CA1134994A - Process for producing hydrocarbon resins having improved color and thermal stability - Google Patents
Process for producing hydrocarbon resins having improved color and thermal stabilityInfo
- Publication number
- CA1134994A CA1134994A CA000318616A CA318616A CA1134994A CA 1134994 A CA1134994 A CA 1134994A CA 000318616 A CA000318616 A CA 000318616A CA 318616 A CA318616 A CA 318616A CA 1134994 A CA1134994 A CA 1134994A
- Authority
- CA
- Canada
- Prior art keywords
- fraction
- petroleum
- weight
- cyclopentadienes
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
Abstract
ABSTRACT
This invention relates to a process for producing a hydrocarbon resin having improved color and thermal stability, which comprises treating a petroleum cracking or reforming fraction containing cationically poly-merizable hydrocarbons and not more than 0.7% by weight, based on the fraction, of cyclopentadienes and having a boiling range of from 140°C to280°C, with 0.8 to 3.0 moles, per mole of the cyclopentadienes, of a dienophile compound having a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond; and then polymerizing the treated petroleum fraction in the presence of a polymerization catalyst.
This invention relates to a process for producing a hydrocarbon resin having improved color and thermal stability, which comprises treating a petroleum cracking or reforming fraction containing cationically poly-merizable hydrocarbons and not more than 0.7% by weight, based on the fraction, of cyclopentadienes and having a boiling range of from 140°C to280°C, with 0.8 to 3.0 moles, per mole of the cyclopentadienes, of a dienophile compound having a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond; and then polymerizing the treated petroleum fraction in the presence of a polymerization catalyst.
Description
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-- 1 .
r~his invention relates to an improved process for producing hydroc~rbon resins. More specifically, it relates to a process for producing hydrocarbo~ resins having greatly reduced coloration and very high thermal stability which consist mainly of aromatic hydrocarbon units~
It has been well ~nown to produce hydrocarbon resins by polymerizing a thermal cracking or ref~rming petroleum fraction containing ~msaturated hydrocarbons using Friedel-Fracts catalysts~ ~he hydroc~rbon resins are classified into aliphatic hydrocarbon resin~ obtained by polymerizing a petroleum fraction containing aliphatic unsaturated hydrocarbons as m~in constituents ana having a boiling range of from -20Co to 100C,, and aromatic hydrocarbon resins obtained by pol~merizing a petroleum --fraction containing aromatic unsaturated hydrocarbons as main constituents and having a boiling range of from 140C to 280C. ~he aromatic hydrocarbon resins have lower thermal stability, stronger offensive odor and ;~
greater coloration than the aliphatic species~ For this reason, it has previously been considered as difficult to use the aromatic hydrocarbon resins i~ applications which require superior thermal stability, a low degree of odor or freedom from odor, or a low degree of coloration, for ~25 example in hot-melt adheslves, pressure-sensitive ad-~hesives, or thermo-fusible traffib paints.
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Methods have previously been sugge8ted for~pre-treatlng a petroleum fractlon~containing unsaturated ;.
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hydrocarbons, mainly alipha-tic unsaturated hydrocarbons, having a boiling point of not more than 280~o and co~-taining at least 5 carbon atoms to remove from it un-desirable components which will worsen the color or hyarocarbon resins and/or form a gel (insoluble polymer), especially cyclo~ienes such as cyclo~entadiene or methyl-cyclopentadieneO For example, UOS. Patent 2,770,613 discloses a method for removing them by pre-heating the fraction at 90 to 140C to dimerize cyclodienes. hc-cording to this method, however, the treating operationis complicated~ an~ because unsaturated hydrocarbon components in an unsaturated hy~rocarbon-containing fraction of the polymeriæation material are re~oved as adducts with cyclopentadienes, the loss of uns~turated hydrocarbons other than cyclopentadienes is great. When this method is applied to the polym~rization of a frac-tion containing aliphatic unsaturated hyarocarbons, some degree of improvement in color is notedO Eowever, even if this method is applied to the polymerization of a petroleum crackin~ or reforming fraction containing :~ :
aromatic unsaturated hydrocarbons having a boiling range of 140 to 280C and containing fairly large amounts of cyclopentadie~es, lt i~s~impossible to obtain a hydro-carbon resm having superior color, high th0rmal stabi-lity and freedom from odorO
Japanese Patent PubIlcatlon No. 21737/68 dls-closes a process for pro~ucing a petroleum resin, which comprises contacting a steam~cracking unsatusated : :
, ~
. ~ .,~ :
petroleum fraction containing 1 to 3~' by weight of cyclo-dienes at room temperature with 0.5 to 2 moles, per mole of the cyclodienes, of maleic anhydri~e to form a cyclo-diene/maleic anhydride adduct, removing the adduct, then removi.ng cyclodiene, and pol~merizing the remainder in the presence of a catalystr Since an unsaturated petroleum fraction containing as large as 1 to ~/o by weight of a c~clodiene such as cyclopentadi.ene is used as a startin~
steam cracking unsaturated petroleum fraction, a large 10` amount of maleic anhydride must be used to pro~uce an adduct of the cyclodienesO As a result, a large quantity of the adduct must be removed9 and the opera.tion becomes complicated~ In addition, the use of a large amount of maleic anhydride in this method tends to corrode the eguipment~ ~urthermore, as ls seen from the Examples ; given in this Japanese Publication, aliphatic hydrocarbon resins obtained from steam-cracking unsaturated petroleum ~: fractions having a boiling range of 20 to 100C and aromatic hydrocarbo.n r~sins obtained from steam-crac~ing :20 unsaturated petroleum fractions having a boiling range of ~: 100 to 200C have a Gardner color number of 9-12 and 14-18, : : respectlvely~ Even when thls method is applled to the polymerization of aromatic unsaturated hydrocarbon-con-~: talning:fractions having a boiling range of 140 to~280C, . ~ .
it is impossible to obtain hydrocarbon resins having good ~: color, very high thermal stability and freedom from odor. - .
:: : Japanese~Patent Publication No. ~9287/61 dis- ~
~: closes~a process for producing a hydrocarbon resin having .`
' ,~
~ ~.3~4 a hi~h acid ~alue an~ a high saponification value by poly-merizing unsatura-ted hy~rocarbons having a boiling range of 20 to 280C obtained during petroleum refining, pe-troleum cracking, and the like after a~ding an unsaturated acid or its anhydrideO This Japanese Patent Publication states that the resulting hydrocarbon resin is light-colored~ However, if an unsaturated hydrocarbon resin-containing fraction having a boiling range of 20 to 280C
obtained during the thermal cracking of petroleum is poly-merized in the presence of an unsaturated acid or itsanhydride without adjusting the content of cyclopenta-dienes in it, it is impossible to obtain a hydrocarbon resin having fully satisfactory color, thermal stability ;
and odor~ as described in the Examples of this Publica-tion.
In an attempt to remedy the aforesaid defects : of the conventional methods, German Offenlegungsschrift No. 2716763 discloses a process for preparing a hydro-carbon resin having improved color and thermal stability, whlch comprises heat-treating a petroleum cracking or reforming fraction containing cationically poly~eriz~able hydrooarbon reslns and having a boiling range of $rom lL~0C to 280C with an a~-unsaturated dicarboxylic acid : ; anhydride at~a~temperature of from 50 to 250C~ and then polymerizin~ the treated petroleum fraction in the presence of a cationic polymerization ca~alyst~ ~ccording to this process, the color,~:odor and thermal stability~of the . ~ .
resulting aromatic~hydrocarbon resin can be improved:to : ,.
'' ..
`~ :
~ , a fairly satisfac-tor~ degreeO ~owever, since the start-ing petroleum fraction is heat-treatecl with an a,~_unsa-turated dicarboxylic acid without removing cyclopentadienes from it in advance~ -the ~ unsaturated dicarboxylic acid anhydride is required in a relatively large amount, and consequently, in order to obtain hydrocarbon resins of good quality, large amounts of the adduct must be removed.
Furthermore, the treatment must be performed under heat, and the corrosion of the equipment becomes a problemO
It is an object of this invention to provide a new process for producing a hydrocarbon resin, which is free from the aforesaid defectsO
Another object of this invention is to provide a process for producin~ hydrocarbon resins having a high level of color and thermal stability.
; ~ Still another object of -this invention is to provide a process for producin~ an aromatic hydrocarbon resin having greatly improved color and thermal sta~ilit~
~ ~ , in which the pretreatment can be performed at relatively low temperatures for relatively shor~ periods of time using the minimized amount of a treating agent such as -maleic anhydride, and the adduct needs not to be removed~ ~
Other objects and advantages of the invention ~ -;
will become~apparent~from the following d~escription.
~ Aocord mg to the present invention, there;is provided a process for produc~ing a hydrocarbon resin~hav-ing improved color and thermal stability, which comprises treating a pe-troleum cracking or reformlng fraction con-:: ~ : : . :
.:
: :: : -~
:: : ~: :
taining ca-tlonically pol~merizahle hydroc~rbons and not more than o.70/o by weigh-t, based on the fraction, of cyclo-pentadienes and having a boiling ran~e of from 1~0C to 280C, with 008 to ~O0 moles, per mole of the cyclopenta-dienes, of a dienophile compound havin~ a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond; and then polym~riæing -the treated petroleum fraction in the presence of a polymerization catalystO
'~he "petroleum crac.~:ing or reformin~ fraction"
used as a starting material in the process of this in-vention denotes a hydrocarbon-containing fraction which is formed as a by-product in the thermal or catalytic cracking (such as steam crackin~;, vapor phase cracLring, or s~nd cracking) or reforming (such as hydror~forming) : 15 of petroleums such as naphtha, gas oils or kerosenea : In the present invention, a petroleum cracking or reform-ing fracti.on having a boiling.ran~e of from 140C -to 280C., preferably from 140C to 2L10C~ iS partcularly - ~ : . . .
used.
q'he petroleum crac~ing or reforming fraction, as will be described in detail hereinbelow, usually COIltainS cyclopentadienes such as cyclopentadiene, meth~l-cyclopentadiene, fulvene, methyl~ulvene~and dimethylfu- . : -lvene, and dicyclopentadienes such as dicyclopentaiene, : 25 methyldicyclopentadiene and dimethyldicyclopentadiene:~in .~ :
addition to other various cationically polymerizable hydro-oarbonsO ~When a fraction having a boiling range of 140 to 280C~is to be formed~b~ fractional distillation of this :
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petroleum cracking or reforming fr~lction~ lower boilirlg products, such as cyclopentadiene or methylcyclopentadiene, formed by gradual decomposition of -the dicyclopentadienes during distillation will usually be contained in the re-sulting ~raction having a boiling range of 140 to 280C
in addition to fulvene, methylfulv~ne and dime-thylfulvene having a boiling point of 140 to 280Cn Accordingly, the petroleum cracking or reforming fraction having a boiling range of from 1~0 to 280C usually contains as much as about 1 to about 7% by weight, particularly 105 to ~ by weight, based on the weigh-t of the fraction, of the cyclopentadienes O
~he present inventors made extensive investiga-tions in order -to produce aromatic hydrocarbon resins having very much improved color, thermal s-tability and odor which can be used as tackifying resins for ho-t~melt .
:~ adhesives and pressure-sensitive adhesives which require the use of aromatic hydrooarbon resins having improved color and thermal stability from a petroleum cxacking or refor:ing fraction containing such large amounts of cyclo-pentadienes and having~a boiling range of 140 to 2soaO
hese Investigations led to the discovery that hydrocarbon ~:
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resins~hav1ng greatly improved color and -thermal stability : :
which meets the above objectives can be obtained by sub- -: 2~ jecting a petroleum cracking or reforming fraction having a boiling range of~from 140 to 280C and containing as high ~: ~ as at least about 1% by weight,based on the fraction, of ~; : : cyclopentadienes such as cyclop~ntadienes methylcyclo- .:
, .
pentadiene, fulvene, meth~lfulvene and dimethylfulvene to a separating operation such as distillakion to adjust its content of the cyclopentadienès to not more than 0.7,b by weight, treating the resulting unsa-turated hydrocarbon-containing petroleum fraction with a specified dienophile compound, and then polymerizing thc tr~ated product.
~ he invention will be described below in greater detail.
~ he fraction containing cationics1ly polymeri-zable hydrocarbons which is used as a raw material for the hydroc~rbon resins is a fraction having a boiling range of l40C to 280C, preferably 140C to 240C, which is obtained as a by-product in the thermal or catalytic cracking (e.gO, steam cracking, vapor phase cracking or l~ sand cracking) or reforming (e.~., hydroreforming) of petroleums such as naphtha, gas oils or keroseneO This fraction con-tains at least about~ 1/J by weight, usually l to 7/, by weight, particularly 1,5 to ~/'~1 by weight, ,~ ~
based on the weight~of the fracti:on,~ of cyclopentadienes.
In the present specification and the appended c1aims, the~term "cDclopentadie~e6" (to~be sometimes referred to hereinbelow as "CP~s") generically denote compounds having a 5-membered carboxylic ring of the following formula ; 25 C~C\
\C--~C~
: .
, :
:, ' , , , ' ~ , ' ; , _ 9 _ (i.e., a cyc]opentadiene ring) in the molecule. ~ypical-ly, CPDs include cyclopentadiene, methylcyclopentadiene, fulvene, methylfulvene, and dimethylfulvene~
~he petroleum cracking or reforming fraction having a boiling range of from 140C to 280C which can be used as a starting material can be obtained by frac-tionall~ distilling a frac-tion containing hydrocarbons having a boiling range of about -20C to ~ 280C. Because dicyclopentadiene, methyldicyclopentadiene and dimethyl-dicyclopentadiene inherently contained in the fraction decompose and distill out during the fractional distilla-tion, cyclopentadienes such as cyclopentadiene, methyl cyclopen-tadiene anA fulvene will be contained in the -~ resulting petroleum cracking or reforming fraction having 15 a boiling range of 14Q to 280C in spite of their lowe~
boiling point. Furthermore, methylfulvene and dimethyl-; fulvene are inherently contained in the petroleum cracking or reforming fraction hav1ng the aforesald boiling rangeO
In many cases, the resulting petroleum cracking or~re-; ~ ~ 20 forming fractlon having a boiling ranBe of 140 to 280C
usually contains l to ~/~ by weight, particularly 105 to 3/, by weight, of the cyclopentadienes. In the present invention, a petroleum crackin~ or reforming fraction :
~ containing at least about l~' by weight, based on the ~ ~
: ~ :
~ 25 weight of the fraction, of cyclopentadienesO
~ , he pe-troleum cracking or reforming fraction having a hoiling range of from 1/-~0C -to 280C also contains c~tionically polymerizabIe hydrocarbons and :
:: .:'. : ,, :,' non-pol~merizable hydrocarbons, most of which contain at least 8 carbon atomsO '~he hy~rocArbons with at least 8 carbon atoms are contained generally in an amount of at least 9C,'~ by weight based on l,he weight of the fraction.
specifically, the composition of the petroleum fraction varies over a broad range according, for example, to the type of the petroleum cracking or reformed and the crack-: ing or reforming conditions~ ~ccordlng to the present invention, a ~raction containing at least 2C/~ by weight, ~ 10 preferably 30 to 75/J by weight, more preferably 3~ to 60/, ; ~ by weight, based on the weight of the fraction, of cation-: ically polymerizable hydrocarbons is advantageously used Hydrocarbons having at le~ast 8 carbon atoms contained in the fraction are almost all aromatic hydro-carbons, the major proportion of which consists ofaromatic hydrocarbons containing 9 or 10 carbon atoms.
The total amount of such aromatic hydrocarbons with 9 or 10 carbon atoms is 50 to 95/~ by weigh-t, usually 60 to 95/ y.
by weight, based on the weight of the fractionO me 20 fraction contains some amounts of aromatic hydrocarbons ~ :~
containing 8 carbon;atoms and more than 10 carbon atoms~
ypical~examples:of th~e cationically pol~meriza~
ble hydrocarbons contained ln the fracbion are cationical~
ly polymerizable:aromatic hydrocarbons containing 8 to 12 :
carbon atoms, such as styrene, ~- or ~-methylstyrene, o~
m-~or p-v my1toluene,~lndene~, methylindene, or divinyl~
~: : benzeneO Other non--typical cationically polymerizable . .
aromatic hydrocarbon~ inclua0 C8 to C12 olefins and/or ~ . ~
, ~3~
diolefins such as dicyclopentacliene or methyldicyclopen-tadiene which are present in mlnor quantltiesr On the o-ther hand, t~pical examples of the non-polymerizable hy~rocarbons contained in the fraction in-clude C8 to C12 aromatic hydrocarbons such as xylene,ethylbenzene, cumene, eth~Jltoluene, n-propylbenzene, -trimethylb~nzene~ indane, me-thylindane, naphthalene, methylnaphthalene, and dimethylnaphthaleneO O-ther ex-amples of the non-pol~merizable hy~rocarbons are C8 to . .
C12 paraffins and/or naphthenes which are present in small amountsO
: As stated hereinabove, the composition of the petroleum cracking or reforming fraction used in this -`~
invention changes over a wide range according~ for ex~
1~ ample, to the petroleum cracked or reformed, and the cracking or reforming conditions, and cannot be definitely ~:
: determined~ Generally, the fraction preferably has a ~: : bromine value of 50 to 90. Fractions having the followi~
cornpositions are especially preferably used. It should 0 be noted however that the present invention is not limited -to the following exempliflcatlon.
~ : :
~E~ Amounts in percent b~g wei~ht Cationically polymerizable aromatic hydroc~rbons~ to 75, preferably 30 to 60 01efins ~io to 5, preferably 1 to 3 ~ther Diolefins1 to 10, preferabl~ 1 to 5 CPDs 1 -to 7, preferably 1~5 to 3 Non-polym~rizable aromatic hydrocarbons15 to 65, preferably 20 to 50 Para~fins and naphthenes 1 to 10, preferably 1 to 5 , 'rypical examples of the olefins and other di-`~ olefins gi~en in the above table are aliphatic and cyclo-aliphatic mono- and di-olefins containing 9 to 12 carbon atoms~ ~he non-polymerizable ~romatic hydroc~rbons are typified by C9 to C12 alkylbenzenes (main components), indane and C9 to Cll derivatives thereof with traces of benzene~ -toluene and ~lene, and naphthalene and Cll -to ;
; 15 C12 deriva-tives thereofO ~ypical examples ~f the paraffins and naphthenes are paraffins and naphthenes containing 9 to 12 carbon atoms.
he cationically polym~rizable aromatic hydro-carbon component in the fraction t~pically consists of the followlng components.
Components moun-ts in:,,~, b~ _ei~h~ (*~ ;
:: Vinyl toluene ) - ~: Indene ~ '~ot~al 30 to ~as, preferably 35 to 70 Styrene ) a-MethylstYrene ~ ~otal ~ to 50. prèferablY 5 to 30 Methylindene~
Methylstyrene ) :
, -:, I ~ ; ; , ~3~
(*) '~he amounts are based on -the total weigh-t of the cationically polymerizable aromatic hydrocarbons.
According to this in~ention, -the pe-troleum craek-ing or reformin~ fraction con-taining CPDs is subjeeted to an operation of removin~ the C~Ds to reduce the content of CPDs to below 0~ by wei~;ht based on the wei~lt of -the fractionr Preferably, this removal can be achieved by fractional distillation. '~he fractional distillation can be performed in a manner known ~ se~ It is effective lO -to perform continuous distillation by a side-cut method shown below. Speeifically, the petroleum crac'king or reforming fraction containin~ C~'Ds is fecl into the middle portion of a distillation tower usually having lO to 20 bubble cap trays. The temperature of the bottom of the 15 tower is acljus-tecl to not more than about 2lOC, preferably 150 to 200C. A low-boiling fraction having coneen-trated CPDs is taken out from the to~ of the tower; the main fraction (to be subjected to the poly~ierization reaction) having a reduced eontent~of CPDs, from the -tep of the 20 tower (from 2nd to 4th~trays when -the number of trays is lO; from 4th to 8-th trays when there are 20 trays); and a high-boil mg fractlon havin~ a low content of polymeriz-able in~redients~fror.l the bottom of the tower. By ~ '-suitably selecting the pressure~of t'he clistillation tower ''~
25 and the reflux ratio, the main ~raction having a very low concentration o~f CPDs can be taken out while mlnimiz-ing the amounts of the~fractions to be wl-thdrawn from~the top and bottom of the -towerO ~he pressure and~reflux -, ~ "
~.
ratio at this time vary accordin~ to -the type of the starting fraction7 and c~nnot be definitely setn Gener-ally, the suitable pressure is 150 to 200 r,~Ig, and the suitable reflux r~tio is from 1 to 5, preferably from 2 to According to this invention, the removal of CPDs can also be performed by -the heat-treatment of petroleum cracking or reforming fraction with an ~,~-unsaturated dicarboxylic acid anhydride and the subsequent removal of the adduct with the acid anhyclride by distillation, as disclosed in Gerrnan 0ffenlegun~sschrift ~oO 2716763 (corresponding to U.S. Patent 4,1()5,8~3); or by the prs-liminary polymeriza-tion of the fracti.on in the presence of a solid acid and tht? subsequent removal of the result-ing polymers of apDs by distillation. '~he removal method . .
~ described in the above Un So Paten-t will be described :.
below at some lengthO .
he a,~-unsa-turated dicarboxylic acld anhydride that can be used in the formèr heat-trea-tment includes or~anic compounds con~tainin~ two carboxyl groups bonded to each other;ln -the .~orm of anh~dride~'~nd an~unsaturated bond, especially~a double bond, between the carbon atoms ~ i (tx-carbon atom~ to which one;of the~carbox~l ~roups is - ;`
bonded and a carbon A tom ad~jacent thereof (1j3-carbon atom).
Suitable~anhydrides~;are allphatic or al1cyclic~a~,8-unsa-turated dicarboxyllc aoid anhydrides containin~ up to~15 carbon atoms, preferably ~to~l0 carbon atoms. Especial-ly preferred;~a,~-unsaturated carboxylic acid anhydrides~
- :.
:
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irclude maleic anhydride, itaconic anhy(~ride~ citraconic anhydride, L~ te-trahydrophthalic anhy~lride, Qnd ~2_ . tetrahydrophthalic ~nhy~l.ride. Cf these, the aliphatic a~_unsaturated dicarboxylic aci~. anhydrides, especially maleic anhydride, are especially suitable.
'~he amount of the ~ unsaturated dicarboxylic acid anhydride is not critical, and can be varied over a ~: wide range accordin~, for example, -to the type of the petroleum fraction to be treated or the -temperature of the heat-treatment. Generally, the amount is at least 0.5/~ by wei6ht, preferably 1 to 205b hy weight, more pre-ferably 2 to l~/o by weight, based on the wei6ht of the ~ cationically polymerizable hydrocarbons i~ the petroleum .~ cracking or reformin6 fraction.
~he heat-treatment of the fr~ction with -the ~
unsaturated dicarboxylic acid anh;ydride is carried out at a temperature of 50 to 250C~, preferablJ 70 to 200Co, ~: most preferably 90 to 1~0C. '~he hea-t-treatment can be performed usuall~ at atmospheric pressure, but if desired, at elevated or reduced pressuresO ~he heat~treatment time is not critical, and ci~n:be varied o~er a wide range according, for example, to the type of the fraction, the type~or amount of the acid anhydride, or the he~at-treat-~
ment temperature. Generally,~the heat--treatm~nt time is .-- -:25 at least 0.5 minute,:preferably 1 minute to 10 hours, more prefe:rably 30 minutes to 5 hours.
he above heat-treatment can also be performed in the presence of 0O005 to 10~ by weight, preferably 0.01 -to 5% by weilght, based on the -total weight of the cationically polymerizable hydrocarbons, of an acid such as Lewis acids or Br~nsted acids (proton acids)O
~he petroleium cracking or re~orming fraction thus hea-t-treated wi-th the a~-unsa-tura-ted dicarboxylic acid anhydride is then distilled to remove the adducts of the CDPs with the acid anhydride in -the petroleum cracking or reforming fraction. ~he distillation can be performed in a manner l~nown ~ se. ~or example, flash dis-tillation suffices if the temperature of the -tower bottom is main-tained at not more than 150C -to inhibit the decomposition of the adducts.
0ne recommended procedure for removing OPDs from the pe-troleum crackin~ and reforming fraction by the 15 preliminary polymerization described hereinabove comprises -~
treating the fraction in the presence of a solid acid~
and then subjecting the treated product to flash distil-la-tion to remove the~polymerized CPDs from the bottom of the distillation towerD Suitable solid acids lnclude silica-alumina and~activated c]ay. ~C~Ds alone can be polymerized wlth a falrly high selectivlty by adding the sol~id acid in an amount~ OD5 to 10 times the we~ght of CPDs to the~petroleum crac';1n~ or reforming frao-tion, and treating the mixture at 0 to~50C for 0~5 to 2~hoursO `-Usual~flash distlllatlon`of the produot results in a fraction free from~GPDsO
By~the above;~operatlon of removing ~PDs, a petroleum cracking~or reformin6 fraction containing ~ -~ L~3~ ¢~
cationically pol~nerizable 'hydroc~r~ons and having a bolling range of ~rom 140 to 280C can 'he obtained which has a CPD content of not more than 007/j by weight 7 pre-ferably 0.01 to 0.5~' by weigh-~, more pref'erably 0.05 toO.
~ by weight, based on the weight of -the fraction.
~ he process of this invention is characterized by treating the resulting pet:roleum cracking or reforming fraction having a decrea~ed content of C'PDs so obtained with a dienophile compound ha-ving a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond~
~ he term "dienophile compound", used h~rein, denotes a compound capable of' easily performs a Diels~
Alder reac~ion with CPPs (dienes) to form adductsO In the present invention, those dienophile compounds which have a carbonyl or cyano group adjacent to a double bond : are usedO Suitable dienophile conpounds for use in the process of this invention are a,~-unsaturated dienophile compounds which contain l to 2 double bonds and adjacent :~
thereto, at least l, preferably l to ~, more preferably
-- 1 .
r~his invention relates to an improved process for producing hydroc~rbon resins. More specifically, it relates to a process for producing hydrocarbo~ resins having greatly reduced coloration and very high thermal stability which consist mainly of aromatic hydrocarbon units~
It has been well ~nown to produce hydrocarbon resins by polymerizing a thermal cracking or ref~rming petroleum fraction containing ~msaturated hydrocarbons using Friedel-Fracts catalysts~ ~he hydroc~rbon resins are classified into aliphatic hydrocarbon resin~ obtained by polymerizing a petroleum fraction containing aliphatic unsaturated hydrocarbons as m~in constituents ana having a boiling range of from -20Co to 100C,, and aromatic hydrocarbon resins obtained by pol~merizing a petroleum --fraction containing aromatic unsaturated hydrocarbons as main constituents and having a boiling range of from 140C to 280C. ~he aromatic hydrocarbon resins have lower thermal stability, stronger offensive odor and ;~
greater coloration than the aliphatic species~ For this reason, it has previously been considered as difficult to use the aromatic hydrocarbon resins i~ applications which require superior thermal stability, a low degree of odor or freedom from odor, or a low degree of coloration, for ~25 example in hot-melt adheslves, pressure-sensitive ad-~hesives, or thermo-fusible traffib paints.
~ .
Methods have previously been sugge8ted for~pre-treatlng a petroleum fractlon~containing unsaturated ;.
~ ~ .
:
:
~13~
hydrocarbons, mainly alipha-tic unsaturated hydrocarbons, having a boiling point of not more than 280~o and co~-taining at least 5 carbon atoms to remove from it un-desirable components which will worsen the color or hyarocarbon resins and/or form a gel (insoluble polymer), especially cyclo~ienes such as cyclo~entadiene or methyl-cyclopentadieneO For example, UOS. Patent 2,770,613 discloses a method for removing them by pre-heating the fraction at 90 to 140C to dimerize cyclodienes. hc-cording to this method, however, the treating operationis complicated~ an~ because unsaturated hydrocarbon components in an unsaturated hy~rocarbon-containing fraction of the polymeriæation material are re~oved as adducts with cyclopentadienes, the loss of uns~turated hydrocarbons other than cyclopentadienes is great. When this method is applied to the polym~rization of a frac-tion containing aliphatic unsaturated hyarocarbons, some degree of improvement in color is notedO Eowever, even if this method is applied to the polymerization of a petroleum crackin~ or reforming fraction containing :~ :
aromatic unsaturated hydrocarbons having a boiling range of 140 to 280C and containing fairly large amounts of cyclopentadie~es, lt i~s~impossible to obtain a hydro-carbon resm having superior color, high th0rmal stabi-lity and freedom from odorO
Japanese Patent PubIlcatlon No. 21737/68 dls-closes a process for pro~ucing a petroleum resin, which comprises contacting a steam~cracking unsatusated : :
, ~
. ~ .,~ :
petroleum fraction containing 1 to 3~' by weight of cyclo-dienes at room temperature with 0.5 to 2 moles, per mole of the cyclodienes, of maleic anhydri~e to form a cyclo-diene/maleic anhydride adduct, removing the adduct, then removi.ng cyclodiene, and pol~merizing the remainder in the presence of a catalystr Since an unsaturated petroleum fraction containing as large as 1 to ~/o by weight of a c~clodiene such as cyclopentadi.ene is used as a startin~
steam cracking unsaturated petroleum fraction, a large 10` amount of maleic anhydride must be used to pro~uce an adduct of the cyclodienesO As a result, a large quantity of the adduct must be removed9 and the opera.tion becomes complicated~ In addition, the use of a large amount of maleic anhydride in this method tends to corrode the eguipment~ ~urthermore, as ls seen from the Examples ; given in this Japanese Publication, aliphatic hydrocarbon resins obtained from steam-cracking unsaturated petroleum ~: fractions having a boiling range of 20 to 100C and aromatic hydrocarbo.n r~sins obtained from steam-crac~ing :20 unsaturated petroleum fractions having a boiling range of ~: 100 to 200C have a Gardner color number of 9-12 and 14-18, : : respectlvely~ Even when thls method is applled to the polymerization of aromatic unsaturated hydrocarbon-con-~: talning:fractions having a boiling range of 140 to~280C, . ~ .
it is impossible to obtain hydrocarbon resins having good ~: color, very high thermal stability and freedom from odor. - .
:: : Japanese~Patent Publication No. ~9287/61 dis- ~
~: closes~a process for producing a hydrocarbon resin having .`
' ,~
~ ~.3~4 a hi~h acid ~alue an~ a high saponification value by poly-merizing unsatura-ted hy~rocarbons having a boiling range of 20 to 280C obtained during petroleum refining, pe-troleum cracking, and the like after a~ding an unsaturated acid or its anhydrideO This Japanese Patent Publication states that the resulting hydrocarbon resin is light-colored~ However, if an unsaturated hydrocarbon resin-containing fraction having a boiling range of 20 to 280C
obtained during the thermal cracking of petroleum is poly-merized in the presence of an unsaturated acid or itsanhydride without adjusting the content of cyclopenta-dienes in it, it is impossible to obtain a hydrocarbon resin having fully satisfactory color, thermal stability ;
and odor~ as described in the Examples of this Publica-tion.
In an attempt to remedy the aforesaid defects : of the conventional methods, German Offenlegungsschrift No. 2716763 discloses a process for preparing a hydro-carbon resin having improved color and thermal stability, whlch comprises heat-treating a petroleum cracking or reforming fraction containing cationically poly~eriz~able hydrooarbon reslns and having a boiling range of $rom lL~0C to 280C with an a~-unsaturated dicarboxylic acid : ; anhydride at~a~temperature of from 50 to 250C~ and then polymerizin~ the treated petroleum fraction in the presence of a cationic polymerization ca~alyst~ ~ccording to this process, the color,~:odor and thermal stability~of the . ~ .
resulting aromatic~hydrocarbon resin can be improved:to : ,.
'' ..
`~ :
~ , a fairly satisfac-tor~ degreeO ~owever, since the start-ing petroleum fraction is heat-treatecl with an a,~_unsa-turated dicarboxylic acid without removing cyclopentadienes from it in advance~ -the ~ unsaturated dicarboxylic acid anhydride is required in a relatively large amount, and consequently, in order to obtain hydrocarbon resins of good quality, large amounts of the adduct must be removed.
Furthermore, the treatment must be performed under heat, and the corrosion of the equipment becomes a problemO
It is an object of this invention to provide a new process for producing a hydrocarbon resin, which is free from the aforesaid defectsO
Another object of this invention is to provide a process for producin~ hydrocarbon resins having a high level of color and thermal stability.
; ~ Still another object of -this invention is to provide a process for producin~ an aromatic hydrocarbon resin having greatly improved color and thermal sta~ilit~
~ ~ , in which the pretreatment can be performed at relatively low temperatures for relatively shor~ periods of time using the minimized amount of a treating agent such as -maleic anhydride, and the adduct needs not to be removed~ ~
Other objects and advantages of the invention ~ -;
will become~apparent~from the following d~escription.
~ Aocord mg to the present invention, there;is provided a process for produc~ing a hydrocarbon resin~hav-ing improved color and thermal stability, which comprises treating a pe-troleum cracking or reformlng fraction con-:: ~ : : . :
.:
: :: : -~
:: : ~: :
taining ca-tlonically pol~merizahle hydroc~rbons and not more than o.70/o by weigh-t, based on the fraction, of cyclo-pentadienes and having a boiling ran~e of from 1~0C to 280C, with 008 to ~O0 moles, per mole of the cyclopenta-dienes, of a dienophile compound havin~ a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond; and then polym~riæing -the treated petroleum fraction in the presence of a polymerization catalystO
'~he "petroleum crac.~:ing or reformin~ fraction"
used as a starting material in the process of this in-vention denotes a hydrocarbon-containing fraction which is formed as a by-product in the thermal or catalytic cracking (such as steam crackin~;, vapor phase cracLring, or s~nd cracking) or reforming (such as hydror~forming) : 15 of petroleums such as naphtha, gas oils or kerosenea : In the present invention, a petroleum cracking or reform-ing fracti.on having a boiling.ran~e of from 140C -to 280C., preferably from 140C to 2L10C~ iS partcularly - ~ : . . .
used.
q'he petroleum crac~ing or reforming fraction, as will be described in detail hereinbelow, usually COIltainS cyclopentadienes such as cyclopentadiene, meth~l-cyclopentadiene, fulvene, methyl~ulvene~and dimethylfu- . : -lvene, and dicyclopentadienes such as dicyclopentaiene, : 25 methyldicyclopentadiene and dimethyldicyclopentadiene:~in .~ :
addition to other various cationically polymerizable hydro-oarbonsO ~When a fraction having a boiling range of 140 to 280C~is to be formed~b~ fractional distillation of this :
. ,~ .~.
.
`:`
3~3~
petroleum cracking or reforming fr~lction~ lower boilirlg products, such as cyclopentadiene or methylcyclopentadiene, formed by gradual decomposition of -the dicyclopentadienes during distillation will usually be contained in the re-sulting ~raction having a boiling range of 140 to 280C
in addition to fulvene, methylfulv~ne and dime-thylfulvene having a boiling point of 140 to 280Cn Accordingly, the petroleum cracking or reforming fraction having a boiling range of from 1~0 to 280C usually contains as much as about 1 to about 7% by weight, particularly 105 to ~ by weight, based on the weigh-t of the fraction, of the cyclopentadienes O
~he present inventors made extensive investiga-tions in order -to produce aromatic hydrocarbon resins having very much improved color, thermal s-tability and odor which can be used as tackifying resins for ho-t~melt .
:~ adhesives and pressure-sensitive adhesives which require the use of aromatic hydrooarbon resins having improved color and thermal stability from a petroleum cxacking or refor:ing fraction containing such large amounts of cyclo-pentadienes and having~a boiling range of 140 to 2soaO
hese Investigations led to the discovery that hydrocarbon ~:
. `
resins~hav1ng greatly improved color and -thermal stability : :
which meets the above objectives can be obtained by sub- -: 2~ jecting a petroleum cracking or reforming fraction having a boiling range of~from 140 to 280C and containing as high ~: ~ as at least about 1% by weight,based on the fraction, of ~; : : cyclopentadienes such as cyclop~ntadienes methylcyclo- .:
, .
pentadiene, fulvene, meth~lfulvene and dimethylfulvene to a separating operation such as distillakion to adjust its content of the cyclopentadienès to not more than 0.7,b by weight, treating the resulting unsa-turated hydrocarbon-containing petroleum fraction with a specified dienophile compound, and then polymerizing thc tr~ated product.
~ he invention will be described below in greater detail.
~ he fraction containing cationics1ly polymeri-zable hydrocarbons which is used as a raw material for the hydroc~rbon resins is a fraction having a boiling range of l40C to 280C, preferably 140C to 240C, which is obtained as a by-product in the thermal or catalytic cracking (e.gO, steam cracking, vapor phase cracking or l~ sand cracking) or reforming (e.~., hydroreforming) of petroleums such as naphtha, gas oils or keroseneO This fraction con-tains at least about~ 1/J by weight, usually l to 7/, by weight, particularly 1,5 to ~/'~1 by weight, ,~ ~
based on the weight~of the fracti:on,~ of cyclopentadienes.
In the present specification and the appended c1aims, the~term "cDclopentadie~e6" (to~be sometimes referred to hereinbelow as "CP~s") generically denote compounds having a 5-membered carboxylic ring of the following formula ; 25 C~C\
\C--~C~
: .
, :
:, ' , , , ' ~ , ' ; , _ 9 _ (i.e., a cyc]opentadiene ring) in the molecule. ~ypical-ly, CPDs include cyclopentadiene, methylcyclopentadiene, fulvene, methylfulvene, and dimethylfulvene~
~he petroleum cracking or reforming fraction having a boiling range of from 140C to 280C which can be used as a starting material can be obtained by frac-tionall~ distilling a frac-tion containing hydrocarbons having a boiling range of about -20C to ~ 280C. Because dicyclopentadiene, methyldicyclopentadiene and dimethyl-dicyclopentadiene inherently contained in the fraction decompose and distill out during the fractional distilla-tion, cyclopentadienes such as cyclopentadiene, methyl cyclopen-tadiene anA fulvene will be contained in the -~ resulting petroleum cracking or reforming fraction having 15 a boiling range of 14Q to 280C in spite of their lowe~
boiling point. Furthermore, methylfulvene and dimethyl-; fulvene are inherently contained in the petroleum cracking or reforming fraction hav1ng the aforesald boiling rangeO
In many cases, the resulting petroleum cracking or~re-; ~ ~ 20 forming fractlon having a boiling ranBe of 140 to 280C
usually contains l to ~/~ by weight, particularly 105 to 3/, by weight, of the cyclopentadienes. In the present invention, a petroleum crackin~ or reforming fraction :
~ containing at least about l~' by weight, based on the ~ ~
: ~ :
~ 25 weight of the fraction, of cyclopentadienesO
~ , he pe-troleum cracking or reforming fraction having a hoiling range of from 1/-~0C -to 280C also contains c~tionically polymerizabIe hydrocarbons and :
:: .:'. : ,, :,' non-pol~merizable hydrocarbons, most of which contain at least 8 carbon atomsO '~he hy~rocArbons with at least 8 carbon atoms are contained generally in an amount of at least 9C,'~ by weight based on l,he weight of the fraction.
specifically, the composition of the petroleum fraction varies over a broad range according, for example, to the type of the petroleum cracking or reformed and the crack-: ing or reforming conditions~ ~ccordlng to the present invention, a ~raction containing at least 2C/~ by weight, ~ 10 preferably 30 to 75/J by weight, more preferably 3~ to 60/, ; ~ by weight, based on the weight of the fraction, of cation-: ically polymerizable hydrocarbons is advantageously used Hydrocarbons having at le~ast 8 carbon atoms contained in the fraction are almost all aromatic hydro-carbons, the major proportion of which consists ofaromatic hydrocarbons containing 9 or 10 carbon atoms.
The total amount of such aromatic hydrocarbons with 9 or 10 carbon atoms is 50 to 95/~ by weigh-t, usually 60 to 95/ y.
by weight, based on the weight of the fractionO me 20 fraction contains some amounts of aromatic hydrocarbons ~ :~
containing 8 carbon;atoms and more than 10 carbon atoms~
ypical~examples:of th~e cationically pol~meriza~
ble hydrocarbons contained ln the fracbion are cationical~
ly polymerizable:aromatic hydrocarbons containing 8 to 12 :
carbon atoms, such as styrene, ~- or ~-methylstyrene, o~
m-~or p-v my1toluene,~lndene~, methylindene, or divinyl~
~: : benzeneO Other non--typical cationically polymerizable . .
aromatic hydrocarbon~ inclua0 C8 to C12 olefins and/or ~ . ~
, ~3~
diolefins such as dicyclopentacliene or methyldicyclopen-tadiene which are present in mlnor quantltiesr On the o-ther hand, t~pical examples of the non-polymerizable hy~rocarbons contained in the fraction in-clude C8 to C12 aromatic hydrocarbons such as xylene,ethylbenzene, cumene, eth~Jltoluene, n-propylbenzene, -trimethylb~nzene~ indane, me-thylindane, naphthalene, methylnaphthalene, and dimethylnaphthaleneO O-ther ex-amples of the non-pol~merizable hy~rocarbons are C8 to . .
C12 paraffins and/or naphthenes which are present in small amountsO
: As stated hereinabove, the composition of the petroleum cracking or reforming fraction used in this -`~
invention changes over a wide range according~ for ex~
1~ ample, to the petroleum cracked or reformed, and the cracking or reforming conditions, and cannot be definitely ~:
: determined~ Generally, the fraction preferably has a ~: : bromine value of 50 to 90. Fractions having the followi~
cornpositions are especially preferably used. It should 0 be noted however that the present invention is not limited -to the following exempliflcatlon.
~ : :
~E~ Amounts in percent b~g wei~ht Cationically polymerizable aromatic hydroc~rbons~ to 75, preferably 30 to 60 01efins ~io to 5, preferably 1 to 3 ~ther Diolefins1 to 10, preferabl~ 1 to 5 CPDs 1 -to 7, preferably 1~5 to 3 Non-polym~rizable aromatic hydrocarbons15 to 65, preferably 20 to 50 Para~fins and naphthenes 1 to 10, preferably 1 to 5 , 'rypical examples of the olefins and other di-`~ olefins gi~en in the above table are aliphatic and cyclo-aliphatic mono- and di-olefins containing 9 to 12 carbon atoms~ ~he non-polymerizable ~romatic hydroc~rbons are typified by C9 to C12 alkylbenzenes (main components), indane and C9 to Cll derivatives thereof with traces of benzene~ -toluene and ~lene, and naphthalene and Cll -to ;
; 15 C12 deriva-tives thereofO ~ypical examples ~f the paraffins and naphthenes are paraffins and naphthenes containing 9 to 12 carbon atoms.
he cationically polym~rizable aromatic hydro-carbon component in the fraction t~pically consists of the followlng components.
Components moun-ts in:,,~, b~ _ei~h~ (*~ ;
:: Vinyl toluene ) - ~: Indene ~ '~ot~al 30 to ~as, preferably 35 to 70 Styrene ) a-MethylstYrene ~ ~otal ~ to 50. prèferablY 5 to 30 Methylindene~
Methylstyrene ) :
, -:, I ~ ; ; , ~3~
(*) '~he amounts are based on -the total weigh-t of the cationically polymerizable aromatic hydrocarbons.
According to this in~ention, -the pe-troleum craek-ing or reformin~ fraction con-taining CPDs is subjeeted to an operation of removin~ the C~Ds to reduce the content of CPDs to below 0~ by wei~;ht based on the wei~lt of -the fractionr Preferably, this removal can be achieved by fractional distillation. '~he fractional distillation can be performed in a manner known ~ se~ It is effective lO -to perform continuous distillation by a side-cut method shown below. Speeifically, the petroleum crac'king or reforming fraction containin~ C~'Ds is fecl into the middle portion of a distillation tower usually having lO to 20 bubble cap trays. The temperature of the bottom of the 15 tower is acljus-tecl to not more than about 2lOC, preferably 150 to 200C. A low-boiling fraction having coneen-trated CPDs is taken out from the to~ of the tower; the main fraction (to be subjected to the poly~ierization reaction) having a reduced eontent~of CPDs, from the -tep of the 20 tower (from 2nd to 4th~trays when -the number of trays is lO; from 4th to 8-th trays when there are 20 trays); and a high-boil mg fractlon havin~ a low content of polymeriz-able in~redients~fror.l the bottom of the tower. By ~ '-suitably selecting the pressure~of t'he clistillation tower ''~
25 and the reflux ratio, the main ~raction having a very low concentration o~f CPDs can be taken out while mlnimiz-ing the amounts of the~fractions to be wl-thdrawn from~the top and bottom of the -towerO ~he pressure and~reflux -, ~ "
~.
ratio at this time vary accordin~ to -the type of the starting fraction7 and c~nnot be definitely setn Gener-ally, the suitable pressure is 150 to 200 r,~Ig, and the suitable reflux r~tio is from 1 to 5, preferably from 2 to According to this invention, the removal of CPDs can also be performed by -the heat-treatment of petroleum cracking or reforming fraction with an ~,~-unsaturated dicarboxylic acid anhydride and the subsequent removal of the adduct with the acid anhyclride by distillation, as disclosed in Gerrnan 0ffenlegun~sschrift ~oO 2716763 (corresponding to U.S. Patent 4,1()5,8~3); or by the prs-liminary polymeriza-tion of the fracti.on in the presence of a solid acid and tht? subsequent removal of the result-ing polymers of apDs by distillation. '~he removal method . .
~ described in the above Un So Paten-t will be described :.
below at some lengthO .
he a,~-unsa-turated dicarboxylic acld anhydride that can be used in the formèr heat-trea-tment includes or~anic compounds con~tainin~ two carboxyl groups bonded to each other;ln -the .~orm of anh~dride~'~nd an~unsaturated bond, especially~a double bond, between the carbon atoms ~ i (tx-carbon atom~ to which one;of the~carbox~l ~roups is - ;`
bonded and a carbon A tom ad~jacent thereof (1j3-carbon atom).
Suitable~anhydrides~;are allphatic or al1cyclic~a~,8-unsa-turated dicarboxyllc aoid anhydrides containin~ up to~15 carbon atoms, preferably ~to~l0 carbon atoms. Especial-ly preferred;~a,~-unsaturated carboxylic acid anhydrides~
- :.
:
;
irclude maleic anhydride, itaconic anhy(~ride~ citraconic anhydride, L~ te-trahydrophthalic anhy~lride, Qnd ~2_ . tetrahydrophthalic ~nhy~l.ride. Cf these, the aliphatic a~_unsaturated dicarboxylic aci~. anhydrides, especially maleic anhydride, are especially suitable.
'~he amount of the ~ unsaturated dicarboxylic acid anhydride is not critical, and can be varied over a ~: wide range accordin~, for example, -to the type of the petroleum fraction to be treated or the -temperature of the heat-treatment. Generally, the amount is at least 0.5/~ by wei6ht, preferably 1 to 205b hy weight, more pre-ferably 2 to l~/o by weight, based on the wei6ht of the ~ cationically polymerizable hydrocarbons i~ the petroleum .~ cracking or reformin6 fraction.
~he heat-treatment of the fr~ction with -the ~
unsaturated dicarboxylic acid anh;ydride is carried out at a temperature of 50 to 250C~, preferablJ 70 to 200Co, ~: most preferably 90 to 1~0C. '~he hea-t-treatment can be performed usuall~ at atmospheric pressure, but if desired, at elevated or reduced pressuresO ~he heat~treatment time is not critical, and ci~n:be varied o~er a wide range according, for example, to the type of the fraction, the type~or amount of the acid anhydride, or the he~at-treat-~
ment temperature. Generally,~the heat--treatm~nt time is .-- -:25 at least 0.5 minute,:preferably 1 minute to 10 hours, more prefe:rably 30 minutes to 5 hours.
he above heat-treatment can also be performed in the presence of 0O005 to 10~ by weight, preferably 0.01 -to 5% by weilght, based on the -total weight of the cationically polymerizable hydrocarbons, of an acid such as Lewis acids or Br~nsted acids (proton acids)O
~he petroleium cracking or re~orming fraction thus hea-t-treated wi-th the a~-unsa-tura-ted dicarboxylic acid anhydride is then distilled to remove the adducts of the CDPs with the acid anhydride in -the petroleum cracking or reforming fraction. ~he distillation can be performed in a manner l~nown ~ se. ~or example, flash dis-tillation suffices if the temperature of the -tower bottom is main-tained at not more than 150C -to inhibit the decomposition of the adducts.
0ne recommended procedure for removing OPDs from the pe-troleum crackin~ and reforming fraction by the 15 preliminary polymerization described hereinabove comprises -~
treating the fraction in the presence of a solid acid~
and then subjecting the treated product to flash distil-la-tion to remove the~polymerized CPDs from the bottom of the distillation towerD Suitable solid acids lnclude silica-alumina and~activated c]ay. ~C~Ds alone can be polymerized wlth a falrly high selectivlty by adding the sol~id acid in an amount~ OD5 to 10 times the we~ght of CPDs to the~petroleum crac';1n~ or reforming frao-tion, and treating the mixture at 0 to~50C for 0~5 to 2~hoursO `-Usual~flash distlllatlon`of the produot results in a fraction free from~GPDsO
By~the above;~operatlon of removing ~PDs, a petroleum cracking~or reformin6 fraction containing ~ -~ L~3~ ¢~
cationically pol~nerizable 'hydroc~r~ons and having a bolling range of ~rom 140 to 280C can 'he obtained which has a CPD content of not more than 007/j by weight 7 pre-ferably 0.01 to 0.5~' by weigh-~, more pref'erably 0.05 toO.
~ by weight, based on the weight of -the fraction.
~ he process of this invention is characterized by treating the resulting pet:roleum cracking or reforming fraction having a decrea~ed content of C'PDs so obtained with a dienophile compound ha-ving a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond~
~ he term "dienophile compound", used h~rein, denotes a compound capable of' easily performs a Diels~
Alder reac~ion with CPPs (dienes) to form adductsO In the present invention, those dienophile compounds which have a carbonyl or cyano group adjacent to a double bond : are usedO Suitable dienophile conpounds for use in the process of this invention are a,~-unsaturated dienophile compounds which contain l to 2 double bonds and adjacent :~
thereto, at least l, preferably l to ~, more preferably
2 -to~3, radlcal selected from the gro p con~isting of a carbox~l;group (-COO~I), a carboxyIic acid anhydride group .' CO-O-CO~ a carboxylic acld ester group ~(-COORl), a ' .
oarboxylic~acld arnlde group (-CON~ 3 3, a carbo~yllc acid imide~group (-CO-NH-CO-), a cyano group (-CN), a O
~ formyl group (-GHO)~and a keto group ( -C- ), and - -: : ':
-generally 3 to 15, preferably 3 to 10, and more preferably 4 to 10, carbon atoms.
Typical examples of the ~,~-unsaturated dieno-phile compounds which can be used in the present invention are ~iven below~
(A) a~-unsaturated carboxylic acids Suitable ~,i3-unsaturated carboxylic acids that can be used in this invention are aliphatic or cycloali-ph~tic a?~-unsaturated mono- or di-carboxylic acids con-tainin~ up to 15, preferably 3 to 10, carbon atomsO
Specific examples include acrylic acid, methacrylic acid, a-ethylacrylic acid, crotonic acid, maleic acid, citra-conic acid, ~ -tetrahydrophthalic acid, and ~2-tetra-hydrophthalic acidO The a, ~-unsa~urated dicarboxylic acids are preferred, and maleic acid is especially preferred~
(B) a,~-Unsaturated carboxylic acid anhydrides In the present invention, aliphatic or cyclo-aliphatic a, ~-unsaturated dicarboxylic acid anhydrides containing generally up to 15 carbon atoms, preferably 4 to 10 carbon atoms, are suitable~ Examples are maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and ~2-tetrahydrophthalic anhydride. The aliphatic a, ~-unsaturated dicarboxylic acid anhydrides, above all maleic anhydride, are preferredO
(C) a,~-Unsaturated carboxylic acid esters ~uitable esters are alkyl esters, particularly lower alkyl esters, of the a ? ~-unsaturated mono- or di-dica~boxylic acids described in paragraph (A) aboveO
~ ~ 3 Specific ex~mples include methylacryla-te, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl c~otonate, dimethyl maleate, diethyl malea-te, dimethyl itaconate, diisopropyl citraconate, and diethyl tetrahyr'rophthalateO
(D) a,~-Unsaturated carboxylic acid amides Suitable amides are amides of the u,~-unsaturated mono- or di-carboxylic acids described in paragraph (A) above, in which the nitrogen a-tom can be substituted by one or two alkyl rroups, particularly lower alkyl groups.
; 10 Specific examples include acrylamide me-thacrylamide, croton~mide, maleinamide, itacont~mide, citraconamide, and tetrah,ydrophthalamide.
(E) a,~-Unsaturated cflrboxylic acid imides Suitable imides are imides of the a,~3-unsatura- -ted dicarboxylic acids de~cribed in paragraph (A) above~
ypical examples are maleimide, ltaconimide~ cltracon-imide, and tetrahydrophthalimide~
-Unsaturated nitriles Suitable nitriles are those containing l ; 20 carbon-carbon double hond and l to 4 cyano groups ad-jacent to the~double bond, and 3 to 10, preferably 3 to~
6, carbon atoms. ~Specific examples are acrylonitrile, methacrylonitrile,;crotononltrile, maleonitrlle, ci-tra- ~
cononitrile~and tetracyanosthyleneO ~' (G3 ~ Unsaturated aldehy~es Suitable aldehydes are those havin~ one carbon-carbon double bond, l or 2 formyl~roups ad~jacent to the double bond?~;an~ 3~to 10, prefer~ably 3~-to 6, carbon~atomsO
~-, :: : :
.
: ; : :~
L~.3~
~o Examples include acroleln, methacrolein, crotonaldehyde and maleic dlaldehyde~
(H) Quinones Suitable quinones are benzoquinone and naph-thoquinone.
~ he term "lower alkyl" used in the presentspecifica-tion deno-tes a linear or branched alkyl ~roup having 1 to 6, preferably 1 to 4, carbon a-toms, and in-cludes, for example, methyl, ethyl, n- or iso-~ropyl, ~: 10 n-, sec-, iso- or tert-butyl, n-pentyl~ iso-amyl, and n-hexyl O
he a~-unsatura-ted dicarboxylic acid anhydrides, especially maleic anhydride, descri~ed in paragraph (B) above can be used especially advantageously in this invention.
he amount of the dienophile compound is no-t ~ . -restricted to: a narrow range~ and c~an be chosen from a wide range.~: However, :even 1f lt i8 used in a larger ~ -: amount than is~necessary, no corresponding technlcal 20~ advantage oan be~obtained~ Such large amoun-ts are wasteful, and:rather`pose a problem of corroding the equlpment.
A~great feature~of the~procesa o~ this i~nvention~
. is~that the~amount o~;the~dienophlle ccmpcund can be reduced~very:muchO hls solves the~:~rcblem of~equipment :corrosion~ and~can eliminate the need for an additional step cf separatin~g the~adducts fcrmed between the dieno~
phlle and c~clcpentadienes.
~L3~
In the present invention, -the dienophile com-pound can be used in an amoun-t of 008 to 3.0 moles, pre~
ferably 1.0 -to 2.5 moles, more prefer3bly 1.~ to 200 moles, per mole of ~PDs conta~ned in the petroleum crack-ing or reforming fraction to be treated~
The dienophile compound needs not to be com-pletely dissolved in the petroleum cracking or reforming frsctionO Desirably, however, it is at least partially soluble in the petroleum fraction under the treating conditions~ When it is substanti~lly insoluble in -tho : petroleum fraction, it is preferred to dissolve it in a solvent compatible with the fraction before adding to ~: the petroleum fraction~
~; ~he treatment of the petroleum fraction with the dienophile compound can be performed by adding the dienophile compound as a liquid, solid, melt or solution to the petroleum fraction, and contacting them intimately :
with each other. ~he treating temperature is not critical, and can be varied widely accord m~ ~to the type of:the 20 dlenophile compound used,~etcO Generally, temperatures ~. ~{
of lO to 150C,:preferably 10 to 100C7 more preferably:
: room~temperature to less than 50C:, are advantageous.
he~trea-tment can be~ effected usu~lly under ;.
atmospheric pressure,~but if req~ired, it may be carried out under elevated or reduced pressures~ ~he time: re-qulred for the treatment is not critlcal, and can:be :
varled~widely according to the amount~o~f CPDs in the ~ :~
petroleum:fraction, the type o~ the dienophile compound, ~ : ::
.3~
~ 22 -e-tc. Since in the presen-t inven-tion, -the amount of CPD~
contained in the petroleum fraction is far smaller than that in fractions treated by conventional me-thods, the treating time can be grea-tly shortened. '~he sufficient trea-ting time is usuall-y at least 30 seconds, preferably l minute to l.0 hour, more preferably 5 minu-tes to 30 minutes, according to the treating temperature.
~ he treatmen-t with the dienophile alone can lead to hydrocarbon resins having very good color and thermal stability, but if desired, this treatment may be carried out in -the presence of a small~less -th~n 1%~
amount of solid acid or ~ewis ~cido ~ he petroleum cr~cking or reforming fraction treated with the dienophile compound in the manner 1~ described above can be directly submitted to a polymeri-zation step in accordance with the process of this inven-tion. ~his is one great adv3ntage of the invention.
The polymerization can be carried out by any ~: . . .
known method used in the production of ordinary hydro-carbon resinsO
Polymerization cat~lysts norm~ally used in th1s invention are Friedel-Crafts cat~lysts such as boron tri- ;
fluoride, boron trifluoride complexes (eOgo ~ boron tri-~.
fluoride/phenol complex), aluminum trichloride, aluminum 2r~ trlbromifle, tin tetrachloride, and titaniumi tetrachloride~
hese pol~merization ca-talysts can be used in an amount of ~enerally Ool to 5~ by wei~ht, preferably 0.5 to 3,~
:
~ by weight, according to their abilitiesO ~-.~ -l'he polymerization can be carried out usually at a temperature of -30 to 80Cu, preferably -10 -to 50C. 7 more preferably 10 to 40C. Atmospheric pressure suffices as the polymerization pressure. If desired, the polgmeri-zation may be carried out at eleva-ted or reduced pressures in the range of 0.1 to 10 atmospheres.
Under the above-mentioned conditions, the poly-merization can be comple-ted usually within 30 mi~utes to 5 hours.
After the polymerization7 the ¢atalyst can be removed by such a treatment as washing with an alkali aqueous solution or with water, an~ the ~nreacted hydro-carbons or low polymers can be removed by a suitable means such as distillation. Advanta~eously, the distillation is carried out genera]ly at a temperature of 150 to 250C.
and 5 mmHg to 100 mm~Ig. As a result, hydrocarbon resins can be obtained as distillation bottoms In the above polymerization, a small amount of .
another monomer copolymerizable with the cationically polymerizable hy~rocarbons can be added to the petroleum fraction in order to modi~y them. For example, a petro-~ :~
leum cracki~g or reforming fraction containing cationical-ly polymerizable C4;or C5~hydrocarbons and having a boll ing range of~-20 to~100C. can be added -to the preheated ; 25 petroleum fraction i~ an amount of 10 to 1O~/Q by weight, preferably 15 to 8~/~ by weightO ~-: The process of the present invention described herem above can~afford~aromatic hydroc~rbon re6ins free : ~ ~J : : , '~
- 2L~ -from poor -thermal stability, strong odor and a high degree of coloration which are -the ~efec-t~ of -the conven-tional aroma-tic hydrocarbon resins. i~he hy(lrocarbon resins ob-tained by the preserlt invention have greatly improved thermal s-tability, coloration and odor, and exhibit higher thermal stability, lesser coloration and lesser odor than aromatic hy~rocarbon resins pr~pared by the process described in Germ~m Offenlegungsschrift ~oO
2716763 (corresponding to UuSO Patent 4,10~J,~3) which discloses -the closest ar-t to the process of this inven-tionO
Another advanta~,re of the process of this inven-tion is that since any catalyst-poisonin,r components present in the starting pe-troleum cracking or reforming fraction can be removed by the heat treatment of the fraction, the amount of the polymerization catalyst can be reduced as compared with the conven-tional methods.
Because of their higrh thermal stability~ little odor and low degrees of coloration, the hydrocarbon resins produced by the process of this invention can be advanta,reously used as binder componen-ts in hot-melt adhesives, pressure-sensitive adhesives, and thermofusible traffic paintsO
~ he following examples specifically illustrate the process o~ the presen-t invention.
Ex~mple 1 A naphtha crac'~ing fraction (A) having a boiling range of 1l~0 to 240C and the following composition was used as a starting materialO
~ h 'rable 1 Composi-tion of naphtha cracking fraction (A) Content (% by weight based on the -total weight of the Com~onents fraction (A) C~clopentadienes 108 S-tyrene 0.9 a-Methylstyrene 1~2 ~-Methyl.styrene .03 Dicyclopentadiene 008 Vin~ltolu.enes (o, m, p) 21~5 Methyldicyclopentadienes 1D2 Dime-thyldicyclopentadienes 1.7 Indene 12 ~ 8 Methylindenes 401 Saturated C8-Cll aromatic hydrocarbons 5307 ~he starting fr~ction (A) was fed in-to a dis--tillation tower having the specification shown in ~able 2~ ;
and distilled under the operating conditions indicated in Table 2. A low-boiling fraction containing cyclopen-tadienes was withdrawn ~rom the top of the tower; a high-boiling fraction, from the bottom of the tower; and a main fraction having a low content of cyclopentadienes, from the 7th tray of the distillation tower.
, " ;,, , ,~ ",~ ",; ," ,j :::: " ; ~ ", , " i "
i' i' ' . ~ . ....
- 26 ~ 3~ q,i`,~,~
~able 2 Specification of the distillRt;ion tower ancl the operating con~itions 'rype of trays ....... O.O....... OO Rubble cap t:rays Number of trays OO.... ..OOO~O... ...10 Tray to which the starting material was fed ~ooo~ 5th from the bottom ~eeding temperature (CO)~OOO~ 108 '~emperature (CO) of the bottom of the tower.O.O...OD... 206 Preissure (mmXg, abs.) of -the bottom of the -tower ~ O~ 250 Temperature (C.) of the top of the tower O..,.~..OO.~0, 96 Pressure of th.e top of the tower (m~Hg, abs~)~OOOO..OO. ,0 200 Reflux ratio ~OO~OOO~O~ OO 2 Tray from which the main fraction was withdrawn OO..OO.0 7 '~emperature (CO) of the tray from which the main fraction was withdrawn .OO~O~O 1~5 By this distillation, 8% by weight of the low- ;
boiling fraction and 21/, by weipht of the high-boiling fractlon were removed from-the starting frac-ti.on (A) to form a main frac-tion (B)o . ,. ,,, .. ; . ., , ., , . . , ,, ,, , ~,. ., , ,-, , ~
a~
'rable 3 Co~posi.tion of the main fraction (B) Content (,~ by weight based on the weight of the Components fraction (B~
Cyclopentadienes 0.2 ~tyrene 5 a-Me-thylst~rene loO
~-Methylstyrene 003 Dicyclopentadiene 0.5 Vinyltoluenes (o, m, p)21 n 8 Methyldicyclopen-tadienes loO
Dime-thyldicyclopentadienes 1.6 Inclene 12.6 Me-thylindenes 2.0 Saturated C~-Cll aromatic hydrocarbons 58.5 ~ aleic anhydride (0.5% by weight corresponding -to 2.0 molar equivalents based on the cyclopentadienes) was added to the main ~raction (B)~ and it was treated at 25C for 30 minutes with stirring ~hen~ 0O5% by weight of a boron trifluoride-phenol complex catalyst was added to the trea-ted fraction~ and the fraction was polymerized at 35C for 2 hours. ~he ca-talyst was then decomposed with a ~k by weight aqueous solution of sodium hydroxide~ ~he polymerization product was washed with water, and distilled at 200C to 210C and 10 mmHg to remove the unreacted componen-ts and polymers having low ,! :
:
degrees of polym~rizationO Thus, a hydrocarbon resin was obta.ined which had the characteristics shown in ~able ].0, Examples 2 t~ and Co~arative ~xample 1 ~he naphtha cracking pertoleum fraction (A) used in Example 1 was clistilled under the same conditions as in Example 1 except that the distilling conditions were c~i~
ch~n~ed as shown in ~able lOo Thus, main fraction,s (C), (D), (E), (F) and (G) having t'he compositions shown in ~ables 4 to ~ below were obtained. EaCh of -the mairl fr,qctions was treated wit'h maleic anhydride under the conditions shown in ~able 10, and polyl~erized and post--trea-ted in the same way as in 'Example lo ~hus, hydrocar bon resins havin~ -the characteristics given in ~able 10 were obtained~
I'able 4 (Example 2) Composition of the fraction (C) Content ~ by weight based on the weight Components of -the fr Cyclopentadienes 0~05 ~tyrene 0~2 a_Methylstyrene 0~8 ~-Methylstyrene ~.2 Dicyclopen-tadiene 005 ;.
Vinyl.toluenes (o ? m, p-) 21.9 ' Meth~ldicyclopentadienes1~2 Dimethyldic~clopentadienes 1,7 Indene 12,7 :' ~e-thylindenes 2,1 Saturated C8 ~ C~ll aroma-tic hydrocarbolls 58~7 :
: . .
i - ?9 -able 5 (E-xample 3) Composi-tion of -the fraction (D~
Content t~', by weigrh-t based on the weight nents o~ the_~rac-tio Cyclopentadienes 0.1 Styrene 004 ~Methylstyrene 09 ~-Methylstyrene 0~2 Dicyclopentadiene 0~6 Vinyltoluenes (o, m, p-)2201 Methyldicyclopentadienesl o 3 Dimethyldicyclopen-tadienes 1.7 Indene 1206 Methylindenes 202 Saturated C8 - Cll aromatic hydrocarbons57.9 Table 6 (Example 4) Co~position of the fraction (~) Content ~/ by waight based on the wei~ht Components of the f Cyclopen-tadienes 005 Styrene 006 ~-Methylstyrene 1.1 ~-Methylstyrene 0~2 Dicyclopentadiene 0.4 Vinyltoluenes (o, m, p-)2104 Methyldicyclopentadienes1.2 Dimethyldicyclopentadienes 106 Indene 12~2 Methylindenes 1,9 Saturated C8 ~ Cll aromatic hydrocarbon 58.9 ~:
-"
- :~o -':r~lble 7 (Example 5) Co~position of the frac-tion (~) Content t% by weight based on the wei~ht Components of the fra "
Cyclopentadienes 007 Styrene 0.8 a-Meth.ylstyrene lol ~-Methylstyrene 002 Dicyclopen-tadiene O,L~
Vinyltoluenes (o, m, p-) 21.0 Methyldicyclopentadienes 102 Dime-thyldicyclopentadienes 1.6 Indene 12n O
Methylindenes 1.8 SatUrated C8 ~ Cll aromatic hydrocarbons 5902 ~able (Compara-tive Exemple 1) Composition of the fraction tG) Content t/~ by wei~ht based on the weight Components of the fraction Cyclopentadienes loO .
Styrene 009 a_Methylstyrene lo 2 I~-Methylstyrene 0~ 2 Dicyclopentadiene 03 Vinyltoluenes (o, m, p-) 2006 :
Methyldicyclopentadienes lol ::
Dimethyldicyclopentadienes 105 Indene 11~7 ~ethylindenes 107 Saturated C8 - Cll aromatic hydrocerbons 59~8 , ~ ~L 3 ~ L~L
a~les 6 to ~ and Com~arative ~xar.~;ples 2 _n~_~
The main fra~tion (~) ha-ving -the compo,sition shown i.n 'rable 6 and used in Exflmple 4 was treated under the conditions indica-ted in Table 1, and then polymerized and post-treated in the same w~sy as in Example 1. Hydro-carbon resins having -the characteristics shown in Table 10 were obtainedu _ m~
The main fraction (B) hi~ving the composition shown in Table 3 ancl-used in Example 1 was -trea-tecl with maleic anhydride in the sam~ way as in Example 1.
mixture consistin~ of ~,0 p~srts by weight of the treated fraction and a naphtha crac~iing fraction having a boiling range of -20C -to ~20C (pol~merizable components 93.6%
by weight) as shown in Table 9 was polymerized in the presence o~ 0O5 p,srt by weiph-t of a boron trifluoride/
phenol complex catalyst, and post-treated in the same way as in Exa~ple 1. A hydrocarbon resin was obtained which had the charcscteristics shown in Table lOo 9~
Ilable 9 ___ Composi-tion of the naphtha cr~cking fraction having a boiling range of -20 to 20C.
(,ontent (0/.~! by weight based on the weight nent of the frac o~
Propylene -5 i 50 -]3utane 0~5 n-Butane 4.6 l-Butene 20~7 iso-Butene 25.5 trans-2-Butene 706 cis-~-Butene 506 1,3-Butadiene 34.2 C5-paraffin 0~8 Exam~les lO_and 11 :.
~ he main fraction (B) havin~ the composition shown in ~able 3 and obtained in Example 1 was treated with each of the a~-unsaturated dicarboxylic acid an-hydrides indicated in ~able 10, and poliymerized and post-treated in the same way as in Example 1 to afford hydro-carbon resins having the characteristics shown in ~able 10.
Examples 12 to 14 The main fraction (B) havin~; the composition shown in Table 3 and obtained in hxample 1 was ^treated ~ :
with maleic anhydride molten at 70C under -the conditions described in ~able 10, c~nd pol~merized and post-treated , , ~ .
. .. . ... . -- ~3 -in -the scq~me way as in Example ]. to afford hydrocarbon resins having the c~aracteristics gi-ven in 'rable 10~
Mc~leic anhydride (408% by weight; corresponding to 2.0 molar equivalen-ts based on cyclopentadienes) was added to the naphtha cracking fraction (A) having the composition given in Table 1 and used in Exa~ple 1, and with stirring, it was treated at 25C for 2 hoursO '~he reaction mixture was then distilled, and a distillate oil having a boiling poin-t of up to 120C'20 mmHg was recovered in a yield of 97~o by weightO ~he resulting distillate oil was polymerized and post-treated in the same way as in Example 1 to afrord a hydrocarbon resin having the characteristics shown in ~able lOo 1~ C mpar~tive Example 5 ~ he procedure of Comparative Example 4 was repeated except that treatment with maleic anhydride was performed at 100C7 and the distillate oil was recovered in a yield of 91~. by weightO A hydrocarbon resin having the characteristics shown in ~able 10 was obtained.
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Comparative olnt Th~rmal Example Yield P Color s~ability (CExo ) (wto/~) _~ (Gardner) (Gar-1ner) Odor Exo 1 38 131 6 10 A
Ex~ 2 39 132 6 ] 0 A
Exo 3 39 131 6 10 A
Ex. 4 39 132 6 10 A
Ex~ 5 38 132 605 11 A
CEx. 1 36 135 9 13 C
@xo 6 37 131 7 11 B
Ex. 7 38 130 6 10 A
Ex 8 3~ 132 6 ~ 5 1005 A-B
CEx. 2 37 130 9 13~ B
CEx. 3 37 134 ~ 5 1205 Exo 9 43 95 5~5 905 A
Ex 10 38 131 6 10 A
Ex7 11 37 130 6 10~5 A
Ex~ 12 39 132 6 10 A
: Ex. 13 38 130 6 IO A
Ex~ 14 3B 131 60 S lOo 5 A
:
CEx. 4 39 132 805 12.5 B ~ :
C~X o 5 37 130 705 12 B ;:
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Maleic acid (0.5~,', by weight; correspondin~; to 2.0 molar equivalents based on the cycl.open-tadienes) was added to the main fraction (B) having the composition shown in 'rable 3 and obtained in ~xarnple 1, and the frac-tion was -treated at 40C for 30 minutes with stirrin~.
'rhe -treated fraction was polymerized an~ post--treated in the same way as in Exarr~le 1 to afford a hydrocarbon resin having -the charac-teristics sho~m in 'r~ble 11 Examples 16 o `'i ~ L~r~ m~le 6 Each of the main fr~ctions (~) to (G) having, -the composi-tions shown in 'rables 4 to 8 respecti~ely was treated with maleic acid under the conditlons indicated in Table 11, and then polymerized ~nd post-treated in the same way as in Example 1~ Thus, hydrocarbon resins having the characteristics shown in Table 11 were obtainedO
h~arl~les 20 to 22 an ~ Ex~~ es Z__nd 8 'rhe main fraction (E) havin~ the con1posi-tion shown in 'rable 6 and used in ~xample 4 was -treated under the conditions shown in 'rable 11, and then polymerized and pos-t-treated in the same way as in Example 14 ',rhus, hydxocarbon resins havin~ the characteristics shown in 'rable 11 were obtainedG
Example 23 'rhe main fraction having -the composition shown in 'rable 3 ancl obtained in Example 1 was treated with maleic acid in the same way as in Example 14 A mixture of 80 parts by weight of -the treated fraction cmd 20 parts by weight of the naphtha crac]cingr fr,action havin~ a boiling . ~ ~. . :, - : ,, .. .. ,: :~ :. ., : :: :
_ ran~e of -20C -to ~20C descri.bed in 'rable 9 (contrlinin~
93.6~ by wei~ht of polymerizable cornponerlts) was poly-merized in -the presence of 0O5 part by weight of a boron -trifluoride/phenol complex ca-talys-t and ~ost--treated in the same way as in Example lo A hy~roc~rbon resin was obtained which had the characteristics described in Table 11..
Examples 24 and 25 'rhe main ~rac-tion havin~ the composition described in 'rable 3 and obtained in ,Example 1 was treated with each of the a~-unsaturated carboxyli,c acids shown in 'rable 11, and polymerized and post-treated in the same way as in ~xample 1~ 'rhus, hydrocarbon resins having the characteristics shown in 'rable 11 were ob-tained.
Examples 26 and 27 'rhe main fraction (B) havin~ -the composition shown in 'rable 3 and obtained in Example 1 was -treated under the conditions shown in 'rable 11, and polymerized and post-treated in the same way as in ~xample lo '~hus, hydrocarbon resins having the characteris-tics shown in Table 11 were obtained.
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(CExo ) _ ~ (C~ Jar~ner) (Gardne.r~Odor Ex. 15 37 133 605 10.5 Exo 16 39 130 6 10 A
Exo 17 38 131 6 10 A
Ex. 18 37 130 60r~ 11 A
Ex. 19 35 130 7 11 A
CEx. 6 31 ].31 10 lL~ C
Ex. 20 37 132 7 11 :B
E~X.21 37 ] 3 6. 5 lOo 5 A
Ex. 22 36 130 7 11 A-B
C~x. 7 37 l~il 9 lL~ B
CEx~ 8 35 132 805 12.5 B
Ex. 23 41 96 5~,5 9.c7 h~x.2L~ 36 132 6 10 A
:Ex. 25 35 130 60 5 lOo 5 A
Exo 26 37 130 6 10 A
Ex~ 27 38 131 7 l O o 5 A
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Example 28 Malei:mi~le (O~L~/C by weight; correspondin~ to 1.5 molar equivalen-ts based on cyclopentadienes) was added to the main frcqetion (B) havin~ the composltion shown in Table 3 and obtained in hx~mple 1, and the fraetion was t,reated a-t 40G for 30 minutes with stirring. The treated fraction was polyrlerized ancl pc)st-treated in the same way as in Example 1 -to afford a hydroearbon resin having the eharacteristics shown in Table 12 10 ~
The naphtha craeking fraction (A) havin~ the eomposition shown in Table l and usecl in Example l was distilled under the same co.nditions as in Example l exeept that the distillin~ conditions were ehanged as shown in ~able 12. ~rhus, the main fraetions (C), (~), (F) and (G) having -the compositions shown in Tables 4 and 6 to 8 respectivel~J were obtained. These main frae-tions were treated with maleinimide uncler -the conditions shown in ~able 12, and then polymerized and post-treated in -the 2(? same way as in Example 1 to afford hydrocarbon resins having th~ characteristics shown in Table 12 Examples_~2 and 33 The main fraction (~) havin~ the eomposition shown in Table 3 and used in Exa~ple l was treated under the concliti~ns shown in Table 12, and polymerized and post-treated in the same way as in Example l to afford h~drocarbon resins having the characteristics shown in Table 12r .
'~ ~ 3 _ /~3 _ ~ he main fraction (B) having the composition shown in ~able 3 and obtained in Example 1 was treated with each of the uns~turated polar compounds described ~n Table 12, and polyrqerized and post-treated in the sarne way as in Example 1 to afford hydrocarbon resins having the characteris-tics shown in ~able 12.
Examples_37 and 38 ~ he main fraction (B) having the composition shown in ~able ~ and obtained in Exarnple 1 was treated with r~al~imide under -the conditions shown in ~able 12, and polymerized and post--treated in the .sarne way as in Example 1 to afford hydrocarbon resins havin~; the charac-teristics shown in ~able 120 ~4~
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o sl o 3) o 1 V ~ ~l El C) r~ a d 0 bD d ~rl Q) ~ ~rl ~rl ~ r--I O (~ ~ O r1 ~I r-l r-lr-l r-l r-l C) O ,~ ~(~1 ~Ir~l r~ N ~ 1 01 r~
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-- L~5 _ :[~ble 12 ( con tinuecl ) . ~ _ ( Exo ) or ~ roc~:rbon re~in __ Compara-tive Soft~nlng 'rhermal ~xampl e Yi~ld P int Co lo r stabil ity (C5~xo ) _ ~ ~ ~ 5~r) ~ Odor Exo 2~3 37 130 6 10 A
~xO 29 3~ 1 31 6 10 1~
Exo 30 37 131 60 5 10. 5 A
EY. 31 36 130 7 11 A
CExo 9 35 133 9 13. r~ C
Exo 32 38 132 6 10 A
Exo 33 37 130 6~ 5 10. 5 A
Ex~ 3L~ 36 131 7 11 A
Ex~ 35 37 132 6 10.. 5 A
Exo 36 39 130 605 10.5 A
Ex. 37 36 130 6 10 A
5xo 38 37 132 60 5 10 . 5 A
. . .
oarboxylic~acld arnlde group (-CON~ 3 3, a carbo~yllc acid imide~group (-CO-NH-CO-), a cyano group (-CN), a O
~ formyl group (-GHO)~and a keto group ( -C- ), and - -: : ':
-generally 3 to 15, preferably 3 to 10, and more preferably 4 to 10, carbon atoms.
Typical examples of the ~,~-unsaturated dieno-phile compounds which can be used in the present invention are ~iven below~
(A) a~-unsaturated carboxylic acids Suitable ~,i3-unsaturated carboxylic acids that can be used in this invention are aliphatic or cycloali-ph~tic a?~-unsaturated mono- or di-carboxylic acids con-tainin~ up to 15, preferably 3 to 10, carbon atomsO
Specific examples include acrylic acid, methacrylic acid, a-ethylacrylic acid, crotonic acid, maleic acid, citra-conic acid, ~ -tetrahydrophthalic acid, and ~2-tetra-hydrophthalic acidO The a, ~-unsa~urated dicarboxylic acids are preferred, and maleic acid is especially preferred~
(B) a,~-Unsaturated carboxylic acid anhydrides In the present invention, aliphatic or cyclo-aliphatic a, ~-unsaturated dicarboxylic acid anhydrides containing generally up to 15 carbon atoms, preferably 4 to 10 carbon atoms, are suitable~ Examples are maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and ~2-tetrahydrophthalic anhydride. The aliphatic a, ~-unsaturated dicarboxylic acid anhydrides, above all maleic anhydride, are preferredO
(C) a,~-Unsaturated carboxylic acid esters ~uitable esters are alkyl esters, particularly lower alkyl esters, of the a ? ~-unsaturated mono- or di-dica~boxylic acids described in paragraph (A) aboveO
~ ~ 3 Specific ex~mples include methylacryla-te, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl c~otonate, dimethyl maleate, diethyl malea-te, dimethyl itaconate, diisopropyl citraconate, and diethyl tetrahyr'rophthalateO
(D) a,~-Unsaturated carboxylic acid amides Suitable amides are amides of the u,~-unsaturated mono- or di-carboxylic acids described in paragraph (A) above, in which the nitrogen a-tom can be substituted by one or two alkyl rroups, particularly lower alkyl groups.
; 10 Specific examples include acrylamide me-thacrylamide, croton~mide, maleinamide, itacont~mide, citraconamide, and tetrah,ydrophthalamide.
(E) a,~-Unsaturated cflrboxylic acid imides Suitable imides are imides of the a,~3-unsatura- -ted dicarboxylic acids de~cribed in paragraph (A) above~
ypical examples are maleimide, ltaconimide~ cltracon-imide, and tetrahydrophthalimide~
-Unsaturated nitriles Suitable nitriles are those containing l ; 20 carbon-carbon double hond and l to 4 cyano groups ad-jacent to the~double bond, and 3 to 10, preferably 3 to~
6, carbon atoms. ~Specific examples are acrylonitrile, methacrylonitrile,;crotononltrile, maleonitrlle, ci-tra- ~
cononitrile~and tetracyanosthyleneO ~' (G3 ~ Unsaturated aldehy~es Suitable aldehydes are those havin~ one carbon-carbon double bond, l or 2 formyl~roups ad~jacent to the double bond?~;an~ 3~to 10, prefer~ably 3~-to 6, carbon~atomsO
~-, :: : :
.
: ; : :~
L~.3~
~o Examples include acroleln, methacrolein, crotonaldehyde and maleic dlaldehyde~
(H) Quinones Suitable quinones are benzoquinone and naph-thoquinone.
~ he term "lower alkyl" used in the presentspecifica-tion deno-tes a linear or branched alkyl ~roup having 1 to 6, preferably 1 to 4, carbon a-toms, and in-cludes, for example, methyl, ethyl, n- or iso-~ropyl, ~: 10 n-, sec-, iso- or tert-butyl, n-pentyl~ iso-amyl, and n-hexyl O
he a~-unsatura-ted dicarboxylic acid anhydrides, especially maleic anhydride, descri~ed in paragraph (B) above can be used especially advantageously in this invention.
he amount of the dienophile compound is no-t ~ . -restricted to: a narrow range~ and c~an be chosen from a wide range.~: However, :even 1f lt i8 used in a larger ~ -: amount than is~necessary, no corresponding technlcal 20~ advantage oan be~obtained~ Such large amoun-ts are wasteful, and:rather`pose a problem of corroding the equlpment.
A~great feature~of the~procesa o~ this i~nvention~
. is~that the~amount o~;the~dienophlle ccmpcund can be reduced~very:muchO hls solves the~:~rcblem of~equipment :corrosion~ and~can eliminate the need for an additional step cf separatin~g the~adducts fcrmed between the dieno~
phlle and c~clcpentadienes.
~L3~
In the present invention, -the dienophile com-pound can be used in an amoun-t of 008 to 3.0 moles, pre~
ferably 1.0 -to 2.5 moles, more prefer3bly 1.~ to 200 moles, per mole of ~PDs conta~ned in the petroleum crack-ing or reforming fraction to be treated~
The dienophile compound needs not to be com-pletely dissolved in the petroleum cracking or reforming frsctionO Desirably, however, it is at least partially soluble in the petroleum fraction under the treating conditions~ When it is substanti~lly insoluble in -tho : petroleum fraction, it is preferred to dissolve it in a solvent compatible with the fraction before adding to ~: the petroleum fraction~
~; ~he treatment of the petroleum fraction with the dienophile compound can be performed by adding the dienophile compound as a liquid, solid, melt or solution to the petroleum fraction, and contacting them intimately :
with each other. ~he treating temperature is not critical, and can be varied widely accord m~ ~to the type of:the 20 dlenophile compound used,~etcO Generally, temperatures ~. ~{
of lO to 150C,:preferably 10 to 100C7 more preferably:
: room~temperature to less than 50C:, are advantageous.
he~trea-tment can be~ effected usu~lly under ;.
atmospheric pressure,~but if req~ired, it may be carried out under elevated or reduced pressures~ ~he time: re-qulred for the treatment is not critlcal, and can:be :
varled~widely according to the amount~o~f CPDs in the ~ :~
petroleum:fraction, the type o~ the dienophile compound, ~ : ::
.3~
~ 22 -e-tc. Since in the presen-t inven-tion, -the amount of CPD~
contained in the petroleum fraction is far smaller than that in fractions treated by conventional me-thods, the treating time can be grea-tly shortened. '~he sufficient trea-ting time is usuall-y at least 30 seconds, preferably l minute to l.0 hour, more preferably 5 minu-tes to 30 minutes, according to the treating temperature.
~ he treatmen-t with the dienophile alone can lead to hydrocarbon resins having very good color and thermal stability, but if desired, this treatment may be carried out in -the presence of a small~less -th~n 1%~
amount of solid acid or ~ewis ~cido ~ he petroleum cr~cking or reforming fraction treated with the dienophile compound in the manner 1~ described above can be directly submitted to a polymeri-zation step in accordance with the process of this inven-tion. ~his is one great adv3ntage of the invention.
The polymerization can be carried out by any ~: . . .
known method used in the production of ordinary hydro-carbon resinsO
Polymerization cat~lysts norm~ally used in th1s invention are Friedel-Crafts cat~lysts such as boron tri- ;
fluoride, boron trifluoride complexes (eOgo ~ boron tri-~.
fluoride/phenol complex), aluminum trichloride, aluminum 2r~ trlbromifle, tin tetrachloride, and titaniumi tetrachloride~
hese pol~merization ca-talysts can be used in an amount of ~enerally Ool to 5~ by wei~ht, preferably 0.5 to 3,~
:
~ by weight, according to their abilitiesO ~-.~ -l'he polymerization can be carried out usually at a temperature of -30 to 80Cu, preferably -10 -to 50C. 7 more preferably 10 to 40C. Atmospheric pressure suffices as the polymerization pressure. If desired, the polgmeri-zation may be carried out at eleva-ted or reduced pressures in the range of 0.1 to 10 atmospheres.
Under the above-mentioned conditions, the poly-merization can be comple-ted usually within 30 mi~utes to 5 hours.
After the polymerization7 the ¢atalyst can be removed by such a treatment as washing with an alkali aqueous solution or with water, an~ the ~nreacted hydro-carbons or low polymers can be removed by a suitable means such as distillation. Advanta~eously, the distillation is carried out genera]ly at a temperature of 150 to 250C.
and 5 mmHg to 100 mm~Ig. As a result, hydrocarbon resins can be obtained as distillation bottoms In the above polymerization, a small amount of .
another monomer copolymerizable with the cationically polymerizable hy~rocarbons can be added to the petroleum fraction in order to modi~y them. For example, a petro-~ :~
leum cracki~g or reforming fraction containing cationical-ly polymerizable C4;or C5~hydrocarbons and having a boll ing range of~-20 to~100C. can be added -to the preheated ; 25 petroleum fraction i~ an amount of 10 to 1O~/Q by weight, preferably 15 to 8~/~ by weightO ~-: The process of the present invention described herem above can~afford~aromatic hydroc~rbon re6ins free : ~ ~J : : , '~
- 2L~ -from poor -thermal stability, strong odor and a high degree of coloration which are -the ~efec-t~ of -the conven-tional aroma-tic hydrocarbon resins. i~he hy(lrocarbon resins ob-tained by the preserlt invention have greatly improved thermal s-tability, coloration and odor, and exhibit higher thermal stability, lesser coloration and lesser odor than aromatic hy~rocarbon resins pr~pared by the process described in Germ~m Offenlegungsschrift ~oO
2716763 (corresponding to UuSO Patent 4,10~J,~3) which discloses -the closest ar-t to the process of this inven-tionO
Another advanta~,re of the process of this inven-tion is that since any catalyst-poisonin,r components present in the starting pe-troleum cracking or reforming fraction can be removed by the heat treatment of the fraction, the amount of the polymerization catalyst can be reduced as compared with the conven-tional methods.
Because of their higrh thermal stability~ little odor and low degrees of coloration, the hydrocarbon resins produced by the process of this invention can be advanta,reously used as binder componen-ts in hot-melt adhesives, pressure-sensitive adhesives, and thermofusible traffic paintsO
~ he following examples specifically illustrate the process o~ the presen-t invention.
Ex~mple 1 A naphtha crac'~ing fraction (A) having a boiling range of 1l~0 to 240C and the following composition was used as a starting materialO
~ h 'rable 1 Composi-tion of naphtha cracking fraction (A) Content (% by weight based on the -total weight of the Com~onents fraction (A) C~clopentadienes 108 S-tyrene 0.9 a-Methylstyrene 1~2 ~-Methyl.styrene .03 Dicyclopentadiene 008 Vin~ltolu.enes (o, m, p) 21~5 Methyldicyclopentadienes 1D2 Dime-thyldicyclopentadienes 1.7 Indene 12 ~ 8 Methylindenes 401 Saturated C8-Cll aromatic hydrocarbons 5307 ~he starting fr~ction (A) was fed in-to a dis--tillation tower having the specification shown in ~able 2~ ;
and distilled under the operating conditions indicated in Table 2. A low-boiling fraction containing cyclopen-tadienes was withdrawn ~rom the top of the tower; a high-boiling fraction, from the bottom of the tower; and a main fraction having a low content of cyclopentadienes, from the 7th tray of the distillation tower.
, " ;,, , ,~ ",~ ",; ," ,j :::: " ; ~ ", , " i "
i' i' ' . ~ . ....
- 26 ~ 3~ q,i`,~,~
~able 2 Specification of the distillRt;ion tower ancl the operating con~itions 'rype of trays ....... O.O....... OO Rubble cap t:rays Number of trays OO.... ..OOO~O... ...10 Tray to which the starting material was fed ~ooo~ 5th from the bottom ~eeding temperature (CO)~OOO~ 108 '~emperature (CO) of the bottom of the tower.O.O...OD... 206 Preissure (mmXg, abs.) of -the bottom of the -tower ~ O~ 250 Temperature (C.) of the top of the tower O..,.~..OO.~0, 96 Pressure of th.e top of the tower (m~Hg, abs~)~OOOO..OO. ,0 200 Reflux ratio ~OO~OOO~O~ OO 2 Tray from which the main fraction was withdrawn OO..OO.0 7 '~emperature (CO) of the tray from which the main fraction was withdrawn .OO~O~O 1~5 By this distillation, 8% by weight of the low- ;
boiling fraction and 21/, by weipht of the high-boiling fractlon were removed from-the starting frac-ti.on (A) to form a main frac-tion (B)o . ,. ,,, .. ; . ., , ., , . . , ,, ,, , ~,. ., , ,-, , ~
a~
'rable 3 Co~posi.tion of the main fraction (B) Content (,~ by weight based on the weight of the Components fraction (B~
Cyclopentadienes 0.2 ~tyrene 5 a-Me-thylst~rene loO
~-Methylstyrene 003 Dicyclopentadiene 0.5 Vinyltoluenes (o, m, p)21 n 8 Methyldicyclopen-tadienes loO
Dime-thyldicyclopentadienes 1.6 Inclene 12.6 Me-thylindenes 2.0 Saturated C~-Cll aromatic hydrocarbons 58.5 ~ aleic anhydride (0.5% by weight corresponding -to 2.0 molar equivalents based on the cyclopentadienes) was added to the main ~raction (B)~ and it was treated at 25C for 30 minutes with stirring ~hen~ 0O5% by weight of a boron trifluoride-phenol complex catalyst was added to the trea-ted fraction~ and the fraction was polymerized at 35C for 2 hours. ~he ca-talyst was then decomposed with a ~k by weight aqueous solution of sodium hydroxide~ ~he polymerization product was washed with water, and distilled at 200C to 210C and 10 mmHg to remove the unreacted componen-ts and polymers having low ,! :
:
degrees of polym~rizationO Thus, a hydrocarbon resin was obta.ined which had the characteristics shown in ~able ].0, Examples 2 t~ and Co~arative ~xample 1 ~he naphtha cracking pertoleum fraction (A) used in Example 1 was clistilled under the same conditions as in Example 1 except that the distilling conditions were c~i~
ch~n~ed as shown in ~able lOo Thus, main fraction,s (C), (D), (E), (F) and (G) having t'he compositions shown in ~ables 4 to ~ below were obtained. EaCh of -the mairl fr,qctions was treated wit'h maleic anhydride under the conditions shown in ~able 10, and polyl~erized and post--trea-ted in the same way as in 'Example lo ~hus, hydrocar bon resins havin~ -the characteristics given in ~able 10 were obtained~
I'able 4 (Example 2) Composition of the fraction (C) Content ~ by weight based on the weight Components of -the fr Cyclopentadienes 0~05 ~tyrene 0~2 a_Methylstyrene 0~8 ~-Methylstyrene ~.2 Dicyclopen-tadiene 005 ;.
Vinyl.toluenes (o ? m, p-) 21.9 ' Meth~ldicyclopentadienes1~2 Dimethyldic~clopentadienes 1,7 Indene 12,7 :' ~e-thylindenes 2,1 Saturated C8 ~ C~ll aroma-tic hydrocarbolls 58~7 :
: . .
i - ?9 -able 5 (E-xample 3) Composi-tion of -the fraction (D~
Content t~', by weigrh-t based on the weight nents o~ the_~rac-tio Cyclopentadienes 0.1 Styrene 004 ~Methylstyrene 09 ~-Methylstyrene 0~2 Dicyclopentadiene 0~6 Vinyltoluenes (o, m, p-)2201 Methyldicyclopentadienesl o 3 Dimethyldicyclopen-tadienes 1.7 Indene 1206 Methylindenes 202 Saturated C8 - Cll aromatic hydrocarbons57.9 Table 6 (Example 4) Co~position of the fraction (~) Content ~/ by waight based on the wei~ht Components of the f Cyclopen-tadienes 005 Styrene 006 ~-Methylstyrene 1.1 ~-Methylstyrene 0~2 Dicyclopentadiene 0.4 Vinyltoluenes (o, m, p-)2104 Methyldicyclopentadienes1.2 Dimethyldicyclopentadienes 106 Indene 12~2 Methylindenes 1,9 Saturated C8 ~ Cll aromatic hydrocarbon 58.9 ~:
-"
- :~o -':r~lble 7 (Example 5) Co~position of the frac-tion (~) Content t% by weight based on the wei~ht Components of the fra "
Cyclopentadienes 007 Styrene 0.8 a-Meth.ylstyrene lol ~-Methylstyrene 002 Dicyclopen-tadiene O,L~
Vinyltoluenes (o, m, p-) 21.0 Methyldicyclopentadienes 102 Dime-thyldicyclopentadienes 1.6 Indene 12n O
Methylindenes 1.8 SatUrated C8 ~ Cll aromatic hydrocarbons 5902 ~able (Compara-tive Exemple 1) Composition of the fraction tG) Content t/~ by wei~ht based on the weight Components of the fraction Cyclopentadienes loO .
Styrene 009 a_Methylstyrene lo 2 I~-Methylstyrene 0~ 2 Dicyclopentadiene 03 Vinyltoluenes (o, m, p-) 2006 :
Methyldicyclopentadienes lol ::
Dimethyldicyclopentadienes 105 Indene 11~7 ~ethylindenes 107 Saturated C8 - Cll aromatic hydrocerbons 59~8 , ~ ~L 3 ~ L~L
a~les 6 to ~ and Com~arative ~xar.~;ples 2 _n~_~
The main fra~tion (~) ha-ving -the compo,sition shown i.n 'rable 6 and used in Exflmple 4 was treated under the conditions indica-ted in Table 1, and then polymerized and post-treated in the same w~sy as in Example 1. Hydro-carbon resins having -the characteristics shown in Table 10 were obtainedu _ m~
The main fraction (B) hi~ving the composition shown in Table 3 ancl-used in Example 1 was -trea-tecl with maleic anhydride in the sam~ way as in Example 1.
mixture consistin~ of ~,0 p~srts by weight of the treated fraction and a naphtha crac~iing fraction having a boiling range of -20C -to ~20C (pol~merizable components 93.6%
by weight) as shown in Table 9 was polymerized in the presence o~ 0O5 p,srt by weiph-t of a boron trifluoride/
phenol complex catalyst, and post-treated in the same way as in Exa~ple 1. A hydrocarbon resin was obtained which had the charcscteristics shown in Table lOo 9~
Ilable 9 ___ Composi-tion of the naphtha cr~cking fraction having a boiling range of -20 to 20C.
(,ontent (0/.~! by weight based on the weight nent of the frac o~
Propylene -5 i 50 -]3utane 0~5 n-Butane 4.6 l-Butene 20~7 iso-Butene 25.5 trans-2-Butene 706 cis-~-Butene 506 1,3-Butadiene 34.2 C5-paraffin 0~8 Exam~les lO_and 11 :.
~ he main fraction (B) havin~ the composition shown in ~able 3 and obtained in Example 1 was treated with each of the a~-unsaturated dicarboxylic acid an-hydrides indicated in ~able 10, and poliymerized and post-treated in the same way as in Example 1 to afford hydro-carbon resins having the characteristics shown in ~able 10.
Examples 12 to 14 The main fraction (B) havin~; the composition shown in Table 3 and obtained in hxample 1 was ^treated ~ :
with maleic anhydride molten at 70C under -the conditions described in ~able 10, c~nd pol~merized and post-treated , , ~ .
. .. . ... . -- ~3 -in -the scq~me way as in Example ]. to afford hydrocarbon resins having the c~aracteristics gi-ven in 'rable 10~
Mc~leic anhydride (408% by weight; corresponding to 2.0 molar equivalen-ts based on cyclopentadienes) was added to the naphtha cracking fraction (A) having the composition given in Table 1 and used in Exa~ple 1, and with stirring, it was treated at 25C for 2 hoursO '~he reaction mixture was then distilled, and a distillate oil having a boiling poin-t of up to 120C'20 mmHg was recovered in a yield of 97~o by weightO ~he resulting distillate oil was polymerized and post-treated in the same way as in Example 1 to afrord a hydrocarbon resin having the characteristics shown in ~able lOo 1~ C mpar~tive Example 5 ~ he procedure of Comparative Example 4 was repeated except that treatment with maleic anhydride was performed at 100C7 and the distillate oil was recovered in a yield of 91~. by weightO A hydrocarbon resin having the characteristics shown in ~able 10 was obtained.
, . . : ~ , ~:~.;39~
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_abl~ 10 (contlnued) - 36 -~xam~le clrocarbon resin ( .h.X O or ^ Hy . ~
Comparative olnt Th~rmal Example Yield P Color s~ability (CExo ) (wto/~) _~ (Gardner) (Gar-1ner) Odor Exo 1 38 131 6 10 A
Ex~ 2 39 132 6 ] 0 A
Exo 3 39 131 6 10 A
Ex. 4 39 132 6 10 A
Ex~ 5 38 132 605 11 A
CEx. 1 36 135 9 13 C
@xo 6 37 131 7 11 B
Ex. 7 38 130 6 10 A
Ex 8 3~ 132 6 ~ 5 1005 A-B
CEx. 2 37 130 9 13~ B
CEx. 3 37 134 ~ 5 1205 Exo 9 43 95 5~5 905 A
Ex 10 38 131 6 10 A
Ex7 11 37 130 6 10~5 A
Ex~ 12 39 132 6 10 A
: Ex. 13 38 130 6 IO A
Ex~ 14 3B 131 60 S lOo 5 A
:
CEx. 4 39 132 805 12.5 B ~ :
C~X o 5 37 130 705 12 B ;:
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, . -,:: , ':: , / - , ' . ' ' , ' : '. ' .,, . . ': .,: ' ' . ',' . : ~ ' . ', ' : . ' . , ,:
1~9k~
Maleic acid (0.5~,', by weight; correspondin~; to 2.0 molar equivalents based on the cycl.open-tadienes) was added to the main fraction (B) having the composition shown in 'rable 3 and obtained in ~xarnple 1, and the frac-tion was -treated at 40C for 30 minutes with stirrin~.
'rhe -treated fraction was polymerized an~ post--treated in the same way as in Exarr~le 1 to afford a hydrocarbon resin having -the charac-teristics sho~m in 'r~ble 11 Examples 16 o `'i ~ L~r~ m~le 6 Each of the main fr~ctions (~) to (G) having, -the composi-tions shown in 'rables 4 to 8 respecti~ely was treated with maleic acid under the conditlons indicated in Table 11, and then polymerized ~nd post-treated in the same way as in Example 1~ Thus, hydrocarbon resins having the characteristics shown in Table 11 were obtainedO
h~arl~les 20 to 22 an ~ Ex~~ es Z__nd 8 'rhe main fraction (E) havin~ the con1posi-tion shown in 'rable 6 and used in ~xample 4 was -treated under the conditions shown in 'rable 11, and then polymerized and pos-t-treated in the same way as in Example 14 ',rhus, hydxocarbon resins havin~ the characteristics shown in 'rable 11 were obtainedG
Example 23 'rhe main fraction having -the composition shown in 'rable 3 ancl obtained in Example 1 was treated with maleic acid in the same way as in Example 14 A mixture of 80 parts by weight of -the treated fraction cmd 20 parts by weight of the naphtha crac]cingr fr,action havin~ a boiling . ~ ~. . :, - : ,, .. .. ,: :~ :. ., : :: :
_ ran~e of -20C -to ~20C descri.bed in 'rable 9 (contrlinin~
93.6~ by wei~ht of polymerizable cornponerlts) was poly-merized in -the presence of 0O5 part by weight of a boron -trifluoride/phenol complex ca-talys-t and ~ost--treated in the same way as in Example lo A hy~roc~rbon resin was obtained which had the characteristics described in Table 11..
Examples 24 and 25 'rhe main ~rac-tion havin~ the composition described in 'rable 3 and obtained in ,Example 1 was treated with each of the a~-unsaturated carboxyli,c acids shown in 'rable 11, and polymerized and post-treated in the same way as in ~xample 1~ 'rhus, hydrocarbon resins having the characteristics shown in 'rable 11 were ob-tained.
Examples 26 and 27 'rhe main fraction (B) havin~ -the composition shown in 'rable 3 and obtained in Example 1 was -treated under the conditions shown in 'rable 11, and polymerized and post-treated in the same way as in ~xample lo '~hus, hydrocarbon resins having the characteris-tics shown in Table 11 were obtained.
~l3 ~9 , a) 0~
L~
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P~ I ~ O ~ r-l r~ N ,1 O O ,1rl rl r~r--l O ~ rl h f~ ,J J =~ J ~ J ~ ~ J ~ J
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rl ~r~ ~r~
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tD tU ~1 0 h `--1, h o ~ CH
h I U~ \ O,r-l N C~CO
rl h r-l ~r~lrlr-lr-lr-l ~D N N N
Q~ t~ ~1, o o ~3 3 ~ tD ~ ~C~ o o X o o ~ r~ X
~u X ~ ~ tu ~ ~ X X X Xr~3 X X X r~
X r l o ~, X vr~r~ lrTlr~l V~r~C13 C13 V V
-- ~0 --O O O U~ r~
~ ~ 1~\
O O O O O
O O O O O
t~
O O O O O
O
rt ~ a~
.~r~
t~
~D 0C~ ~ r-l r~ c) 0 ~tJ
r~t~ 0 t~ r~l t~
~r-l rd O ~1 tD ~-J t~ rdP:,~D = (D
0 '1-~
0 r ~ ~ V t~ 0 0 0 ~I t~
t~ '' O ~ o ~ O O
O O O O O
,t~ :
o J ~ J ~ ~ tD
r~
'~ ;
~D
~1 ~1 ~1 ~I rl h rd r~l ~ ~0 .~ ..
~1 t~ O~) CO ~0 CO O~) ~ ' _~
a) ~ ~ ~ ~D C' r~ 0~
F~ ~ '~
o o ~ ~ r.
X ~ ~
. , , ,.:: .' .. .: .. . ,. " ` :; ;; ~ ` " ' , ": : -`' ::, . !' -- L~l --Table 11 ~ con tinu~?d ) ( xamp) 1e ~dro_rb n_e ~3in Comparative Softening ~hermal !~xample Yie] d P in Color ~; tabil i-t~
(CExo ) _ ~ (C~ Jar~ner) (Gardne.r~Odor Ex. 15 37 133 605 10.5 Exo 16 39 130 6 10 A
Exo 17 38 131 6 10 A
Ex. 18 37 130 60r~ 11 A
Ex. 19 35 130 7 11 A
CEx. 6 31 ].31 10 lL~ C
Ex. 20 37 132 7 11 :B
E~X.21 37 ] 3 6. 5 lOo 5 A
Ex. 22 36 130 7 11 A-B
C~x. 7 37 l~il 9 lL~ B
CEx~ 8 35 132 805 12.5 B
Ex. 23 41 96 5~,5 9.c7 h~x.2L~ 36 132 6 10 A
:Ex. 25 35 130 60 5 lOo 5 A
Exo 26 37 130 6 10 A
Ex~ 27 38 131 7 l O o 5 A
: : " ' ' : ' ` ~ ,,, ',: . :: ' ' : , i, . "
_ L~
Example 28 Malei:mi~le (O~L~/C by weight; correspondin~ to 1.5 molar equivalen-ts based on cyclopentadienes) was added to the main frcqetion (B) havin~ the composltion shown in Table 3 and obtained in hx~mple 1, and the fraetion was t,reated a-t 40G for 30 minutes with stirring. The treated fraction was polyrlerized ancl pc)st-treated in the same way as in Example 1 -to afford a hydroearbon resin having the eharacteristics shown in Table 12 10 ~
The naphtha craeking fraction (A) havin~ the eomposition shown in Table l and usecl in Example l was distilled under the same co.nditions as in Example l exeept that the distillin~ conditions were ehanged as shown in ~able 12. ~rhus, the main fraetions (C), (~), (F) and (G) having -the compositions shown in Tables 4 and 6 to 8 respectivel~J were obtained. These main frae-tions were treated with maleinimide uncler -the conditions shown in ~able 12, and then polymerized and post-treated in -the 2(? same way as in Example 1 to afford hydrocarbon resins having th~ characteristics shown in Table 12 Examples_~2 and 33 The main fraction (~) havin~ the eomposition shown in Table 3 and used in Exa~ple l was treated under the concliti~ns shown in Table 12, and polymerized and post-treated in the same way as in Example l to afford h~drocarbon resins having the characteristics shown in Table 12r .
'~ ~ 3 _ /~3 _ ~ he main fraction (B) having the composition shown in ~able 3 and obtained in Example 1 was treated with each of the uns~turated polar compounds described ~n Table 12, and polyrqerized and post-treated in the sarne way as in Example 1 to afford hydrocarbon resins having the characteris-tics shown in ~able 12.
Examples_37 and 38 ~ he main fraction (B) having the composition shown in ~able ~ and obtained in Exarnple 1 was treated with r~al~imide under -the conditions shown in ~able 12, and polymerized and post--treated in the .sarne way as in Example 1 to afford hydrocarbon resins havin~; the charac-teristics shown in ~able 120 ~4~
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, I ~1 ^
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~ 07 r~ r~ r~ r~ r~ r~ r~ r~ r~ r~ r~ r~
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, ~ ~ . . O ~ O O ~ .
O tlS ~J ~J \J ~J ~J
P
tl .~ r~
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E~ ~r~ O ~1 q) ~ ~ ~a r' ~ ~D r ~ ~ ~J ~
~ d rl r ~ O
(~J~ ,~ ~
r-l~ O ~ ~a 0 ta f-l ,~
~ D ~ -- -- = -- -- -- ~ C~
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I I ~
do 0 `` ~u Lr~ O
~rl O d ~ ~ oLr~ o ~ ~ N r~
q~ ~ p~ a) r~ O ~ ~ ~o O ~ ~ O O O r~
0 U~
h 0 ~rl 0 r~ ,D ~ Lr` N~r~ Lr`~Lr LO. Lr~ Lr Ll` L
~7 0 0 ~ o ~ ~ O ~ ~ ~ o o o O 1~1 I ~ O ~ r~ r-l O O ~i r-l r~ r-l r-l Q) p~r~ ~~:t J ~ ~ ~ ~ ~ t r~
o sl o 3) o 1 V ~ ~l El C) r~ a d 0 bD d ~rl Q) ~ ~rl ~rl ~ r--I O (~ ~ O r1 ~I r-l r-lr-l r-l r-l C) O ,~ ~(~1 ~Ir~l r~ N ~ 1 01 r~
~D 0 h ~3 ~rl ~ ~3: O
~ r~ ~a) a) 4~ o r-l~rl 1I h O~Q ~ ..
rl ~ ~
rl ~r ~ r~ ) 0~ r-l 0 ~ ~ 0 i~ Fl rl ~
~rl o O ~ O~CO Lr~ ~D Lr~ 1~ CO COCO CO C() ) CO
1~ c~ c.) O r-l r~ C) ~ r-l h ~1 ~rl O a~ 4~ 0 h`
o~q~ I
h I C~ 0~\ 0 r-l (~ C~l ~ ~ Lt~~) C~ 00 ~ O ~ ~ C~ ~ ~N~ ro ~^, ~ ~ ~ r~ N~
r-l h rl~
o jr~ O O O ~C ~ O O
$ -r ~ v ra ~ ) ~ ~ rT~
-- L~5 _ :[~ble 12 ( con tinuecl ) . ~ _ ( Exo ) or ~ roc~:rbon re~in __ Compara-tive Soft~nlng 'rhermal ~xampl e Yi~ld P int Co lo r stabil ity (C5~xo ) _ ~ ~ ~ 5~r) ~ Odor Exo 2~3 37 130 6 10 A
~xO 29 3~ 1 31 6 10 1~
Exo 30 37 131 60 5 10. 5 A
EY. 31 36 130 7 11 A
CExo 9 35 133 9 13. r~ C
Exo 32 38 132 6 10 A
Exo 33 37 130 6~ 5 10. 5 A
Ex~ 3L~ 36 131 7 11 A
Ex~ 35 37 132 6 10.. 5 A
Exo 36 39 130 605 10.5 A
Ex. 37 36 130 6 10 A
5xo 38 37 132 60 5 10 . 5 A
. . .
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a hydrocarbon resin having im-proved color and thermal stability, which comprises treating a petroleum cracking or reforming fraction containing cationically polymerizable hydrocarbons and not more than 0.7% by weight, based on the fraction, of cyclopentadienes and having a boiling range of from 140°C to 280°C, with 0.8 to 3.0 moles, per mole of the cyclopentadienes, of a dienophile compound having a carbon-to-carbon double bond and a carbonyl or cyano group adjacent to the double bond at a temperature of from room temperature to less than 50°C; and then polymerizing the treated petroleum fraction in the presence of a polymerization catalyst.
2. The process of claim 1 wherein said petroleum fraction is prepared by removing cyclopentadienes from a petroleum cracking and reforming fraction containing cationically polymerizable hydro-carbons and at least about 1% by weight, based on the fraction, of the cyclopentadienes, and having a boiling range of from 140°C to 280°C until the content of the cyclopentadienes drcreases to not more than 0.7% by weight based on the fraction.
3. The process of claim 2 wherein said removal of the cyclopentadienes is carried out by fractional distillation.
4. The process of claim 1 wherein said petroleum fraction contains 0.01 to 0.5% by weight, based on the fraction, of the cyclopentadienes.
5. The process of claim 1 wherein said dienophile compound is selected from the group consisting of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides, esters, amides and imides thereof, .alpha.,.beta.-unsaturated nitriles, .alpha.,.beta.-unsaturated adehydes and quinones.
6. The process of claim 1 wherein said dienophile compound is an .alpha.,.beta.-unsaturated dicarboxylic acid anhydride.
7. The process of claim 6 wherein said .alpha.,.beta.-unsaturated dicarboxylic acid anhydride is selected from aliphatic or alicyclic .alpha.,.beta.-unsaturated dicarboxylic acid anhydrides containing up to 15 carbon atoms.
8. The process of claim 6 wherein said .alpha.,.beta.-unsaturated di-carboxylic acid anhydride is a member selected from the group con-sisting of maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride.
9. The process of claim 6 wherein said .alpha.,.beta.-unsaturated di-carboxylic acid anhydride is maleic anhydride.
10. The process of claim 1 wherein the amount of said dienophile compound is 2 to 2.5 moles per mole of the cyclopentad-ienes.
11. The process of claim 1 wherein said treatment of the petroleum fraction is carried out for at least 30 seconds.
12. The process of claim 11 wherein said treatment of the petroleum fraction is carried out for 1 minute to 1 hour.
13. The process of claim 1 wherein the petroleum fraction contains at least 20% by weight, based on the fraction, of the cationically polymerizable hydrocarbons.
14. The process of claim 1 wherein said polymerization is carried out at a temperature of from -30°C to +80°C in the presence of a Friedel-Crafts catalyst.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP155,578/77 | 1977-12-26 | ||
| JP15557877A JPS5937002B2 (en) | 1977-12-26 | 1977-12-26 | Method for producing hydrocarbon resin |
| JP10382878A JPS5531827A (en) | 1978-08-28 | 1978-08-28 | Preparation of hydrocarbon resin |
| JP10382978A JPS5531828A (en) | 1978-08-28 | 1978-08-28 | Preparation of hydrocarbon resin |
| JP103,829/78 | 1978-08-28 | ||
| JP103,828/78 | 1978-08-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134994A true CA1134994A (en) | 1982-11-02 |
Family
ID=27310086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000318616A Expired CA1134994A (en) | 1977-12-26 | 1978-12-27 | Process for producing hydrocarbon resins having improved color and thermal stability |
Country Status (6)
| Country | Link |
|---|---|
| CA (1) | CA1134994A (en) |
| DE (1) | DE2856335C2 (en) |
| FR (1) | FR2412573A1 (en) |
| GB (1) | GB2012287B (en) |
| IT (1) | IT1101749B (en) |
| NL (1) | NL7812514A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036999C (en) * | 1994-06-10 | 1998-01-14 | 兰州大学 | Process for producing solid petroleum resin with light colour |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB743886A (en) * | 1952-10-01 | 1956-01-25 | Exxon Research Engineering Co | Improvements in or relating to process for preparing petroleum resins |
| FR1088401A (en) * | 1952-10-31 | 1955-03-07 | Standard Oil Dev Co | Manufacture of petroleum resins |
| DE1091330B (en) * | 1956-07-19 | 1960-10-20 | Exxon Research Engineering Co | Process for the production of resins by polymerizing steam-cracked petroleum fractions |
| DE1112633B (en) * | 1959-11-04 | 1961-08-10 | Exxon Research Engineering Co | Process for the production of petroleum resins |
| FR1247502A (en) * | 1959-11-16 | 1960-12-02 | Exxon Research Engineering Co | Process for preparing petroleum resins from distillates resulting from steam cracking operations |
| GB1043406A (en) * | 1962-05-23 | 1966-09-21 | Nippon Oil Co Ltd | The preparation of petroleum resins |
| FR1378046A (en) * | 1963-06-04 | 1964-11-13 | Aquitaine Petrole | Preparation of resins from petroleum products |
| DE1645507A1 (en) * | 1967-01-23 | 1970-08-06 | Masaki Takahara | Process for the production of naphtha resins |
| US3855187A (en) * | 1970-08-12 | 1974-12-17 | Exxon Research Engineering Co | Method for preparing resin feed |
| US4105843A (en) * | 1976-04-15 | 1978-08-08 | Mitsui Petrochemical Industries Ltd. | Process for producing hydrocarbon resins having improved color and thermal stability by heat treatment with an α,βunsaturated anhydride |
-
1978
- 1978-12-22 GB GB7849855A patent/GB2012287B/en not_active Expired
- 1978-12-22 NL NL7812514A patent/NL7812514A/en not_active Application Discontinuation
- 1978-12-26 FR FR7836306A patent/FR2412573A1/en active Granted
- 1978-12-27 DE DE2856335A patent/DE2856335C2/en not_active Expired
- 1978-12-27 CA CA000318616A patent/CA1134994A/en not_active Expired
- 1978-12-27 IT IT31333/78A patent/IT1101749B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FR2412573B1 (en) | 1984-02-24 |
| DE2856335C2 (en) | 1983-01-20 |
| NL7812514A (en) | 1979-06-28 |
| IT1101749B (en) | 1985-10-07 |
| DE2856335A1 (en) | 1979-06-28 |
| GB2012287B (en) | 1982-07-07 |
| FR2412573A1 (en) | 1979-07-20 |
| IT7831333A0 (en) | 1978-12-27 |
| GB2012287A (en) | 1979-07-25 |
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