CA1112792A - Application of cumylphenol and derivatives thereof in plastic compositions - Google Patents

Abstract

Abstract of the Disclosure Cumylphenol and its ester derivatives may be used as accelerators in amine-cured epoxy systems.
Also, cumylphenol and its derivatives have been discovered to be useful as reactive diluents for epoxy, phenol and urethane resins. The glycidyl ether, a new composition of matter, is also useful as a reactive diluent for urethane resins. Additionally, the ester derivatives are non-reactive plasticizers for urethane and the benzoate and higher acyl ester for rigid polyvinyl chloride. The benzoate and higher acyl esters are also new compositions.

Description

This invention relates to the use o~ cumylphenol and derivatlves thereof as acceIerators, reactive diluents and non-reactive plasticizers.
~ ore specifically, this invention teaches the use of cumylphenol, admixtures thereof (particularly with alpha-methylstyrene dimer) and cumylphenyl esters as a replacement for nonylphenol and dinonylphenols as accelerators for amine-cured epoxy resins. The use of the nonylphenols as accelerators is well known and is descrihed in U.S. Patents 3,637,902;
3,740,373; and 3,763,102. It has been found that the cumylphenol per se is a much more effective accelerator than nonylphenol and that the mixture thereof with alpha-methylstyrene dimer provides a low-cost accelerator useful for controlling cure rates and improving the impact resistance of the resultant epoxide composition. Admixtures of cumylphenol and alpha-methylstyrene dimer may be readily obtained as a by-product from the cor~lmercially used process for making cumene from phenol. In this process, this by-product appears as a bottoms product in the purification of the cumene along with other high molecular weight products. ~he desired admixture may be separated by conventional vacuum distillation of the bottoms or the bottoms may be used directly without purification.
In another embodiment of the invention, cumylphenol and derivatives thereof have been found useful as reactive diluents for epoxy, furan and phenolic resins. Thus the present inventlorl provides a polymerizable composition which comprises an epo~y, phenolic or furan resin in admixture with 10 to 100 parts by weight of cumylphenol or its ester or ~
glycidyl derivati.ves for each 100 parts by weight of resin.
In another aspect the invention provides a polymeric composition which comprises a copolymer of (A) 100 parts by - _ : : : :
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weight of an epoxy, phenollc or furan resin, and (B) 10 to 100 parts by weight of cumylphenol or its ester or glycidyl derivatlves.
In preferred embodiments such polymeric compositions are provided wherein the ester is the acetate or benzoate ester.
The glycidyl ether derivative may also serve this function for urethane resins~ These ethers are new compositions of matter and provide a low cost replacement for conventionally employed co-monomeric materials. In certain instances, their use improves the chemical and physical properties of the cured resins. Thus the invention provides in one aspect a polymeric composition which comprises a copolymer of cumylphenyl glycidyl ether and a urethane resin. In another aspect the - invention provides a polymeric composition which comprises an admixture of from 10 to 100 parts by weight of cumylphenyl glycidyl ether or a cumylphenyl ester and 100 parts of a urethane resin.
In still another embodiment of the invention, it has been found that esters of cumylphenol are useful as non-reactive plasticizers for polyurethanes. The benzoate and thehigher acyl esters, which are unique compounds î may be used for rigid polyvinyl chloride. Here again the cost of the finished resin may be markedly reduced. Thus the present invention provides as novel compounds cumylphenyl benzoate and alkyl esters of cumylphenol wherein the alkyl ~roup has 6 to 10 carbon atoms. In another aspect the present invention provides a polymerizable composition which comprises vinyl chloride resin and a plasticizing amount of the benzyl or a higher alkyl ester of cumylphenyl. In still a further aspect the invention provides a rigid polyvinyl chloride having improved processing

- 2 -, properties containing a plasticizing amount of the benzyl or a higher alkyl es-ter of cumylphenol.
The derivatives of cumy:Lp~enol which are useful in the invention may be represented by the following ~ormula:

C ~ ~ OR, ~ l~3 ~

wherein R is an acyl group, C-R', where P~' is an alkyl, aryl, or aralkyl group having 1 to 12 carbon atoms, or a glycidyl group having 3 to 6 carbon atoms. ~ore preferably, R' is a methyl, an ethyl, or a long chain alkyl group, and the glycidyl 0 group is~CH2CH-CH20 Certain of these compounds are well known in the art. The acetyl derivative is described by Tsivunin et al., Biol. Akliv-. Soldin. 1968, 172-5 (Russ.). However, some are new compositions of matter, viz., the glycidyl ether, the benzoate ester and the higher acyl esters of cumylphenol.
Of this latter group, the most important are the esters where R' has from 6 to 10 carbon atoms.

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, ~ere the cun~lphenol or its esters are used as accelerators for amine-cured epoxy syster~s, the a~ount of the cum~l~henol .~aterials may ra~ge frorn 5 to 30~, prcferably from 10 to 20~, based on the ~leight 3 5of resin to be cured. Any o~ the conventional amine~
curing syster.s may be used, e.g.~ aliphatic poly~lines, aro~atic poly~nes and polya~ino~ide.
In this application~ the epoxy resin in the liquid stake is placed in a reactor and mixed ~ith the 10amine-curing syste~. Generally lro~ 5 to 50 parts of curative are used along with the cumAylphenol accelerator.
The reac~ion mass is heated to a te~perature in the range of from 0 to 250 C. at pressures from 10 ~m ~g to 5 atm. until the desired cure is achieved.
Where the c~ylphenol derivatives are vsed as reactive diluents, they ~ay be present in from about 10 to about 200 parts per 100 parts of the resin, pre~erably from about 20 to about 50 parts.
In non-reactive plasticiæer applications, from 15 to 50 wt. ~, preferably from 20 to 40 ~ , of the a~propriate ester o~ the c~ylphenol is used based on total weight o~ resin~
In the applications of ~he invention where the c~mylphenols are used as reactive diluents or non-reactive plasticizers~ the cvmylphenol co~ovnd is initiall~
blended with the appropriate resin along ~ith other desired components. The blend is ~ee~d to the polymerizing reactor and the resin polymerized in accordance with known ~;
techniques for the partlcular resin.

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Where the cumyl phenols ~re used as reactive diluents for epoxy resins, any known curing system may be used. If an amine system is used, the cumylphenol may also have an accelerating effect; however, other curing systems? e.g., anhydrides, are fully acceptable.
The resins which are cured and for~ed in the practice of the invention, with the exception of polyvinyl chloride, may be generically re~erred to as "liquid thermoset resins H By this term is meant resins which are in the liquid state under conditions of application and include casting resins9 i.e ~ liquid monomers or incompletely polymerized polymers, usually containing catalysts or curing agents, capable of becoming hard after they are cast in molds; and coating resins, i e.~ liquid monomers or incompletely polymerized polymers, optionally in a solvent or non-solvent ex~ender, whlch are capable of applicatlon by casting, potting, brushing~ rolling, spraying or dipping. These include paints~ varnishes, enamels, lacquers, and casting and potting resins.
The resins of particular interest in the instant ~i invention are epoxy resins, furans, phenolics, urethanes and polyvinyl chloride. These may briefly be described as follows:
A wide variety of epoxy resins are described in U.S. Patent 2,698,315, issued December 28, 1954; U.S.
Patent 2,707~708, issued May 3, 19553 and U.S. Patent 2,705,223, issued March 29~ 1955. These resin are commonly : :

complex ~olym~ric reacJion proc~ucts of polyhJ~dric alcoho~s l~it~l polyfunctional halo~Jrdrins such as epichlorohydrin and glyceryl dichlorohydiin. The products obtained ~ay contain tertnina.l epoxy grovps, or terr~nal epoxy groups and ter~.inal primary hydrox-rl groups See, for exa~nple, CQlEnn 6 of U.S. Patent 2,872,4283 issued ~ebruar~ 3, 1959.
The furan resins are the ~osetti.ng resins obtained pri~.arily by the condensation pol~nerizztion of furfural alcohol in tre presence of a strong ~cid, soInetines in com~,ination ~7ith for~.aldeh~de or furLural.
The terrn also includes resins rnade b~ condensin~ phenol Wit;l ~uri~ryl alcohol or furfural~ and furfuryl-ketone polymers.
Phenolic resins are a ~a-~ily o~ thert~oset resins nade by the reaction of phenols wi'Gh aldehydes such as formaldehyde~ acetalder.yde, or furfuLal in the presence of either acidic or basic catalys~s. ~or castingJ, B-staOe resins are generally used. Exarnples of the henols are di- and triTialen'G phenols such as cresol, resorcinol and cardanol. In casting resin applicztions, a large excess o~ ~ornaldehyde is generally used Wi ~h sodiu~ hydroxide as the catalyst. ~he reaction is usually car-ied ou~ at about 6L~ C. .
The polyurethanes are z fær:lily of resins produced - by reacting cliisocyznztes with orOznic cor~.~ounds contzinin two or ~nore active a~o~s to fo~m. ~ol~ners having free Ir isocyanate groups. A detailed descrip~ion of these resins is given in U.S. Patent 3,0~0,137~ issued Oc~ober 23, 1962.
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Thcse ~roups, under the influence Of heat or catalyst, will react ~,rith eac~ o~her or ~!ith ,;a'er, glycols, etc,, to fo~m ther~osetting materials, Rigid polyvinyl chloride resins optionally contain extenders, pigments~ stabilizers anfi a small proportion of plasticizers ~.~hel~ein the p~oportion of plasticizer is ~.
insufficient to reduce tensile modulus belo~,r about 2000 psi.
The follol~rin~ t~o exa~ples sho:J the e~bodiments of the invention relating to the use of cumylphenols as ~
accelerato~s in amine-cured epoxy systems: .
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EX~L!'(1.~ 1 e This exam~le sho~ls the use of a blend ol 6G~
cumylphenol, 34~ alpha-rneth~lstyre~e dimer and 6~
acetophenone as an accelerator for the cure of epoxy 5 resins. The composition has the follo.~nrr properties:
Specific C-ravity at 25 C.1.052 Viscosity at 25 C , cps 99 Distillation Range (5$-~5~ AS~I D~85), C.236~327 1~ Flash Point COC, F. 275 Hydroxyl M~rnber 171 -Avg. ~iIolecular T/~Jeight (Calc.) 209 Gardner Color 9-10 Pou~ Point, F. Below 40 Tests were per~or~ed with Epon 82~ (trademarl.~ of Shell Chemical Co.), an epoxy resin having an epoxy equivalent of 185 to 192 ~ith t~ro curatives, namely, diethylenetriamine and triethylenetetramine. The admixture of the invention was compared to conventional accelerators, namely, nonylphenol an~ dinonylphenol. ~he co~positions are shown in the follo~ing table alOng with the gel tim0, cure time, and Shore D hardness o~ the cured co~posi,ions.

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The above data sho~ th~t the c~ylphenol blend has a superior cure rate as co.~.~2.red t~ n the unaccelerated runs. This ma~erial also shors su~er~or~y to the d~-nonylphenol accelerator but is about 10-20~ slo~rer than the nonylphenol. Consi.dering the ready availability of the a~oresaid blend and the fact th~ it con~2i~s considerably ~y less of the phenolic co~pound than the pure nQnylphenol, its activity as an accelerator is particularly outsts.n~ing ;~X~

Example 2 Four epoxy resin formulations ~.Jere prepared, the first without an accelerator; the second l~i~h the prior ar~ accelerator, nonylphenol; and the last ~''70 with dif~erent levels of high purit~ c~yl~henol. The c~yl-phenol had the ~olloT~ring physical ~roner~ies:
Appear~nce: ~ight tan cryst211ine .~aterial Specific Gravity~ 25/25 G. .094 ~lash Point, COC~ F. 345 Drop Melting Point~ F. 154 Table II belo~ shows the speci,ic cD.~ osition of the ~ormulations, the gel and cure ti~.es, and ~he Shore D
hardness of the cured material:
able II
1 2 3 L~
Epon 828 100 100 100 100 Triethylenetetramine 12 12 12 12 Nonylphenol - 20 ~ -Cu~ylphenol - - 20 10 ~ir Gel Ti~e, min~ 68 281LL.5 22 Cure Time, min~ 150 107 78 95 Shore D Hardness, 24 hrs , at 20~ C85 85 93 89 g _ I

'J'''~2 The above table not only shows the improved cure and gel times achieved b~ u~ing the c~nylpnenol, but it also shows that~ at only half the level of the prior art acceleratorg improvement is realized. Furthermore, the cumylphenol, particularly at the level of For~ulation No. 4, i~proves the Shore D hardness~ a result not realized with the nonylphenol.

~ he following ~x~mples 3 to 10 illustrate the effectiveness of the cumylphenols as reactlve diluen-ts for epoxy, furan~ phenolic and urethane resins Exa~ple 3 This exam~le shoTrs the effec~ of c~mylphenol and its derivatives on the physical properties of epoxy resins.
Formulations were prepared using Epon 828 (average viscosit~, 16,00C centipoise) epoxy resins, 100 parts; trieth~lene-tetramine as a curative, 12 parts; and Berkley ~1 sand in amounts shown in the folloNing table; and with cumylphenol ; and its acetate and glycidyl ether derivatives. The compressive strength and the tensile strength of compositions~
cured at ambient temperature~ were measured af~er five days The following table shows the ~ormulations and the results obtained:

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Table III
Parts Co~npree~sive Tensile by Strength, Strength, Addltive IJei~htEpoYySand E~ ~si M
None - 88 200 12.0 0,9 _ 88 250 10.9 o.76 " 88 300 9.~ 0.71 Cumylphenol 22 66 200 17.3 1,2 " 22 66 250 16,9 1,0 22 66 300 16.5 0,91 ~ .
22 66 350 15,8 0.82 " 22 66 400 NP 23P
Cumylphenyl 22 66 200 19.4 1.65 22 66 250 18,1 1.51 " 22 66 300 1~.3 1,38 ?2 66 1~00 14.8 1.16 " 22 66 450 12.1 0.94 - 20 " 22 66 500 ~P NP
Cumylphenyl Glycidyl Ether 22 66 200 14.6 1.08 22 66 250 13.7 o.98 " 22 66 300 12.1 0.92 " 22 66 400 9.9 o 83 NP = non-pourable - : ~ .

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The above table clearly sho~rs that the co~pressive stren~th and the tensile strength are markedly i~.~proved by subs~ituting the c~ylphenol or its deril~atives for a portion of vhe epoYy co.~position The table further shows that 400, 500 and 450 ~arts ~:~ere added in the cases of the cu~ylphenol, the c~nylphenyl acetate and tne cumylphenyl glycidyl ether, respectively, ,J
before the non-pour~ble condition occurred. This shows that the additives o~ the invention all have an effect ol reducing the viscosity o~ the mix-ture This is o~
great ad~antage, since it permits hi~her 102di;ig and lower cost co~posi~ions Exa~ple 4 Two anhydride cure epoxy resin for~ulations were prepared, the first using a reactive diluent known in the art, cresyl glycidyl ether, and the second acetyl p-cumylphenol ol the invention The co~.positions and ~lexural strength o~ the product cured ~or 20 minutes at 375 F. are shown in the table below Table IV

, ~poxy 6010 80 8~ -Cresyl glycidyl ether 20 -Acetyl para-cumylphenol - 20 Dodecylsuccinic anhydride 50 50 IjJ
~lexural strength 13.5 M 20 3 M

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'-' ' ' ~h~7'~`P~ i ' The ~,ove table sho~s that in comparison to the reactive diluents of the prior art the acetate ester of c~mylphenol results in a product having a substantially higller flexural strength. Additionally, this example shows the application of cu~ylphe,~ol derivatives in anhydride-cured epoxy resins, as ~ell as the amine-cured system sho~,~n in Example 3, ~,:
Exa~ple 5 ,~t This example sho~s the effect of acetyl p-cumyl-phenol on the viscosity of epoxy flooring compounds. A
control compound containing 100 parts of Resiplex 1628 (trademark of Resyn Corp. for an epoxy resin havin~ a viscosity of 12~000 cps) was admixed with 20 parts of an accelerated proprietary aliphatic polyamine hardener (Cela,nese 874) and 160 parts of Colorquartz ~28 (trademark of 3M Co.), Additional compositions were formulated~ the first containing 65 parts of the Resiplex and 35 parts of the acetyl p-cumylphenol, and the second 50 parts each of the Resiplex and the acetyl p-cumylphenol. It was ~ound that the sand content could be increased to 260 and 300 parts in these compositions, respectively~ without adversely affecting the "trowel feel" of the composition. Sav~ngs are realized not only in increasing the amount of filler present but by using the lo~ c05~t acetyl p-cumylphenyl derivative in place of the expensive epoxy resin.

Example 6 - ~ /' '' This example sho~7s the use o~ cu~.ylphenyl derivatives '~
as a replacement for furfuryl alcohol in furfural epoxy s~stems. Four fo~ulations were prepared. The first formulation served as a control and represents a typical t - 13 _ l 7~

epoxy~f-lrfural system usin~ a phenyl ~lycidyl ether-modifi.ed resin. ~o~mulatio~ 2 is ~ubstantially the same as the first, but shoTs the use of a less e ~ensive unmodified epo~y resin. Formulations 3 and 4 sho~/ the application of the instant invention ~rrereby the acetyl p-c~mylphenol serves to replace the ~urfuryl alcohol.
Table V shows the specific com~ositions er.~loyed. The viscosity of the formulations and their p`nysical properties were tested.
Table V
Formulation 1 2 3 4 Epoxy 6004* 73 _ _ 44 E~oxy ~0'0* _ 73 4L~ _ Furfuryl Alcohol27 27 _ _ Acetyl p-C~ylphenol ~ ~ 23 29 Grade~ ~and (Pre-~lende~d) 375 370 376 37 Methylene dianiline (Pr-e-bIended) 24 24 24 24 * Ciba-Geigy trademark of epoxy resins Formulation 2 ~fas o little use sinci~ it was not pumpable. On the other hand, For~vla.tion 3 had a Viscosi'Gy comparable to Formulation 1, and Formulation ~ was even less viscous than the control. Furthermore, the ph~sical ~ ~ properties~ such as hardness, tensile and compressive ; 25 strength, of FormuIations 3 and ~ we~e all within +10~ of the control~ again with Formulation ~ shot~!ing a slight edge ; ~ Example 7 ~
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This e~ample shoT~Js the use o~ the cu~ylphenol, its derivatives~ and blends tne~eo~ as a replacement for i .
~ur~uryl alcohol in a typical furane resin system. Table VI beloT:J shows the compositions tes~ed:

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The acetyl p-c~lylphenol as co~pared ~rith the furfural-lur~ryl alcohol control had i~proved flexibility as ~ell ~s i~pact rebound and che~ical properties. On the other hand, the c~ylphenol provided a very hard material with so~ewhat i~proved i~act and rebound properties and very good chemical resistanceO Finall~, the cu~ lphenol blend resulted in a harder material with good i~pact and chemical resistance and i~proved rebound properties, Considerin~ the substantially lo~,Jer cost o~
the materials discussed herein, the i~proved chemical and physical properties are particularly surprising, The properties obtained are co~parable to phenolic resins.
S~ill another advantage is tha~ one can use an unmodiLied epox~ resin (5010) rather than the phenyl glycidyl ether-modiiied resin (~004) conventionally used ; in such coating compositions.

Exa~le 8 -To show the usefulness of cu ~ lphen~l derivatives f~r replacing the phenolic co~onent in ba~ing resins~
five formulations ~ere prepared. ~he first consisted of the conventional epoxy phenolic co~position; the second, third and fourth showed the replæcement ol 25~, 5C~ and 75~ of the phenolic resin with the acetyl p-cumwlphenol;
and the last sho~ed co~.nplete replæcement, The specific co~positions are sho-~n in the followin~ table:
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Table ~TII
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Formula.tions 1 2 3 4 5 Epon 828 Epo.~:y P~esin 37 5 37.5 37.5 37 5 37 5 Bakelite Phenolic Resin, ~ 2620 25.5 19.1 12.7 6.4 Acetyl p-cumylphenol - 61412.7 19.1 25,5 Melamine 25.0 25.0 25.025.0 25.0 Solvent 220.0 220.0 220.0220.0 220.0 The compounds o~ the invention, na~ely, those in Formulations 2 through 5, cured and behaved co.Y.~lparably to the control. Where the control ~ad a shel~ life of .
approximately three months, each ol these latter formulationi, had shelf lives exceeding three m.onths with no incre~s~ in viscosity observed.
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Exa~nple 9 Part I
This example shows the e~Lect of the addition of cumylphenol as a modi~ier using a con~entional phenolic resin A basi formulation was prepared containing the 20 following:
: Phenolic Resin Bakelite, ~BRNA-5345 100 parts Colorquartz ~28300 parts ..
: Toluene sul~onic acid 5 parts Hexame-hylenetetra~ine 10 parts ~he aforesaid formulation was cu-red for ten m~nutes ~
at 375 F. and the tensile stren6th co~Toared to formulation~ ~ ;
wherein 10 and. 20 parts by ~,reight of fur ural:c~mylphenol (2:3 dr~r weight)~ mono~ner mixture Jere used with 90 and 80 30 parts, respectively, of ~he phenolic resin.

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Tensile strength on the three cured compositions sho;~ed 350, 430 an~ 490 for the unmodified resin~ the 90:10 and the 80:20 rnodified resins, respectively. This clearly sho~ls that the monomer mixture is use~ul in irnproving the physical characteristics of phenolic systems~

Par Using the basic for~ulation described in Part I, various proportions of the phenolic resin were replaced by equal ~eights OL' the monomer mixtures shown belo~r .
In each case, the monomer mixture contained 2 parts o~
furfural and 3 parts of phenolic monor~er. The tensile strength o~ each ~ormulation was tested. The co~position of the for~ulations are shown in the table below.
Table VIII
_ Mono~e~r Mixture Added Tensile Parts Replaced ~lir~ture Strength, psi - None 350 Furfural:cumylphenol 570 Fur~ural:cu~ylphenol 730 100 Furfural:cumylphenol 910 Fur~ural:cumylphenyl acetate 380 100 Furfural:cu~ylphenyl acetate 560 Furfural:nonylphenol 380 100 Fur~ural:nonylphenol 480 ' .
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The above table sho~rs that the replacement o~
the phenolic resln b~ the furl~ral c~m~lphenol monomer mixtures results in continuall~ pro~ed tensile strength, up to the point ~lhere, when the phenolic resin is co~pletely replaced, a co~osition havin~ almost three times the tensile stren~th is obtained ~n ';he case o~
the cu~ylphenyl acetate, an i~.provemen~ is nc~ed~ but not to as great a degree as with the c~lphenol monomer ~ixture In contrast, the use of the ~ur~ural-nonylphenol mixture, a mixture not within the sco?e o the ~nstan-~invention, shows co~parati~ely li~tle i.~prove~ent in properties The use of the ~onomer mi~tures of the in~Jention t~
replace all or part of the phenolic resins resul~s in advantages other than the mere tensile s~rength inprovement.
For example, these mixtures are more easily handled because they are ~ore fluid than the phenolic resin per se.
Additionally~ t~e furfural-cu~ylphenol monomers may be used under conditions where the conventional ~henolic resins' constituent monomers cannot because of the latters' high volatility and toxicity r~

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Example 10 This exampl; sho~s the use of eumylphenyl glycidyl ether as a reactive diluent ~or polyurethane.
- Part I
The cumylpnenyl glycidyl ether was prepared as follo~s: A 3-liter flask equipped ~ith a mechanical stirrer, thermometer, addition funnel, and external heating and cooling devices was charged sequentially with 1 liter of benzene~ 1 liter of 4 5 wt. ~ aquedus sodium hydroxide and 1 mole of cumylphenol. The c~ylphenol benzene dispersion formed after mixing was cooled to 10-15 C., mixed and maintained at 10-15 C. during the addition of 1.1 moles of epichlorohydrin over a four hour period. After the addition of the ch~ohydrin, the reaction mix was ~armed to 50 C. for 8 hours. The two phases which formed were separated and the water phase discarded. The organic phase was thrice washed with cold water and the residual organic material fractionated.
One hundred ninety grams (71 mole ~) of a pale yellow oil havlng a boiling point at 5 mm Hg of 258-263 C. was obtained. The oil had an Epoxide Number determined by MgCl~-HCl titration of 3.72 meq/g~ while the theoretical Epoxide Number for cumylphenyl glycidyl ether is 3.73 meq~g.
Part II
Five polyurethane compositions containing 100 parts by weight of polyurethane (Adiprene C~l, trademark of E. I.
DuPont deNemours & Co.), a reaction product of diisocyanate .
and polyalkyIene ether glycol, 30 parts of HAF carbon black~
'! 1 part of mercaptobenzothiazole, 4 parts of 2,2l-benzothiazyl disulfide, 0.5 part of zinc chloride-2,2'-benzothiazyl ' i disulfide~ 0.75 par-t of sulfur and 0.5 part of ca~mi~m stearate ~3-ere prepared. The first ~ormulation contained no plasticizer or reactive diluent. Second, third and fourth formulations were also prepared, these containing dioctyl phthalate (DOP), dioctyl sebecate (DOS) and a heavy aromatic naphtha oil diluent (Sundex 790~ a trademark o~ Sun Oil Company), respectively. The flrst two of these materials are conventionally knoT~Jn non-reactive plasticizers, while the fourth is a reactive plasticizer. 3 To a fifth formulation, 15 parts by weight o~ the cumyl-phenyl glycidyl ether (CGE) of ~he invention ,ras added The co~positions were cured for 60 minutes at 140 C.~
an~ the phycical properties tested. The results are sho~n in the following table:
Table IX

` : Plasticizer None DOPDOS Na~htha CGE
300~ Modulus psi 285019001750 1700 1810 Tensile psi 405038003550 4550 5200 Elongation at Break ~l'20 470 460 540 530 Hardness Durometer A 70 62 61 62 67 The above data clearly show that the cumylpheny~
glycidyl ether of the invention ~as effective in reducing the modulus of the polyurethane formulation. They further show that it is substantially better than the other ;
plasticizers~ since the cured com osition has a much better tensile strength and, of the composiJions tested~
there is the least loss of hardness. This combination of properties is particularly use~ul, as will be readily ' !

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. l,-recogni7ed by one skilled in the art~ and raost surprising and ur.expected. Further~ore, even in the case of the naphtha oil, the other reactive diluent, the tensile strength was much better This may be attributable to the glycidyl ether i~proving the cure. ~r The following Examples 11 to 13 show the use of certain cumylphenol derivatives as non-reactive plasticizers for the specified resins.

Example 11 3 This example shows the use of acetyl p-c~mylphenol as a non-reactive plasticizer ~or urethane resin. The follo~:ling for~ulations were prepared:
Table X
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Formulation 1 2 3 4 ~ . .
Polyurethane resin* 100 100100 100 Dioctyl phthalate - 25 - -Diethyleneglycol dibenzoate - - 25 Acetyl p-cumylphenol - - - 25 300~ Modulus, psi 1570 1040 11101070 Elongation~ ~ 760 920 900940 Tensile, psi 8500 4580 52705750 * A polytetramethylene ether glycol-based ~;
thermoplastic having a Shore A hardness of 90.

The above data show that the acetyl p-c~mylphenol , provides a combination o~ higher elongation and much higher tensile strength and similar modulus efficiency as co~pared with widely kno~ plasticizers for u~ethanes.

t ~xa~ple 12 Tnis e~anple shows the u~ility of p-c~ylphenyl ben~oate as a processing aid and lubricant for the extrusion of rigid PVC.
Part I
Cwmylphenyl benzoate is ~repared in ~ccordance with the ~ollowing procedure: one mole of c~ylphenol ~,ras dissolved in 600 ml o~ benzene containing 1.2 moles of triethylamine in a 2~ ter stirred glass reactQr equipped with external heating and cooling devices. The reaction mass was cooled to and maintained at 15-20 C. during .
the addit-lon of 1.1 moles of benzoyl chloride over a period of 1.5 hours After com~letion o~ addition, 'he resulting slurry ~Jas heated to and maintained at 40-45 C.
f~r 1 hour~ and thereafter cooled to ambient temperature and filtered. The filter ca~e was washed with 200 ml o~
~oluene and the combined washings and filt~ate distilled to give 214.9 g (68 mole ~) of a pale yello-r oil having a boiling point at 0.5 ~m Hg of 261-265 C., a specific -gra~ity at 55 C. of 1.082, and a viscosity at 55 C. of 215 cps. On standing, the oil solidified to form a while solid having a melting point of 43-46.5 C.
Part II
,.
The follo~Jing ~ormulations were premixed in a high inter,sity nixer (Disona) and ambient temperature and extruded through a standard type 4" pipe die at 180 ~10 C., at a fixed power input. The physical proper~ies of the ; ~ extludate and the rate of extrusion are also shown in the I ~able belo~,:
., j :

7~,~
Table_ XI
Formulations 1 2 PVC resin* 100 100 Triphenyl phosphite (stabilizer) o,5 o,5 Diphenyl phthalate (processing aid) 1.0 -Calcium stearate 1.0 1.0 Oxidized polyethylene 0.2 -10 (Allied Chemical Corp, AC 629A) ~ax (Hoechst XL165) 1.0 2~2 Cumylphenyl benzoate - 1,0 Extrusion Rate, inches/min. 8" 10,4"
Impact Strength, psi 20~ 210 Flexural Strength, psi 16.2M l9.1M

* VC 100, Bordon Chemical trademark for a low to medium molecular ~eight resin.

The addition of the benzoate ester resulted in a 24~ extrusion rate improvement and an 18~ flex strength improve~ent~ without any s2crifice ol impact strength.
Other experiments show that the benzoa~e ester is unique in this regard and that similar improvements do not result from other cumylphenol derivatives.
~ ~ .
Example 13 ~; ~ 25 Thls exampie sho~rs the use of a higher alkyl ester i of cumylpheno:L as a non-reactive plasticizer for polyvinyl ; chLoride.
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7~

Part I
Cumylphen~l 2-ethylhe.canoate ~as prepareà in accordance with the following procedure: a 2-liter flask equipped with a mechanical agitator, a ten theoretical plate fractionating column, an automa~ic reflux splitter pot vapor ther~o~eters and thermo-controllers, a condenser, receivers, and external heating and cooling devices, ~,las charged ~ith 2 moles of c~myl-phenyl acetate~ 5 moles of 2-ethylhexanoic acid and 5 grams of 98~ sulfuric acid Heat was supplied externally and the distillate was collected at a 20:1 reflux ratio at a vapor te~perature below 120 C. at atmospheric pressure A total of 61~ cc of distillate was collected in 24 hours. The residual pot contents were cooled to ambient temperature and extracted 5 times with 2 liters of 8~ sodi~ b.icaxbona~e dried over anhydrous Na2S0~ and fractionated to give 408 g (58 mole ~) of a pale yello~ish oil~ The oil had a boiling point at 0.2 mm Hg of 252-257 C.j a specific gravity 20/20 of 1.045 and a saponification value of 2.82 meq/g. The cumylphenyl 2-ethylhexanoate ester has a theoretical saponification value of 2.~5 meq/g.
Part II
To show the efficacy of the 2-ethylhexanoate ester as a plasticizer for flexible polyvinyl chloride, 100 parts of a mediu~ molecular weight PVC resin was a~mixed , with 40 parts by weight of 5 micron calcium carbonate, t , and 2 parts by weight of Ther~ozard S stabilizer (a trade-mark of M & T Chemicals, Inc.). Three for~ulations were 30~ prepared. The first contained 30 parts by weight of tri- ~t - 25 - ~.
. , ............ ,, l 7~

etilylene glycol dibenzoate, the second 30 parts by weight of dioctyl phthalate, and the third 30 parts by welght of the cumylphenyl 2-ethylhexanoate of the invention. The following table sho~s the physical properties of the blend after cure:
Table_XIII ~

3 ~ .
Plasticizer TGD DOP CPE

Hardness Shore Scale 78 75 76 . b, 100% Modulus 1550 1320 1350 Tensile Strength~
psi 2350 1890 2510 Elongation 290 310 340 The above table clearly sho~s that the compound of the invention effectively reduces the ~odulus of the formulation. In comparison to the other plas.ticizers~
the 2-ethylhexanoate ester--containing for~ulation has .
the best tensile strength and percent elongation.

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Claims (6)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A polymeric composition which comprises (A) a urethane, phenolic or furan resin and (B) a cumylphenyl glycidyl ether or a cumylphenyl ester.

2. The polymeric composition of claim 1 wherein the composition is a copolymer of component (A) and component (B), and component (A) is a phenolic or furan resin.

3. The polymeric composition of claims 1 or 2 wherein there are present from 10 to 100 parts by weight of component (B) per 100 parts by weight of component (A).

4. The polymeric composition of claim 1 wherein the cumylphenyl ester is an acetate or benzoate.

5. The polymeric composition of claim 1 wherein the composition is a copolymer of component (A) and component (B), component (A) is a urethane resin, and component (B) is a cumylphenyl glycidyl ehter.

6. The polymeric composition of claim 1 wherein component (A) is a urethane resin and component (B) is a plasticing amount of an ester of cumylphenol.