to 200,000, or mixtures thereof, may be used for the process aocord~ng to the invent~on. Homopolymers of a diene, copolymers o~ at least two con~ugated dienes, copolymers of at least one con~ugated diene and at least one other olefinic monomer, polymers obtained by ring-opening poly-merization of a cycloolefin, copolymers of a cyclic, uncon-~ugated diene and at least one other olefinic monomer, polymers obtained by partial hydrogenation of the above-mentioned polymers, or mixtures thereof, may be used. More particularly, suitable rubbers are natural rubber, syn-thetic rubbers, such as polybutadiene, styrene/butadiene rubbers, acrylonitrile/butadiene rubbers, partly hydrogen-ated acrylonitrile/butadiene rubbers, polychloroprene, isoprene/isobutylene rubbers, halogenated copolymers of isoprene and isobutylene, ethylene/propylene/diene rubber~
propylene oxide/allyl glycidyl ether copolymers, polyocten-, .~ .:
Le A 26 793 ~ ~ ~`'~
202~.t21 ; ~:
' : , : ' : -ylene and polynonbornene.
It is preferred to use polymers in the form of a terpolymer of 20 to 60% by weight propene, 40 to 80% by weight ethene and 1.5 to 13% by weight of a C~ 2~ diene, 5preferably a 5-alkylidene-2-norbornene, in which the al~cylidene group contains 2 to 5 carbon atoms, having a molecular weight Mn of greater than 40,000.
Copolymers of 55 to 85S by weight butadiene and 15 to ;
45% by weight acrylonitrile, in which 90 to 999~ of the 10double bonds present have been saturated by hydrogenation, are also preferred. Within this group, copolymers of 55 to 70% by weight butadiene and 30 to 45% by weight acrylo-nitrile, in which 93 to 97% of the double bonds present have been saturated by hydrogenation, are particularly lSpr-f-rred.
Particularly suitable rubbers according to the inven- ~;
tion are rubbers having Mooney viscosities of at least 30 and pr-fe,rably 30 to 150 (as measured in accordance with DIN 53 523 (Part 1-3); ASTM-D 1646-74 at 100-C) in addition 20to the required Mn of at least 40,000 and preferably 40,000 to 200,000.
F~r the process according to the invention, the ratio of phenols to rubbers ahould be gauged in such a way that 1 to 5 phenolic OH is used in the reaction mixture for 25every phenolic OH group in the reaction product.
The process according to the invention is carried out in the absence of a solvent by intensive mixing of the components. Mixing is carried out in a mixing unit of the -kind typically used in the processing of rubber or plas-30tics, including for example reaction screws, extruders or knoaders. The reaction time is between 1 and 30 minutes.
After the reaction, excess phenol, if any, may be removed in a vacuum stage, by stripping with steam or by extraction with a solvent.
35The mixing temperature is between 50 and 150-C and Le A 26 793 6 -r~ 202~1:121 I
preferably between 70 and 130-C. The reaction product i8 cooled and may then be granulated or compacted in known manner.
The following substances known EÇL se may be used as S additional additives during or after the reaction according to the invention: stabilizers, such as antiagers, anti-fatigue agents and anti-ozonants, plasticizers, fillers, pigments, factices, release agents or powdering agents and the vulcanization auxiliaries typically used in the rubber industry.
The rubbers obtainable by the process according to the -~
invention may be vulcanized to moldings of any kind by standard methods of vulcanization.
The moldings obtained, for example in the form of lS s-als, may be industrially used in the same way as normal rubber articles. ~
However, the rubbers obtainable in accordance with the ~ -lnv-ntion may al-o be used without preliminary vulcaniza-tion as a mixing component in other rubbers, for example to improve their tackiness. - ;; v , ,; , :: .
' ~ ,;,.; ",:,.. ' ;'.,. ;:, ~3xamDle-s " ,': ' " i, :,.~ '`: ' :"
Exam~le 1 ; 25 ~ In a twin-screw extruder equipped in its end zone with i ~`
;~ a vacuum evaporation unit to remove the excess phenol, an EPDM resin (copolymer consisting of 50% by weight ethylene, ~ -41% by weight propylene and 9% by weight 5-ethylidene- -bicyclo-(2.2.1)-hept-2-ene, Mooney viscosity ML (1+4) at ~1 ;~ ~ lOO'C - gO, Mn approx. 95,000) i5 mixed with 9% by weight ~ -of a mixture o~ phenol and methanesulfonic acid (99:1) at a cylinder temperature of 90-C. The exit temperature is -~
approx. 120'C and the average residence time to the vacuum `~
stage approx. 12 minutes. The issuing strand is passed ; ;~
- - ,-: . " , Le A 26 793 7 : ~
~ 2024121 through a water bath, air-dried and then granulated with addition of 1% by weight talcum. According to IR measure-ments, the bound phenol content is 2.8 to 3.2% by weight.
The free-flowing granules dissolve without gel formation and can be sheeted out.
EX~1Ç 2 An EPDM resin (copolymer consisting of 68% by weight ethylene, 27% by weight propylene and 5% by weight 5-ethylidenebicyclo-(2.2.1)-hept-2-ene, Mooney viscosity ML
(114) at lOO-C - 85, Mn approx. so,ooO) is treated as in Example 1. In~tead of talcum, however, bisphenol A poly-¢arbonate powder i8 used for powdering. According to IR
measuremQnts, the bound phenol content is 1.9 to 2.5% by woight. The product dissolves without gel formation and can be sheeted out.
~' '.
Example 2 is repeated without the addition of powder-lng agents. The granules remain free-flowinq through rapid cooling to approx. 20-C.
ExamDle 4 10% by weight bisphenol A polycarbonate powder is added to the EPDM resin of Example 1 during introduction into the screws. The granules obtained remain free-flowing without powdering.
~xample 5 800 g of the EPDM resin of Example 1 are masticated in a 1.3 liter Pomini kne~der at a ~acket temperature of 60~C
and at a rotational speed of 40 l/minute. After 1 minute, 72 g phenol, 7.2 g methanesulfonic acid and another 100 g EPDM resin are added and mixed for another 8 minutes. The melt temperature rises to 90 - lOO'C. The product i9 Le A 26 793 8 ~ 20241~
. ....
ejected into a water bath. After removal of the excess phenol by extraction with toluene/methanol, the bound phenol content is 3.2% by weight, as determined by IR
6pectroscopy. The product dissolves without gel formation S and ean be sheeted out.
Exam, D~6 A total of 900 g of an HNBR resin (copolymer of 43% by weight aerylonitrile and 57% by weight butadiene, Nooney viseosity ML (1+4) at lOO-C - 75, Nn approx. 70,000, r-dueed by hydrogenation to 4~ of the original double bond eontent) are treated as in Example 4. The bound phenol eontent is 3.8~ by weight, a- determined by IR spectro~
~eopy. The produet di~-olves without gel formation and ean lS b- ~heeted out.
`.:,: " ' ExamDle 7 2.12 g b1--(4-hydroxyphenyl)-di-ulfide are added to, and mixed for 10 minutes with, 45 g of the EPDM resin of Exampl- 1 in a 70 ml kn-ader at a ~aeket temperature of 120-C and at a rotational speed of S0 l/min. The erude produot i~ xtraeted with tolu-ne/ethanol: the ¢ontent of phenolie group- i- 2.8% by weight, as determined by IR-speetroseopy.
ExamDle 8 2.3 g isopropenyl phenol are added to, and mixed for 0 minutes with, 45 g of the EPDM resin of Examplell inla '`` 70 ml kneader at a jacket temperature of 120-C and at a rotational speed of S0 l/min. The crude product is ex-traeted with toluene/ethanol; the content of phenolic group- ls 1.7% by weight, a- determined by IR-spectroscopy.
Le A 26 793 9
Claims (2)
1. A process for the production of a rubber containing 5 to 60 phenolic OH groups, characterized in that rubbers containing 3 to 250 double bonds per 1,000 carbon atoms in the rubber are reacted in bulk with phenols, optionally in the presence of a catalyst, for 1 minute to 30 minutes at temperatures of 50 to 150°C.
2. Rubbers obtainable by the process claimed in claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3928660 | 1989-08-30 | ||
| DEP3928660.6 | 1989-08-30 | ||
| DEP4000625.5 | 1990-01-11 | ||
| DE19904000625 DE4000625A1 (en) | 1989-08-30 | 1990-01-11 | METHOD FOR PRODUCING RUBBER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024121A1 true CA2024121A1 (en) | 1991-03-01 |
Family
ID=25884552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2024121 Abandoned CA2024121A1 (en) | 1989-08-30 | 1990-08-28 | Process for the production of rubbers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0418556A1 (en) |
| JP (1) | JPH03106901A (en) |
| CA (1) | CA2024121A1 (en) |
| DE (1) | DE4000625A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5688887A (en) * | 1992-05-26 | 1997-11-18 | Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
| US6043401A (en) * | 1992-05-26 | 2000-03-28 | Bp Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5455307A (en) * | 1992-04-03 | 1995-10-03 | Exxon Chemical Patents Inc. | Polymeric stabilizers for polyolefins |
| DE69330163T2 (en) * | 1992-05-26 | 2001-11-29 | Bp Amoco Corp | REACTIVE VISCOSE OLEFIN POLYMERS AND COPOLYMERS OF LOW MOLECULAR WEIGHT AND METHOD FOR THE PRODUCTION THEREOF |
| GB9318170D0 (en) * | 1993-09-02 | 1993-10-20 | Kodak Ltd | Antimicrobial polymers and compositions containing them |
| US6984604B2 (en) | 2001-11-26 | 2006-01-10 | Invista North America S.A.R.L. | Supported bis(phosphorus) ligands and their use in the catalysis |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1595385B1 (en) * | 1966-02-09 | 1969-09-18 | Albert Ag Chem Werke | Process for the production of phenolic conversion products from isoprene copolymers |
| DE2210058A1 (en) * | 1971-07-19 | 1973-02-01 | Reichhold Albert Chemie Ag | Unsatd resin prodn |
| US4070402A (en) * | 1976-03-15 | 1978-01-24 | Standard Oil Company | Terpolymer alkylated phenol |
-
1990
- 1990-01-11 DE DE19904000625 patent/DE4000625A1/en not_active Withdrawn
- 1990-08-17 EP EP90115744A patent/EP0418556A1/en not_active Withdrawn
- 1990-08-24 JP JP22140290A patent/JPH03106901A/en active Pending
- 1990-08-28 CA CA 2024121 patent/CA2024121A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5688887A (en) * | 1992-05-26 | 1997-11-18 | Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
| US6043401A (en) * | 1992-05-26 | 2000-03-28 | Bp Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4000625A1 (en) | 1991-03-07 |
| EP0418556A1 (en) | 1991-03-27 |
| JPH03106901A (en) | 1991-05-07 |
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