CA2015648A1 - Use of polymers which contain units derived from 4-hydroxystyrene or 4-acetoxystyrene as reinforcing resins and adhesion promoters in rubber mixtures - Google Patents
Use of polymers which contain units derived from 4-hydroxystyrene or 4-acetoxystyrene as reinforcing resins and adhesion promoters in rubber mixturesInfo
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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
- C08L21/00—Compositions of unspecified rubbers
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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Abstract
Abstract HOE 89/F 136 Polymers which contain units of 4-hydroxystyrene and/or of 4-acetoxystyrene, where appropriate in a mixture with other comonomer units, in particular butadiene, can be used in place of phenolic or resorcinol resins as reinforcing resins and adhesion promoters in rubber mixtures. These polymers are distinguished by the fact that, coupled with at least equally good effectiveness, they do not release any phenolic materials into the environment on incorporation into rubber mixtures.
Description
2~
HOECHST AKTIENGESELLSCHAFT IIOE 89/F 136 Dr.GM/PP
lDe~cription Use of polymer~ which contain unit~ derived from 4-hydroxystyrene or 4-acetoxystyrene aa reinforcing resin~
S and adhesion promoters in rubber mixtures It is known to add reinforcing resins to mixtures of natural or synthetic rubber to improve their mechanical properties, in particular the hardne~s and the stre~s values. Adhe~ion pxomoters are used to improve the adhesion of w lcanized rubbers to steel cord, especially to brass-coated or galvanized steel cord. Cros~linkable phenolic resins, in general novolaks, and resor~inol or resorcinol preconden~ates are uæed for thesa purposes in combination with formaldehyde-releasing substance~ or with substances ~hich react with the phenolic resins, resorcinol or the re~orcinol precondensates via methylene or methylol groups with cros~linking, for example hexa-methylenetetramine and methylol group-containing or - forming melamine and urea resin~, w~ich may be partially or completely etherified. The rubber mixtures can be based on natural rubber or the known synthetic rubber~. The reinforcing resin~ and adhesion promoters are mixed into the rubber mixtuxes at elevated temper-ature. Sirice the precondensates always contain free phenol or resorcinol, expen6ive precautions must be taken with thi~ proces3 to ensure that these phenoli~ material~
do not get into the environment. Thi~ is particularly the ca e when u~ing free resorcinol. Moreover, resorcinol precondensates, because of their hygroacopic nature, usually contain water. Thi~ make~ their incorporation into the rubber mixture more difficult and impairs the propertie~ of the vulcanized material prepared therefrom.
The ob~ect of the invention was, therefore, to make available reinforcing resin6 and adhesion promoters for rubber mixtures, which, while having at least equally good effectiveness, do not release phenolic material~
2~L5~ ~
into the environment and can b~ ea~ily i~corporated into bber mixture~.
It ha~ now been found thqt polymer~ which contain units w]hich are derived from 4-acetoxystyrene or 4-hydroxy-styrene, which may be ring-sub~tituted, are suitable as rleinforcing resins and adhe~ion promoters for rubber mixtures, which is described in more detail in the following text.
Polymers which contain 6uch unit~ are disclo~ed in European Patent 277,721. Accordin~ to thi~ patent they are obtained by free radical polymerization of 4-acetoxy-styrene, where appropriate in a mixture with other polymerizable monomer~, in an aqueous mediu~. The cor-responding 4-hydroxystyrene polymer~ are obtained from these by saponification. The polymer~ obtained in this way are usable for the purposes of the invention.
However, it is difficult to obtain them free from ~alt and emulsifier, for which rea~on free radical or thermal polymerization in organic solvents i8 preferred for the pre~ent purpose.
The polymer~ to be used according to the invention contain units of the formula (I) (~2)n The symbols have the following meaning:
R1 is hydrogen or an acetyl group CH3C0-R2 is hydrogen or an alkyl or alkoxy group having 1 to 4 carbon atoms or halogen or C.N and n iB an integer from 1 to 4 with the proviso that if n ~ 1 the radicals RZ can be identical or diff-erent, and ~hat at least in some of the unit~ of the formula (I) there i~ a hydrogen atom st least in one of the po~itions vicinal to the R1-0- group.
In preferred embodiment~ Rl i8 only hydrogen or only acetyl, R2 only hydrogen and therefore n = 4. Polymer~ in which Rl repre~ents acetyl ~xclusively react relatively sluggishly with the crosslinking agents mentioned above for the known phenol and re~orcinol re~in~, whilst the pure 4-hydroxy compound~ are comparable in their reactivity with the known reinforcing resins. The reactivity can be influenced in a controlled manner by the degree of saponification.
The properties of the polymer~ to be used in accordance with the invention can be modified during their pr2para-tion not only by the d~gree of ~aponification but also by copolymerization with the co-use of comonomers of the formul~ (II) R3~ R4 C=C (II) R3 ~ ~ R3 in whîch the sym~ols have the following meanings ~3 are identic~l or diff~rent radical~ from the group comprising hydrogen or an alkyl or an alkoxy group having 1 to 4 carbon atoms or halogen or -C-N or -CO~H or -CVO(Cl-C4-alkyl) or ~ (R3)p p being an integer from 1 to 5, ~nd R4 = R3 ox a group _~ -C
~3 - R3 M~nomer~ of the formula (II) are olefin~, con~ugated ~ienes, ~tyrene and ~tyrene derivatives, or example ethylene, vinyl chloride, 1,3~butadiene, Z-methyl-1,3-butadiene (i~oprene), 5,5-dimethyl-1,3-hexadiene, 2-chloro-1,3-butadiene (chloroprene), 1-phenyl-1,3-buta-diene, 1-cyano-1,3-butadiene, styrene and alpha-mèthyl-~tyrene~ Styrene i8 preferred and butadiene, isoprene and chloroprene are particularly preferred, e~pecially butadiene from the latter group. ~he incorporation of units which are derived from the 1,3-dienes lead~ to the co-vulcanizing in of the polymer into the vulcani~ed material during vulcanization.
Cyclopsntadiene and dicyclopentadiene, which copolymerize particularly ea3ily with 4-acetoxy~tyrene, are al30 very suitable a~ comonomers.
By the co-use of comonomers the degree of oros~linking of the polymers can be regulated ~uring the reaction with cro~linking agents. However the amount of the comonomers used should be at most three time6 the molar amount of, and preferably not more than the same ~olar amount as, the 4-acetoxystyrene.
The molecular weight of the polymers should be between about 1000 and about 150,000. If a molecular weight of about 150,000 i8 exceeded ~ticky pxoducts, which are difficult to handle, ~re obtained, in particular if 1,3-dienes are used as comonomers. ~ower molecular wei~ht product~ can als~ be sticky if the proportion of 1,3-dienes i~ very high.
As already ~entioned, the polymers or copol~mer~ can be prepared by polymerization in an aqueous medium.
Preferably, however, the polymerization i~ carried out in organic ~olvent~ ~uch a~ i~ooctane, dodecane, benzene, toluene, xylene, cumene, methyl e~h~l ketone, methyl isobutyl ketone, diisoamyl ketone, ethyl acetate, ~s~
propanol or butanol. Preferred solv~nts for the polymer-i2ation are toluene, xylene or cumene.
T]he polymerization can be carried out under the action of h~at or by mean~ of free radicals. In general the free radical polymerization proceed~ at lower temperatures and conseguently at lower pressure. The free radical-forming agents u~ed are known organic peroxides or azo compound~, such as di~anzoyl peroxide, di-tert.-butyl peroxide, dilauroyl peroxide, cumene hydroperoxide, tert.-butyl hydroperoxide and azudiisobutyronitrile, preferably di-tert.-butyl peroxide, in amounts of up to about 5 ~ by weight, preferably up to 2 % by weight, relative to the total weight of the monomers.
In general the temperature for the free radical poly-lS meri~ation is 80-220C. The pres6ure i8 dependent on the temperature and on the nature of the ~olvent used.
Significantly higher temperatures can be neces~ary for thermal polymerization.
The polymerization can be carried out in such a way that the total amount of monomers and catalyst in a suitable solvent i~ initially introduced and warmed until the reaction starts. It i~ al80 possible initially to intro-duce the solvent on it~ own, to preheat it to a tempera-ture ~uitable for starting the reaction and to meter in monomers and catalyst. All proce~se3 known from ~olution polymerization technology can be u~ed.
To ad~ust the molecular weight the known regulators are u~ed, in particular ~ulfur compounds such as thio-alcohQls, in particular mercaptoethanol or 1-dodecanethiol, thioacids ~uch a~ mercaptoacetic acid, ordisulfides such as xanthogen disulfides. 1-Dodecanethiol in a~ounts of up to 3 % by weight, relative to the total amount of mon~mer~ preferred.
On completion of the polymerization the polymer can be 2~
obtained a~ solid resin by distilling off the solvent. It can be employed without furth~r purification for the use according to the inven~ion.
The resctivity towards methylene donors, such as hexa-methylenetetramine, and towards melamine or urea re~in~becomes considerably higher if the 4-acetyloxy-~tyrens unit6 contained in the polymer are entirely or partially ~aponified to 4-hydroxy-~tyrene units, by which mean~
polymers are obtained which posse~s the structure of a polymeric phenol.
~o carry out the ~aponification an aqueous ~olution or ~u~pension of a base, for example ~odium hydroxide, potas6ium hydroxide, calcium hydroxide or aluminium hydroxide or also ammonia, can be added directly to the solution obtained from the polymerization and, depanding on the solvent, the saponification can be curried out in the homogeneous or heterogeneou6 phase. It i8 al80 possible first to obtain the polymer by removing the solvent and to saponify this in the aqueous phase. The saponified polymers are usually ~oluble in aqueous bases and can be precipitated by ~cidification with a strong acid. The precipitate is filtered off and carefully washed and dried.
However, it is particularly advantageous to carry out the polymerization in a water-immi~cible solvent, 6uch as toluene, ~ylene or cum~ne, to carry out the 6aponifica-tion using an aqu~ou~ base in heterogeneous phase and to separate aqueou~ and organic phase~ before acidification.
~he polymer~ are ussd in~tead of known reinforcing resins and adhesion promoters in the known natura} and synthetic rubber mixture~, which mi~ture~ are u~ed for the production of automobile tire~ and of industrial rubber article~.
The crosslinking agents used are the ~ame compound~ as ale u~ed with ~he known phenolic and resorcinol re~inH.
Preferably hexamethylenetetramine and mel~mine re~in~, in p2lrticular hexamethoxymethylmelamine, are used. The ~nount of eros~linking agent ~uitable for the ~pecific purpose mus~ be determined in pre-trials, which are s.~mple to carry out. It can, for example, be 2-60 ~ ~y w~ight, relative to the weight of the polymer u~ed.
The rubber mixtures can contain the additive~, fillers, and auxiliarie~ which are customsry ~nd known in the relevant industry and c~n be proce~sed ln the customary manner.
The following examples serve to illustrate the invention without restricting it.
Rxample 1 1080 g of xylene, 10.8 g of di-tert-butyl peroxide and 810 g of p-acetoxystyrene (5 ~ol~) are initially intro-duced into a 3 - l1ter autoclave. 135 g ~2.5 mols) of butadiene are pumped into this mixture at room tempera-ture. The mixture i~ then heated to 140C over a period of 1 hour. After holding the reaction mixture at 140eC
for 4 hours the pressura, which initially rose to 8 bars, has fallsn to 3.4 bars. To complete the reaction the reaction mixture i8 then heated to 180C for a further half hour, a pressure of 4.4 bars developing. The mixture 25 iB allowed to cool to 140C, the pressure i8 released and the solvent is di~tilled off, the temper~ture of the reaction mixture being increased to 200-C. In order to remove the re~idual 801vent the autoclave i8 evacuated to 50 mbar at thi~ temperature for a further half hour.
After cooling, the re~ultant copolym~r i8 iEolated a~ a gla~s-like solid re~in i~ 95 % yield (relative to the mon~mers used). It contains the monomer units p-acetoxy-styrene and butadiene in the molar ratio 1:0~5, has a X~5fi ~
~elting point of 95C and an ~verage molecular weight (~) of 52,000.
~xampleB 2-5 are prepared analogously to Example 1:
E~cample Molar rstio Melting Yield 4 S acetoxy- point styrenesbuta-diene ~C
__ _ _ 2 1 : 0.25 10~ 95 22,000 3 1 : 0.75 87 90 66,000 4 1 2 1.0 80 87 380,000 1 s 2.0 79 75 365,000 ~xample 6 The procedure is analogous ~o Example 1~ except that 21.6 g (z 2 % by weight, relative to monomers) of n-dodecylmercaptan are added a~ molecular weight regulator.
A copolymer of glass~like appearance i~ obtained in 100 % yield; melting point 68C, average molecular weight (M") 19, 000 .
The following products ~re prepared analoyou~ly to Example 6:
E~ample Molar ratio Addition Yield N~
acetoxy- of regu-~tyrene: lator in butadiene by weight 7 1 s 1 1 95 49,00~
8 1 s 2 1 B7 106,000 9 1 s 1 2 g4 36,000 1 ~ 2 2 89 56,000 11 1 s 3 ~ 92 260,000 ~ample 12 1000 g of xylene are initially introduced into a 3 -liter autocl~ve~ Over a period of 3 hour~, lG00 g of p-acetoxyatyrene, which contains 10 g of di-tert-butyl ~0~
_ 9 _ peroxide and 20 g of n-dodecylmercaptan, are pumped into the solvent, which has been heated to 200C. The mixture ~B ~tirred for a further 1 hour at 200C and the pre~sure i8 cautiously relea~ed (the internal pre~ure i8 about 4.5 bar~), the ~olvent beginning to distil off. Any still volatile component~ are removed by evacuatlng to 60 mbar for one and a half hours~ After cooling, 950 g of a gla~s-like product with a melting point of S0C are obta~ned (yields 9S ~). It ha~ an averaqe molecular lC weiyht M~ of 4000.
~sampl~ 13 190 g of solid resin from Example 1 are used. The pro duct, comminuted to pea-size, is 3u~pended in 270 g of 33 % sodium hydroxide solution. The suspen~ion is then warmed to 90C, the polymeric sslid resin 810wly begin-ning to di~solve. After di~olution has taken place, the solution i8 ~ub~equently stirred for a further ~ hour~ at 90C. The ~olution, cooled to 20C, i~ then added drop-wise to 200 ml of 37 % hydrochloric acid, the hydroxyl group-containing ~opolymer precipitating out. It i8 i~olated by filtering off, washed acid-free with a large amount of water and dried in an oven at 50C to con~tant weight. 147 g (100 % yield) of a colorless powder are obtained, which begin~ to melt above 100C.
~ample 14 The procedure i~ in accordance with Example 1, except that the ~olvent i~ not d~tilled off. 402 g of this ~olution are stirred for 4 houra at 90-C with 80 g of sodium hydroxide, which ~ 8 dis~olved in 300 g of water.
The mixture i~ then allowed to cool ~o 20~C and the organic pha~e (xylene) i8 ~eparated off. The alkaline aqueous ~olution iB added dropwi~e to 490 ~ of ice-cold 20 ~ sulfuric acid, during which addition the temperature should not rise above 10C.~rhe hydroxyl group-containing copolymer which has precipitAted out is filtered off, 2~
washed salt- and acid-free with a large amount of water and dried at 50C in an oven to con~tant weight. 147 g of a pale yellow-colored powder i~ obtained, which begin~ to mlelt from 100C ~yield quantitative).
E,xample 15 1616 g of a 50 ~ copolymer solution in xylene are pre-pared in accordance with Example 3. 348 g of ~odium hydroxide in 1410 g of water are added to this solution and the 2-phase mixture i~ heated to 80C. After one hour the mixture i~ allowed to cool to 20C and 848 g of 37 %
hydrochloric acid are added dropwise over a period of 2 hours at such a rate that the temperature doe6 not rise above 20C. The precipitate i8 filtered off with suction and eubsequently washed twice with 1000 g of cold water.
It is then dried to constant weight at 50C in a vacuum oven. 633 g (100 % yield) of a colorless powder with a melting point of 100C are obtained.
Exa~ple 16 950 g o~ homopolymer are prepared in accordance with Example 12. The comminuted product, with the addition of 200 g of xylene, is heated to 90~C with 465 g of sodium hydroxide in 1800 g of water. After one hour, the mixture is allowed to cool to 20C and the product i5 precipi-tated out with 1131 g o~ 37 % h~drochloric acid. It is filtered off with suction, wa~hed acid-free with water and dried to con~tant weight at 40C in a vacuum oven.
695 ~ (100 ~ yield) of a colorless powder with a melting point of 85C are obtained.
~ample 17 Acetyl ~roup-containing copolymers with a high butadiene content are prepared in accordance with Example 4, 5, 10 and 11. ~he products are ~aponified in accordance with Example 13 or 14. Hydroxyl group-containin~ copolymer~
are obtained in quantitative yield.
T:he copolymer~ are ~ticky ~nd therefore difficult to handle and pr~ces6.
~ample 18 400 g of xylane are initially introduced into a 3 1 autoclave. Over a period o~ 3 hour6 a mixture of 600 g (3.7 mols) of p-acetoxy~tyrene, 200 g (1.9 mols) of ~ty-rene, 8 g of dibenzoyl peroxide, 16 g of n-dodecyl-mercaptan and 200 g of xylene is pumped into the solvent, which has been heated ~o 180C. The mixture is allowed to react further for a further 1 hour at 180C and the pressure is cautiou~ly released, the ~olvent beginninq to distil off. Any still volatile component~ are re~oved by evacuating to 60 mbar for one and a half hour~. After cooling, 802 ~ (99 % yield) of a glass-like product with a melting point of 76C ~re obtained.
~ample 19 700 g of the copolymer prepared in Example 18 were comminuted and heated for 1 hour at 90CC with 200 g of xylene, 302 g of ~odium hydroxide and 1220 g of water.
~he mixture was then diluted with 3000 g o~ cold water and 370 g of 37 % hydrochloric acid were added dropwi~e over a period of one hour. After filtering off with ~uction and drying at 50C under vacuum, a colorless powder with a melting point of 138C wa~ obtained.
The product~ described in the previou~ Hection were then te~ted to determine their ef~ect in the rubber mixture~.
A ba~e batch having the ~ollowing composition (PbW 5 parts by weight) wa~ u~ed ~ ~tarting mixture, of which ~0 a relatively large amount was prepareds 100 PbN natural ~ubber 40 P~W carbon black 15 PbW active ~ilica 5 PbW zinc oxide 1 PbW ~tearic acid 1 PbW anti-aging agent TID prepare the various individual mixture~ the particular products to be te~ted wers mixed into the ba~e batch at temperatures between about 80 and 100C and then homogeneou~ly di~per~ed for about 10 minute~ a~ a temperature of about 120C. The mixing-in of 4 PbW of sulfur and 0.8 PbW of nc~elerator and of the melamine resin u~ed as curing agent then followed at temperatures below lOO~C.
After vulcanization, carried out under the conditions specified for the particular test 3eries, the test piece~
obtained were examined for the following propertie6 using the methods customary in the indu~try:
- ultimate tansile 6trength, elongation at break and ~tres~ value~ in accordance with DI~ 53504 - Shore A hardness according to DIN 53505 - rebound resil~ence a~cording to DIN 53512 20 - tear-out ~orce and dsgree of covering in the eteel cord adhesion test.
~he resul~s of the last-mentioned adhe~ion tes~, which wa~ carried out using a te~t arrangement in accordance with the recommendation of the 8tandards Committee deeignated ISO DP 56003.3, are particularly important.
For this purpose steel cord with a 4 x 0.25 construction with a copper content of the bra~s coating of 67 % wa~
embedded in the adhe~ion mixture in special molds and this adhe~ion mixture wa~ then vulcani~ad. The ~amples were then stored under different test conditions and the force nece~sary to tear-out the steel cord filaments from the rubber mixture wa8 then measured. The mean value for the force required to tear out the steel cord fr~m the vulcanized material, calculated from 10 individual te8t8 in each case, i8 guoted a~ the te~t re~ult and aclditionally the degree of cover~ng i~ sub~ectively a~s~sed. The latter iB to be under~tood to mean th~ area oiE pulled-out cord covered with rubber, which iB
sl~ectively e~timated in grading~ of 10 ~ (i.e. grading 1l, 2, 3... 10 denotes 10, 20, 30.~.100 ~ covered cord area). Thus, better adhesion of the rubber mixture to ~he ~teel cord i8 accompanied by high~r te~t figure~ both for t]he tear-out force and for the degree of covering.
A~ i~ to be seen from the result~ in Table 1, the rubber mixtures prepared with ~ho product~ sccording to the invention in accordance with ExRmple 13, 15 and 16 achieve higher degrees of covering than the comparison with re~orcinol. In particular after heat-aging for 14 days at 90C, the comparative mix~ure with resorcinol lS shows a decrea~e from 80 % to about S0 ~, whilst the mixtures prepared with the copolymer~ change by not more than 10 % to degrees of covering of 70 to 90 ~. If, in order to ~imulate unfavorable conditions in practice, the vulcanization time iB increa~ed threefold, even more pronounced differences between the comparison and the mixture~ according to the invention are then revealed.
The degree of covering before additional exposure to heat fall~ to about 40 % in the ca~e of the resor~inol-containing mixture, whilst the mixture~ according to the invention achie~e 70 to 100 %. After a heat-aging at goaC
o~er a period of 14 day~, the latter decline to degree~
of c~ering of 60 to 90 ~ and are thus clearly better than the compari~on with approximately 30 ~.
2 ~ J- r8 Tllbl~ 1 ~lxtur , pr p-rad ol4nd~on ~ltb poly~or ~coordl~g lYtur-to 8~ cpleYltb ~3 lS 16 _ h~ount of copolyoor or r- orclnol add-d ~PbW~ 2 5 2 5 2 5 2 5 ~Dunt Or alaxl~o ru-ln ddnd(PbW) 3 85 3 55 3 85 3 85 V~lc~nl~tlou ~t ~5 Clrln) ~0 60 60 60 UltiJat- tonJll- tr-ngtb(~Po~17 18 19 16 tlongatlon ~t bx~ ) 380 390 ~10 dOO
8tr-~- q~lu-~t 10 ~ lona~tlon (~p~) 1 1 1 0 1 1 0 9 50 t olongatlon (~p ) 2 2 1 9 2 0 1 7 100 ~ olong~tlon ~p~) 3 5 3 2 3 3 2 7 Robound r--lll nc~ (DIR 53512) ~ 0 30 abor A b rdno-- (DI~ 53505) 67 66 68 72 I-~r-out toro~ l~ c~ l)/oogro- of covarlng ~rt r torng~ 3 d/Z3 C 370/9 390/D 3~0/9 ~00/8 l~ d/~O C 180/9 170/7 19Q/8 Z20/S
3-told vulc~nl~ntion tl Alt r ntorn~o 3 dt23 C 310tlO 320t8 350t7 330 1~ dt50 C 200t9 170t6 l90t7 190t3 65 PbW or hox eothcxy3 tbyln l~lno p r 35 PbW 91118-
HOECHST AKTIENGESELLSCHAFT IIOE 89/F 136 Dr.GM/PP
lDe~cription Use of polymer~ which contain unit~ derived from 4-hydroxystyrene or 4-acetoxystyrene aa reinforcing resin~
S and adhesion promoters in rubber mixtures It is known to add reinforcing resins to mixtures of natural or synthetic rubber to improve their mechanical properties, in particular the hardne~s and the stre~s values. Adhe~ion pxomoters are used to improve the adhesion of w lcanized rubbers to steel cord, especially to brass-coated or galvanized steel cord. Cros~linkable phenolic resins, in general novolaks, and resor~inol or resorcinol preconden~ates are uæed for thesa purposes in combination with formaldehyde-releasing substance~ or with substances ~hich react with the phenolic resins, resorcinol or the re~orcinol precondensates via methylene or methylol groups with cros~linking, for example hexa-methylenetetramine and methylol group-containing or - forming melamine and urea resin~, w~ich may be partially or completely etherified. The rubber mixtures can be based on natural rubber or the known synthetic rubber~. The reinforcing resin~ and adhesion promoters are mixed into the rubber mixtuxes at elevated temper-ature. Sirice the precondensates always contain free phenol or resorcinol, expen6ive precautions must be taken with thi~ proces3 to ensure that these phenoli~ material~
do not get into the environment. Thi~ is particularly the ca e when u~ing free resorcinol. Moreover, resorcinol precondensates, because of their hygroacopic nature, usually contain water. Thi~ make~ their incorporation into the rubber mixture more difficult and impairs the propertie~ of the vulcanized material prepared therefrom.
The ob~ect of the invention was, therefore, to make available reinforcing resin6 and adhesion promoters for rubber mixtures, which, while having at least equally good effectiveness, do not release phenolic material~
2~L5~ ~
into the environment and can b~ ea~ily i~corporated into bber mixture~.
It ha~ now been found thqt polymer~ which contain units w]hich are derived from 4-acetoxystyrene or 4-hydroxy-styrene, which may be ring-sub~tituted, are suitable as rleinforcing resins and adhe~ion promoters for rubber mixtures, which is described in more detail in the following text.
Polymers which contain 6uch unit~ are disclo~ed in European Patent 277,721. Accordin~ to thi~ patent they are obtained by free radical polymerization of 4-acetoxy-styrene, where appropriate in a mixture with other polymerizable monomer~, in an aqueous mediu~. The cor-responding 4-hydroxystyrene polymer~ are obtained from these by saponification. The polymer~ obtained in this way are usable for the purposes of the invention.
However, it is difficult to obtain them free from ~alt and emulsifier, for which rea~on free radical or thermal polymerization in organic solvents i8 preferred for the pre~ent purpose.
The polymer~ to be used according to the invention contain units of the formula (I) (~2)n The symbols have the following meaning:
R1 is hydrogen or an acetyl group CH3C0-R2 is hydrogen or an alkyl or alkoxy group having 1 to 4 carbon atoms or halogen or C.N and n iB an integer from 1 to 4 with the proviso that if n ~ 1 the radicals RZ can be identical or diff-erent, and ~hat at least in some of the unit~ of the formula (I) there i~ a hydrogen atom st least in one of the po~itions vicinal to the R1-0- group.
In preferred embodiment~ Rl i8 only hydrogen or only acetyl, R2 only hydrogen and therefore n = 4. Polymer~ in which Rl repre~ents acetyl ~xclusively react relatively sluggishly with the crosslinking agents mentioned above for the known phenol and re~orcinol re~in~, whilst the pure 4-hydroxy compound~ are comparable in their reactivity with the known reinforcing resins. The reactivity can be influenced in a controlled manner by the degree of saponification.
The properties of the polymer~ to be used in accordance with the invention can be modified during their pr2para-tion not only by the d~gree of ~aponification but also by copolymerization with the co-use of comonomers of the formul~ (II) R3~ R4 C=C (II) R3 ~ ~ R3 in whîch the sym~ols have the following meanings ~3 are identic~l or diff~rent radical~ from the group comprising hydrogen or an alkyl or an alkoxy group having 1 to 4 carbon atoms or halogen or -C-N or -CO~H or -CVO(Cl-C4-alkyl) or ~ (R3)p p being an integer from 1 to 5, ~nd R4 = R3 ox a group _~ -C
~3 - R3 M~nomer~ of the formula (II) are olefin~, con~ugated ~ienes, ~tyrene and ~tyrene derivatives, or example ethylene, vinyl chloride, 1,3~butadiene, Z-methyl-1,3-butadiene (i~oprene), 5,5-dimethyl-1,3-hexadiene, 2-chloro-1,3-butadiene (chloroprene), 1-phenyl-1,3-buta-diene, 1-cyano-1,3-butadiene, styrene and alpha-mèthyl-~tyrene~ Styrene i8 preferred and butadiene, isoprene and chloroprene are particularly preferred, e~pecially butadiene from the latter group. ~he incorporation of units which are derived from the 1,3-dienes lead~ to the co-vulcanizing in of the polymer into the vulcani~ed material during vulcanization.
Cyclopsntadiene and dicyclopentadiene, which copolymerize particularly ea3ily with 4-acetoxy~tyrene, are al30 very suitable a~ comonomers.
By the co-use of comonomers the degree of oros~linking of the polymers can be regulated ~uring the reaction with cro~linking agents. However the amount of the comonomers used should be at most three time6 the molar amount of, and preferably not more than the same ~olar amount as, the 4-acetoxystyrene.
The molecular weight of the polymers should be between about 1000 and about 150,000. If a molecular weight of about 150,000 i8 exceeded ~ticky pxoducts, which are difficult to handle, ~re obtained, in particular if 1,3-dienes are used as comonomers. ~ower molecular wei~ht product~ can als~ be sticky if the proportion of 1,3-dienes i~ very high.
As already ~entioned, the polymers or copol~mer~ can be prepared by polymerization in an aqueous medium.
Preferably, however, the polymerization i~ carried out in organic ~olvent~ ~uch a~ i~ooctane, dodecane, benzene, toluene, xylene, cumene, methyl e~h~l ketone, methyl isobutyl ketone, diisoamyl ketone, ethyl acetate, ~s~
propanol or butanol. Preferred solv~nts for the polymer-i2ation are toluene, xylene or cumene.
T]he polymerization can be carried out under the action of h~at or by mean~ of free radicals. In general the free radical polymerization proceed~ at lower temperatures and conseguently at lower pressure. The free radical-forming agents u~ed are known organic peroxides or azo compound~, such as di~anzoyl peroxide, di-tert.-butyl peroxide, dilauroyl peroxide, cumene hydroperoxide, tert.-butyl hydroperoxide and azudiisobutyronitrile, preferably di-tert.-butyl peroxide, in amounts of up to about 5 ~ by weight, preferably up to 2 % by weight, relative to the total weight of the monomers.
In general the temperature for the free radical poly-lS meri~ation is 80-220C. The pres6ure i8 dependent on the temperature and on the nature of the ~olvent used.
Significantly higher temperatures can be neces~ary for thermal polymerization.
The polymerization can be carried out in such a way that the total amount of monomers and catalyst in a suitable solvent i~ initially introduced and warmed until the reaction starts. It i~ al80 possible initially to intro-duce the solvent on it~ own, to preheat it to a tempera-ture ~uitable for starting the reaction and to meter in monomers and catalyst. All proce~se3 known from ~olution polymerization technology can be u~ed.
To ad~ust the molecular weight the known regulators are u~ed, in particular ~ulfur compounds such as thio-alcohQls, in particular mercaptoethanol or 1-dodecanethiol, thioacids ~uch a~ mercaptoacetic acid, ordisulfides such as xanthogen disulfides. 1-Dodecanethiol in a~ounts of up to 3 % by weight, relative to the total amount of mon~mer~ preferred.
On completion of the polymerization the polymer can be 2~
obtained a~ solid resin by distilling off the solvent. It can be employed without furth~r purification for the use according to the inven~ion.
The resctivity towards methylene donors, such as hexa-methylenetetramine, and towards melamine or urea re~in~becomes considerably higher if the 4-acetyloxy-~tyrens unit6 contained in the polymer are entirely or partially ~aponified to 4-hydroxy-~tyrene units, by which mean~
polymers are obtained which posse~s the structure of a polymeric phenol.
~o carry out the ~aponification an aqueous ~olution or ~u~pension of a base, for example ~odium hydroxide, potas6ium hydroxide, calcium hydroxide or aluminium hydroxide or also ammonia, can be added directly to the solution obtained from the polymerization and, depanding on the solvent, the saponification can be curried out in the homogeneous or heterogeneou6 phase. It i8 al80 possible first to obtain the polymer by removing the solvent and to saponify this in the aqueous phase. The saponified polymers are usually ~oluble in aqueous bases and can be precipitated by ~cidification with a strong acid. The precipitate is filtered off and carefully washed and dried.
However, it is particularly advantageous to carry out the polymerization in a water-immi~cible solvent, 6uch as toluene, ~ylene or cum~ne, to carry out the 6aponifica-tion using an aqu~ou~ base in heterogeneous phase and to separate aqueou~ and organic phase~ before acidification.
~he polymer~ are ussd in~tead of known reinforcing resins and adhesion promoters in the known natura} and synthetic rubber mixture~, which mi~ture~ are u~ed for the production of automobile tire~ and of industrial rubber article~.
The crosslinking agents used are the ~ame compound~ as ale u~ed with ~he known phenolic and resorcinol re~inH.
Preferably hexamethylenetetramine and mel~mine re~in~, in p2lrticular hexamethoxymethylmelamine, are used. The ~nount of eros~linking agent ~uitable for the ~pecific purpose mus~ be determined in pre-trials, which are s.~mple to carry out. It can, for example, be 2-60 ~ ~y w~ight, relative to the weight of the polymer u~ed.
The rubber mixtures can contain the additive~, fillers, and auxiliarie~ which are customsry ~nd known in the relevant industry and c~n be proce~sed ln the customary manner.
The following examples serve to illustrate the invention without restricting it.
Rxample 1 1080 g of xylene, 10.8 g of di-tert-butyl peroxide and 810 g of p-acetoxystyrene (5 ~ol~) are initially intro-duced into a 3 - l1ter autoclave. 135 g ~2.5 mols) of butadiene are pumped into this mixture at room tempera-ture. The mixture i~ then heated to 140C over a period of 1 hour. After holding the reaction mixture at 140eC
for 4 hours the pressura, which initially rose to 8 bars, has fallsn to 3.4 bars. To complete the reaction the reaction mixture i8 then heated to 180C for a further half hour, a pressure of 4.4 bars developing. The mixture 25 iB allowed to cool to 140C, the pressure i8 released and the solvent is di~tilled off, the temper~ture of the reaction mixture being increased to 200-C. In order to remove the re~idual 801vent the autoclave i8 evacuated to 50 mbar at thi~ temperature for a further half hour.
After cooling, the re~ultant copolym~r i8 iEolated a~ a gla~s-like solid re~in i~ 95 % yield (relative to the mon~mers used). It contains the monomer units p-acetoxy-styrene and butadiene in the molar ratio 1:0~5, has a X~5fi ~
~elting point of 95C and an ~verage molecular weight (~) of 52,000.
~xampleB 2-5 are prepared analogously to Example 1:
E~cample Molar rstio Melting Yield 4 S acetoxy- point styrenesbuta-diene ~C
__ _ _ 2 1 : 0.25 10~ 95 22,000 3 1 : 0.75 87 90 66,000 4 1 2 1.0 80 87 380,000 1 s 2.0 79 75 365,000 ~xample 6 The procedure is analogous ~o Example 1~ except that 21.6 g (z 2 % by weight, relative to monomers) of n-dodecylmercaptan are added a~ molecular weight regulator.
A copolymer of glass~like appearance i~ obtained in 100 % yield; melting point 68C, average molecular weight (M") 19, 000 .
The following products ~re prepared analoyou~ly to Example 6:
E~ample Molar ratio Addition Yield N~
acetoxy- of regu-~tyrene: lator in butadiene by weight 7 1 s 1 1 95 49,00~
8 1 s 2 1 B7 106,000 9 1 s 1 2 g4 36,000 1 ~ 2 2 89 56,000 11 1 s 3 ~ 92 260,000 ~ample 12 1000 g of xylene are initially introduced into a 3 -liter autocl~ve~ Over a period of 3 hour~, lG00 g of p-acetoxyatyrene, which contains 10 g of di-tert-butyl ~0~
_ 9 _ peroxide and 20 g of n-dodecylmercaptan, are pumped into the solvent, which has been heated to 200C. The mixture ~B ~tirred for a further 1 hour at 200C and the pre~sure i8 cautiously relea~ed (the internal pre~ure i8 about 4.5 bar~), the ~olvent beginning to distil off. Any still volatile component~ are removed by evacuatlng to 60 mbar for one and a half hours~ After cooling, 950 g of a gla~s-like product with a melting point of S0C are obta~ned (yields 9S ~). It ha~ an averaqe molecular lC weiyht M~ of 4000.
~sampl~ 13 190 g of solid resin from Example 1 are used. The pro duct, comminuted to pea-size, is 3u~pended in 270 g of 33 % sodium hydroxide solution. The suspen~ion is then warmed to 90C, the polymeric sslid resin 810wly begin-ning to di~solve. After di~olution has taken place, the solution i8 ~ub~equently stirred for a further ~ hour~ at 90C. The ~olution, cooled to 20C, i~ then added drop-wise to 200 ml of 37 % hydrochloric acid, the hydroxyl group-containing ~opolymer precipitating out. It i8 i~olated by filtering off, washed acid-free with a large amount of water and dried in an oven at 50C to con~tant weight. 147 g (100 % yield) of a colorless powder are obtained, which begin~ to melt above 100C.
~ample 14 The procedure i~ in accordance with Example 1, except that the ~olvent i~ not d~tilled off. 402 g of this ~olution are stirred for 4 houra at 90-C with 80 g of sodium hydroxide, which ~ 8 dis~olved in 300 g of water.
The mixture i~ then allowed to cool ~o 20~C and the organic pha~e (xylene) i8 ~eparated off. The alkaline aqueous ~olution iB added dropwi~e to 490 ~ of ice-cold 20 ~ sulfuric acid, during which addition the temperature should not rise above 10C.~rhe hydroxyl group-containing copolymer which has precipitAted out is filtered off, 2~
washed salt- and acid-free with a large amount of water and dried at 50C in an oven to con~tant weight. 147 g of a pale yellow-colored powder i~ obtained, which begin~ to mlelt from 100C ~yield quantitative).
E,xample 15 1616 g of a 50 ~ copolymer solution in xylene are pre-pared in accordance with Example 3. 348 g of ~odium hydroxide in 1410 g of water are added to this solution and the 2-phase mixture i~ heated to 80C. After one hour the mixture i~ allowed to cool to 20C and 848 g of 37 %
hydrochloric acid are added dropwise over a period of 2 hours at such a rate that the temperature doe6 not rise above 20C. The precipitate i8 filtered off with suction and eubsequently washed twice with 1000 g of cold water.
It is then dried to constant weight at 50C in a vacuum oven. 633 g (100 % yield) of a colorless powder with a melting point of 100C are obtained.
Exa~ple 16 950 g o~ homopolymer are prepared in accordance with Example 12. The comminuted product, with the addition of 200 g of xylene, is heated to 90~C with 465 g of sodium hydroxide in 1800 g of water. After one hour, the mixture is allowed to cool to 20C and the product i5 precipi-tated out with 1131 g o~ 37 % h~drochloric acid. It is filtered off with suction, wa~hed acid-free with water and dried to con~tant weight at 40C in a vacuum oven.
695 ~ (100 ~ yield) of a colorless powder with a melting point of 85C are obtained.
~ample 17 Acetyl ~roup-containing copolymers with a high butadiene content are prepared in accordance with Example 4, 5, 10 and 11. ~he products are ~aponified in accordance with Example 13 or 14. Hydroxyl group-containin~ copolymer~
are obtained in quantitative yield.
T:he copolymer~ are ~ticky ~nd therefore difficult to handle and pr~ces6.
~ample 18 400 g of xylane are initially introduced into a 3 1 autoclave. Over a period o~ 3 hour6 a mixture of 600 g (3.7 mols) of p-acetoxy~tyrene, 200 g (1.9 mols) of ~ty-rene, 8 g of dibenzoyl peroxide, 16 g of n-dodecyl-mercaptan and 200 g of xylene is pumped into the solvent, which has been heated ~o 180C. The mixture is allowed to react further for a further 1 hour at 180C and the pressure is cautiou~ly released, the ~olvent beginninq to distil off. Any still volatile component~ are re~oved by evacuating to 60 mbar for one and a half hour~. After cooling, 802 ~ (99 % yield) of a glass-like product with a melting point of 76C ~re obtained.
~ample 19 700 g of the copolymer prepared in Example 18 were comminuted and heated for 1 hour at 90CC with 200 g of xylene, 302 g of ~odium hydroxide and 1220 g of water.
~he mixture was then diluted with 3000 g o~ cold water and 370 g of 37 % hydrochloric acid were added dropwi~e over a period of one hour. After filtering off with ~uction and drying at 50C under vacuum, a colorless powder with a melting point of 138C wa~ obtained.
The product~ described in the previou~ Hection were then te~ted to determine their ef~ect in the rubber mixture~.
A ba~e batch having the ~ollowing composition (PbW 5 parts by weight) wa~ u~ed ~ ~tarting mixture, of which ~0 a relatively large amount was prepareds 100 PbN natural ~ubber 40 P~W carbon black 15 PbW active ~ilica 5 PbW zinc oxide 1 PbW ~tearic acid 1 PbW anti-aging agent TID prepare the various individual mixture~ the particular products to be te~ted wers mixed into the ba~e batch at temperatures between about 80 and 100C and then homogeneou~ly di~per~ed for about 10 minute~ a~ a temperature of about 120C. The mixing-in of 4 PbW of sulfur and 0.8 PbW of nc~elerator and of the melamine resin u~ed as curing agent then followed at temperatures below lOO~C.
After vulcanization, carried out under the conditions specified for the particular test 3eries, the test piece~
obtained were examined for the following propertie6 using the methods customary in the indu~try:
- ultimate tansile 6trength, elongation at break and ~tres~ value~ in accordance with DI~ 53504 - Shore A hardness according to DIN 53505 - rebound resil~ence a~cording to DIN 53512 20 - tear-out ~orce and dsgree of covering in the eteel cord adhesion test.
~he resul~s of the last-mentioned adhe~ion tes~, which wa~ carried out using a te~t arrangement in accordance with the recommendation of the 8tandards Committee deeignated ISO DP 56003.3, are particularly important.
For this purpose steel cord with a 4 x 0.25 construction with a copper content of the bra~s coating of 67 % wa~
embedded in the adhe~ion mixture in special molds and this adhe~ion mixture wa~ then vulcani~ad. The ~amples were then stored under different test conditions and the force nece~sary to tear-out the steel cord filaments from the rubber mixture wa8 then measured. The mean value for the force required to tear out the steel cord fr~m the vulcanized material, calculated from 10 individual te8t8 in each case, i8 guoted a~ the te~t re~ult and aclditionally the degree of cover~ng i~ sub~ectively a~s~sed. The latter iB to be under~tood to mean th~ area oiE pulled-out cord covered with rubber, which iB
sl~ectively e~timated in grading~ of 10 ~ (i.e. grading 1l, 2, 3... 10 denotes 10, 20, 30.~.100 ~ covered cord area). Thus, better adhesion of the rubber mixture to ~he ~teel cord i8 accompanied by high~r te~t figure~ both for t]he tear-out force and for the degree of covering.
A~ i~ to be seen from the result~ in Table 1, the rubber mixtures prepared with ~ho product~ sccording to the invention in accordance with ExRmple 13, 15 and 16 achieve higher degrees of covering than the comparison with re~orcinol. In particular after heat-aging for 14 days at 90C, the comparative mix~ure with resorcinol lS shows a decrea~e from 80 % to about S0 ~, whilst the mixtures prepared with the copolymer~ change by not more than 10 % to degrees of covering of 70 to 90 ~. If, in order to ~imulate unfavorable conditions in practice, the vulcanization time iB increa~ed threefold, even more pronounced differences between the comparison and the mixture~ according to the invention are then revealed.
The degree of covering before additional exposure to heat fall~ to about 40 % in the ca~e of the resor~inol-containing mixture, whilst the mixture~ according to the invention achie~e 70 to 100 %. After a heat-aging at goaC
o~er a period of 14 day~, the latter decline to degree~
of c~ering of 60 to 90 ~ and are thus clearly better than the compari~on with approximately 30 ~.
2 ~ J- r8 Tllbl~ 1 ~lxtur , pr p-rad ol4nd~on ~ltb poly~or ~coordl~g lYtur-to 8~ cpleYltb ~3 lS 16 _ h~ount of copolyoor or r- orclnol add-d ~PbW~ 2 5 2 5 2 5 2 5 ~Dunt Or alaxl~o ru-ln ddnd(PbW) 3 85 3 55 3 85 3 85 V~lc~nl~tlou ~t ~5 Clrln) ~0 60 60 60 UltiJat- tonJll- tr-ngtb(~Po~17 18 19 16 tlongatlon ~t bx~ ) 380 390 ~10 dOO
8tr-~- q~lu-~t 10 ~ lona~tlon (~p~) 1 1 1 0 1 1 0 9 50 t olongatlon (~p ) 2 2 1 9 2 0 1 7 100 ~ olong~tlon ~p~) 3 5 3 2 3 3 2 7 Robound r--lll nc~ (DIR 53512) ~ 0 30 abor A b rdno-- (DI~ 53505) 67 66 68 72 I-~r-out toro~ l~ c~ l)/oogro- of covarlng ~rt r torng~ 3 d/Z3 C 370/9 390/D 3~0/9 ~00/8 l~ d/~O C 180/9 170/7 19Q/8 Z20/S
3-told vulc~nl~ntion tl Alt r ntorn~o 3 dt23 C 310tlO 320t8 350t7 330 1~ dt50 C 200t9 170t6 l90t7 190t3 65 PbW or hox eothcxy3 tbyln l~lno p r 35 PbW 91118-
Claims (8)
1. The use of polymers which contain units of the formula (I) ( I ) as reinforcing resins and adhesion promoters in rubber mixtures, the symbols R1, R2 and n in formula (I) having the following meaning:
R1 is hydrogen or an acetyl group CH3CO-R2 is hydrogen or an alkyl or alkoxy group having 1 to 4 carbon atoms or halogen or -C=N and n is an integer from 1 to 4, with the proviso that if n > 1 the radicals R2 can be identical or different, and that at least in some of the units of the formula (I) there is a hydrogen atom in at least one of the positions vicinal to the R1-O- to the R1-O-group.
R1 is hydrogen or an acetyl group CH3CO-R2 is hydrogen or an alkyl or alkoxy group having 1 to 4 carbon atoms or halogen or -C=N and n is an integer from 1 to 4, with the proviso that if n > 1 the radicals R2 can be identical or different, and that at least in some of the units of the formula (I) there is a hydrogen atom in at least one of the positions vicinal to the R1-O- to the R1-O-group.
2. The embodiment as claimed in claim 1, wherein the polymer comprises units in which R1 is an acetyl group, R2 is hydrogen and n = 4.
3. The embodiment as claimed in claim 1, wherein the polymer comprises a mixture of units in which R1 is hydrogen or an acetyl group, R2 is hydrogen and n = 4.
4. The embodiment as claimed in claim 1, wherein the polymer comprises units in which R1 and R2 are hydrogen and n = 4.
5. The embodiment as claimed in claim 1, wherein the polymer is a mixed polymer that contains units of the formula I, and, in addition, units which are derived from monomers of the formula (II) (II) in which the symbols have the following meaning:
R3 are identical or different radicals from the group comprising hydrogen or an alkyl or an alkoxy group having 1 to 4 carbon atoms or halogen or -C=N or -COOH or -COO(C1-C4-alkyl) or in which p is an integer from 1 to 5, and R4 = R3 or a group
R3 are identical or different radicals from the group comprising hydrogen or an alkyl or an alkoxy group having 1 to 4 carbon atoms or halogen or -C=N or -COOH or -COO(C1-C4-alkyl) or in which p is an integer from 1 to 5, and R4 = R3 or a group
6. The embodiment as claimed in claim 5, wherein copolymers are used which contain units of 4-hydroxystyrene and/or of 4-acetoxystyrene and of butadiene.
7. The embodiment as claimed in claim 6, wherein the copolymer has an average molecular weight Mw of not more than about 150,000.
8. The embodiment as claimed in claim 1, wherein copolymers are used which contain units which are derived from cyclopentadiene or dicyclopentadiene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3914388.0 | 1989-04-29 | ||
| DE3914388A DE3914388A1 (en) | 1989-04-29 | 1989-04-29 | USE OF POLYMERS CONTAINING UNITS DERIVED FROM 4-HYDROXY OR 4-ACETOXYSTYRENE AS REINFORCING RESINS AND LIABILITY PROMOTORS IN RUBBER COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2015648A1 true CA2015648A1 (en) | 1990-10-29 |
Family
ID=6379879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002015648A Abandoned CA2015648A1 (en) | 1989-04-29 | 1990-04-27 | Use of polymers which contain units derived from 4-hydroxystyrene or 4-acetoxystyrene as reinforcing resins and adhesion promoters in rubber mixtures |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0396027B1 (en) |
| JP (1) | JPH02305835A (en) |
| KR (1) | KR900016343A (en) |
| AT (1) | ATE112791T1 (en) |
| CA (1) | CA2015648A1 (en) |
| DE (2) | DE3914388A1 (en) |
| ZA (1) | ZA903218B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266635A (en) * | 1993-02-26 | 1993-11-30 | Shell Oil Company | Impact resistant polycarbonates containing elastomers having phenolic groups |
| KR100332915B1 (en) * | 1997-12-23 | 2002-10-25 | 주식회사 포스코 | Process for producing styrene polymer chelate adhesive, for coating steel sheets, having improved adhesive force and corrosion resistance |
| US7011872B2 (en) | 2001-08-24 | 2006-03-14 | Baxter International Inc. | Method and process for enhancing properties and medical tubing performance in a polybutadiene material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4129557A (en) * | 1976-05-26 | 1978-12-12 | Sumitomo Chemical Company, Limited | Process for producing copolymerized resins |
-
1989
- 1989-04-29 DE DE3914388A patent/DE3914388A1/en not_active Withdrawn
-
1990
- 1990-04-26 DE DE59007422T patent/DE59007422D1/en not_active Expired - Fee Related
- 1990-04-26 EP EP90107980A patent/EP0396027B1/en not_active Expired - Lifetime
- 1990-04-26 AT AT90107980T patent/ATE112791T1/en not_active IP Right Cessation
- 1990-04-27 JP JP2110707A patent/JPH02305835A/en active Pending
- 1990-04-27 CA CA002015648A patent/CA2015648A1/en not_active Abandoned
- 1990-04-27 KR KR1019900005961A patent/KR900016343A/en not_active Application Discontinuation
- 1990-04-27 ZA ZA903218A patent/ZA903218B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02305835A (en) | 1990-12-19 |
| ATE112791T1 (en) | 1994-10-15 |
| ZA903218B (en) | 1991-02-27 |
| DE59007422D1 (en) | 1994-11-17 |
| KR900016343A (en) | 1990-11-13 |
| EP0396027A1 (en) | 1990-11-07 |
| EP0396027B1 (en) | 1994-10-12 |
| DE3914388A1 (en) | 1990-11-08 |
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