PETROLEUM RESINS AND THEIR PREPARATION

Abstract: Petroleum resins containing copolymerised limonene have improved softening points.

Description: The present invention relates to new improved petroleum resins and a process for their production. In particular the invention relates to resins suitable as tackifiers for elastomers and useful in hot melt formulations. Petroleum resins obtained by the polymerisation of C5 dienes such as pentadiene 1,3 and/or isoprene are well known as is their use as tacktfiers for elastomers and as components in hot melt formulations. It is known that SIS block copolymers (block styrene-isoprene copolymers such as Shell Cariflex TR 1107) can be tackified by petroleum resins of narrow molecular weight distribution produced by controlling the polymerisation conditions with branched reactive olefins, substi- tuted aromatics or tertiary alkyl halides, see for example our prior patent applications 31878175 and 33705/75. These previously described petroleum resins of narrow molecular weight distribution tackify oil extended random SBR (styrene-butadiene) copolymers and provide very good tackifying properties for the SIS block copolymers. However, they also have a low cohesive strength in pressure sensitive adhesives based on natural rubber. They do not however tackify oil free SBR elastomers of either random or block thermoplastic nature (e.g. SBS block copolymers). Other petroleum feed additives for example dicyclopentadiene, methyl cyclopentadiene dimers or thermal polymers obtained from cvclodiene comer, rlch streams as described in our Patent Specification U.K. l,4S6,211 are known as a means of making resins of high softening point. However the resins produced in this way have degradated resin Gardner colour and wax compatability. Moreover even if they increase the cohesive strength of pressure sensitive adhesives based on natural rubbers and slightly tackify SIS block copolymers they do not tackifv other SBR copolymers. One disadvantage of these earlier techniques is that the presence of the molecular weight controlling additive tends to reduce the softening point of the resin thus rendering it unsuitable for certain pressure sensitive adhesives particularly those where cohesive strength (shear adhesion) is important. It has been proposed to overcome this problem by carrying out the polymerisation in a paraffinic solvent which is not entirely satisfactory and increases costs and reduces plant capacity. In our copending application No. 97941/78 we suggest that these disadvantages may be overcome by the copolymerisation of carene with the petroleum resin feed. We have now found that similar benefits may be obtained if limonene is used instead of carene. U.S. 3,466,267 patent describes the manufacture of resins by spiking a concentrate of a mixture of limonene and carvestrene with 10 to 50 percent by weight of piperylene. According to this patent if less than 10 percent by weight of piperylene is used the resin has an undesirably low softening point whilst if more than 50 wt.% by weight of the resin is employed softening points are lowered and the resin yields from the polymerisation are uneconomically low, the ratio of limonene to carvestrene varies from 1:0.66 to about 1:10. We have now found that a satisfactorily high resin softening point (70 to 1600C and preferably 100 to 1300C) resin is achieved when more than 50 Wt./° by weight of piperylene is combined with limonene without any need for carvestrene addition and that the resin yield is acceptable and has good colour stability. We have also found that the resin quality may be further improved when the limonene and piperylene or other C5 conjugated diolefins such as isoprene are combined with branched olefins as transfer agents for resin molecular weight control. The present invention therefore provides a process which comprises copolymerising using a vriedel Crafts catalyst (1) a petroleum resin feed comprising C5 olefins and diolefins, C6 olefins and diolefins or a mixture of C5 and C6 olefins and diolefins, said feed being obtained from the cracking of petroleum feedstock and (2) limonene in the absence of carvestrene. The present invention further provides a process which comprises copoiymerising using a Friedel Crafts catalyst (1) 2 petroleum resin feed comprising C olefines and diolefins, C6 olefins and diolefins or a mixture of C5 and C6 olefins and diolefins, said feed being obtained from the cracking of petroleum feedstocks and (2) limonene the petroleum resin feed comprising at least 40 wt.% of the combined weight of the resin feed and limonene. The present invention further provides the petroleum resin prepared according to the processes described above. The C or C6 diolefin and olefin containing feed used in our process may be obtained from the cracking of petroleum feedstock: Such feedstocks include naphthas, kerosene, gas oil and vacuum gas oil. These feedstocks usually boil in a range of from 20 0C to 4500C. The petroleum feedstock is cracked, preferably in the presence of steam, and the recommended cracking temperature is between 5000 and 87O0C. The product which contains unsaturated hydrocarbons usually boiling in the range of 200 to 2400C, preferably 200 to 130QC, usVally is thereafter subjected to fractionation to remove 2 to C4 light ends. The feedstock may thereafter be subjected to thermal soaking at a temper- ature of between 1000C and 1600C, preferably 1200 t 1400C, e.g. about 1300C. The thermal soaking preferably takes 0.5 to to & hours, e.g. 0.5 to 1 hour. Low temperatures are preferred in order to limit the cyclic diene (Cyclopentadiene and Methylcyclopentadiene) co-dimerization with C5 linear conjugated dienes (isoprene and pentadienes 1,3 cis- and trans-). After fractionation and if curried out thermal soaking, the feedstock is preferably subjected to distillation to remove cyclic conjugated diolefins which are gel precursors (cyclopentadiene and methylcyclopentadiene being removed as dimers). After distillation one obtains an overhead naphtha which usually boils in the range from 25 to 1100C, e.g. 25 to 80 C, the best results being achieved with a 25-700C cut. This overhead naphtha comprises mainly C5 diolefins such as isoprene and 1,3 cis- and trans- pentadienes, C5 to C6 monoolefins and aromatics for example benzene. In general the overhead naphthas have the following compostiors: % by weight Total paraffins 1.0 to 41.5 Total diolefins 35.5 to 14.5 Total olefins 33.5 to 13.0 Total aromatics 30.0 to 31.0 Isoprene 16.5 to O Pentadiene 1,3 15.5 to 4.5 Cyclopentadiene 1.0 to 2.i the exact composition depending on the nature of the petroleum feedstock which is subjected to steam cracking. The feed could be significantly isoprene free provided this com pound is previously recovered through any conventional extraction process such as extractive distillation or azeotropic distillation. In such cases the properties of the resins produced are better than those obtained with isoprene-containing feeds. Moreover, depending on the final boiling point of the feed cut the feedstock could be substantially free of benzene. Cyclopentene contents are generally.below 3 wit.. If thermal soaking has been carried out the cyclodiene dimmers which are produced are generally not included in the feed to be polymerised, because they are detrimental to the specific properties of the resins. However, if required for special applications they can be left in the resin feed, the distillation step previously mentioned being carried out before the thermal soaking step. In our preferred process 50.1 to 99 wt.% more preferably 50.1 to 85 wt.% of piperylene and/or isoprene based on the combined weight of C5 conjugated diolefins and limonene should be used. The limonene used may be a concentrate obtained from gum or crude sulphate turpentine by rectification, such a concentrate generally contains from 50 to 85 çt.7 of limonene. Two samples of a typical stream were found to contain: d- Pinene 0.2 t.% 0.1 wt.% Camphene 0.1 wt.% pinene 0.1 wt.% S- 3 Carene 6.9 wt.% 5.0 wt.% g- Terpinene 3.0 wt.% 3.3 wt.% p - Cymene 5.5 wt.% 5.1 wt.% Limonene 74.3 wt.% 78.8 wt.% - - Terpinene 1.1 wt.% 1.1 wt.% Terpinolene 1.5 3.2 wt.% We found that the use of limonene narrows the molecular weight distribution of the resin at the same time increasing the softening point of the resin. Other unsaturated cyclic monomers may also be included in the copolymerisation. For example one or more of norbornene, vinyl-norbornene, dicyclopentadiene, methyl cyclopentadiene dimer, vinyl cyclohexane, tetrahydroindene and other terpenes such as pinene may be included. The techniques of the present invention are equally applicable to resin production process which employ other agents to narrow the molecular weight distribution such as the branched reactive olefins of our application 33705/75 to achieve extremely narrow distribution without reduction of softening point. Similarly the limonene may be incorporated into systems which uses a solvent to keep up softening points or the need for the solvent may be obviated by the use of the limonene. The ratios of the amount of limonene and petroleum resin feed to the amount of branched olefine used may be varied to obtain resins of any desired softening point within the range 600C to 1400C. Where branched olefins are used a broad (e.g. C5-C8) fraction of our U.K. application 33705/75 may be used. The preferred branched olefins are oligomers of propylene and butylenes obtained with phosphoric acid catalysts (called U.O.P. olefins) or from a Fluid Catalytic Cracker (F.C.C. olefins) or from stream cracking. Typical compositions are shown in Tables l and 2. Other chain transfer agents such as the alkyl halides of our U.K. application 31878/75 may also be used. Similarly oxygenated transfer agents may be used such as mono-, dior tri-substituted phenols the substituent being a C1 to C30 or preferably C1 to Ss s,raishb ai or branched chain hydrocarbyl group e.g. methyl, ethyl, propyl, butyl, amyl or their secondary or tertuary isomers, (e.g. 2,6 ditertiary-butyl-4-methyl phenol), alcohols, esters, dialkyl ethers, alkaryl ethers, the alkyl group in the ether-being C1 to C30, preferably C1 to C6 straight or branched chain hydrocarbyl group e.g. methyl, ethyl, amyl or their secondary or tertiary isomers, (e.g. anisole), organic acids or anhydrides (e.g. maleic anhydride). When used the oxygenated transfer agent should preferably have a boiling point lower than 300 C. If low boiling point compounds e.g. diethyl ether, are used the polymerisation temperature and pressure should be carefully chosen so as to maintain them in the liquid state. The most efficient compounds in the presence of AIC3 are dialkyl ethers or an alkaryl ether, such as anisole since they act as solvent for the catalysts. Since the polymerisation is usually carried out between 30 to 800C, any such additive should be of adequate boiling point in order to maintain it in the liquid phase. The amount of oxygenated compound used as transfer agent can vary from 0.1 to 5 wt.%. preferably 0.5 to 2 wt.%, based on the weight of petroleum resin feed. They are generally less attractive than branched chain reactive aliphatic olefins previously described. In addition C8-C10 polymerisable unsaturated aromatic monomers such as styrene, -methyl styrene, vinyl toluene, indene, methyl indene (see U.S. 4,078,132) may also be included in the polymerisation mixture which we find improves the compatibility of resin especaially for use in hot melt applications. Chloro and polar styrene (e.g. methoxy styrene) derivatives are other potentially attractive monomers. The resin feed and the limonene are mixed and polymerised using a Friedel Crafts catalyst, for example aluminium chloride, aluminium bromide or a liquid aluminium chloride/hydrochloric acid alkyl substituted aromatic hydrocarbon complex, the aromatic hydrocarbon being for example o-xylene, mesitylene, ethyl benzene, isopropyl benzene and other short or long chain alkyl benzenes. The alkyl chain can be linear or branched and can vary from 1 to 30 carbon atoms. The atomatic hydrocarbon may be mono- or polyalkylated for example diisopropyl benzene, para tertiary butyl benzene and similar compounds. Acid liquid AlCl3 sludges obtained as by-products during the alkylation of benzene or any other substituted aromatics (e.g. toluene or xylenes) with branched chain olefins can be direcly used as catalyst for the above described polymerisation process. The branched chain olefins which are for example, produced via the boron trifluoride oligomerisation of propylene and/or butylene and fractionation, e.g. C12 olefins or C24 olefines, can be alkylated with aromatics producing in situ sludge. As an example the acidic sludge available from a dodecylbenzene plant provided similar results to the preformed o-xylene AlC13/ HC1 liquid complex. These liquid complexes are slightly more efficient than AlCl3 powder at equivalent concentration and provide slightly higher resin yields and lower resin molecular weight. Therefore, the amount of limonene required for narrowing the resin molecular weight is significantly reduced. Moreover when by-product sludges are available in plant site, the catalyst cost is reduced and such a process is particularly attractive although powdered AlCl3 results in resin having better Gardner colour. The Friedel Crafts catalysts may also be dissolved in polar solvents, for example AlCl3 or AlBr3 may be dissolved in ethers such as diethyl ether or anisove, acetates such as ethyl acetate, nitrobenzene, phenols, anhydrides and fatty acids. These catalyst solutions are however less preferred being generally less active mixtures of those polar solvents and the aromatic or chlorinated solvents may also be used. In the polymerisation process the amount of catalyst may vary from 0.25 to 3.0 wt.% preferably 0.5 to 1.5 wt.% based on the weight of the mixture to be polymerised. The optimum concentration depends on the nature of the solvent which affects the solubility of the catalyst as well as on the stirring efficiency inside the polymerisation reactor. High catalyst concentration reduces the resin molecular weight distribution and therefore limits the amount of limonene required for controlling the resin molecular weight. Other Friedel Crafts catalysts like titanium tri- or tetrachloride, tin tetrachloride, boron trifluoride, boron trifluoride complexes with organic ethers, phenols or acids can also be used but they lead to rather low resin yields and large quantities of liquid oligomers of low value are obtained. Even though these oily oligomers can be upgraded as reactive plasticizer or liquid plasticizer such catalysts are not recommended. Other possible catalysts can be acidic clays. Usual polymerisation temperatures are between -200C and 1000C, preferably between 300 and 800C. After polymerisation the residual catalyst may be removed by for example, washing with aqueous solution of alkali, ammonia or sodium carbonate, or by the addition of an alcohol such as methanol and subsequent filtration. The final resin may be stripped of unreacted hydrocarbons ("raf- finate" rich in benzene and/or paraffins/unreactive olefins) and low molecular weight oil oligomers by stream stripping or vacuum distillation. The finished product is a substantially non-aromatic unsaturated thermoplastic hydrocarbon resin. It usually has a softening point of from 700C to 1600C, preferably 1000 to 130 C. The resins obtained can be used in many applications which require low viscostiy, good flexibility and elongation before or especially after chemical modification with polar compounds such as phenols, unsaturated anhydrides such as maleic anhydride or unsaturated acids (e.g. fumaric acid). These resins are designçd for a wide range of end uses and applications. They can be applied to paper, metal, thermoplastic films (cellophane, polyesters, PVC, woven or non woven fabrics, glass etc. ad for boning such materials together). Typical application are hot melts, carpet backing, coating with drying oil formulations, book binding, paper sizing or in any applications involving natural or synthetic resins and/or rubbers such as caulks, sealants or rubber tackification. More especially they may be used as tackifiers with natural rubber or synthetic rubbers such as polyisoprene. EPDM, butyl, chorobutyl, bromobutyl, neoprene and block copolymers for example styrene/isoprene rubber (Shell Cariflex TR 1107) mixtures of such rubbers. Even though these resins are significantly non-aromatic they provide outstanding tackiness with such elastomers and high resin/rubber ratio can be used to reducing the adhesive formulation cost (the resin being significantly cheaper than the block thermoplastic styrene/isoprene/ styrene rubber). Other applications involving such resin properties are pressure sensitive adhesives, hot melt adhesives, low temperature adhesives, label adhesives, latex adhesives, surgical tapes and masking tapes where they may be blended with polymers such as ethylene/vinyl acetate copolymers optionally blended with wax. Thus, hot melt adhesives and latex adhesives can be prepared from styrene - isoprene block copolymers and a tackifying resin. The low softening point aliphatic petroleum resins are a replacement for aromatic resins or resin and terpene derivatives. The present invention is illustrated but in no way limited by reference to the following examples. Example 1 The limonene rich stream described above, a piperylene rich stream comprising: Pentadiene 1:3 Trans 48.5 wt.% Pentadiene 1:3 Cis 23.6 wt.% Cyclopentene 17.5 wt.% Cyclopentane ' 8.1 wt.% Others (Paraffins/olefins etc) 2.3 wt.% and/or a fluid catalytic cracker olefine stream of Final Boiling Point 100 C containing: 33.90 wt.% Paraffins 0.33 wt.% diolefines 58.40 wt.% olefins 0.11 wt.% aromatics Total C4 17.15 wt.% were fed to a 2 litre glass reactor in the ratios given in Table 1 below. The reactor was fitted with a mechanical stirrer, a cooler and catalyst injection device. 1 wt.% of powdered AlCl3 as catalyst based on the total weight of the feed was injected into the reactor which was then held at 500C for 90 minutes. The solvent used contained: 99.44 wt.% paraffins 0.50 wt.% aromatics 0.06 wt. unknown and contained 10 parts per million of sulphur. The properties of the resins obtained are also given in Table 3. Example 2 The effect of the presence of both limonene and fluid catalytic cracked olefins on the softening point and the molecular weight distribution with and without the paraffinic solvent was assessed using the reactor used in Example 1. The pentadiene 1:3 feed consisted of: Pentadiene 1:3 Trans 42.7 wt.% Pentadiene 1:3 Cis 24.2 wt.X Cyclopentene 17.5 wt.% Cyclopentane 8.5 wt.% Others 7.1 wt.% and the polymerisation conditions were as in Example 1. The results are shown in the following Table 4, together with the properties of the products obtained (same test methods as in Example 1). Example 3 For comparison purpose the effect of Limonene andA -3 Carene are shown respectively in Table 5 and 6. The pentadiene 1,3 feed composition and the polymerisation conditions were those of Examples 1 and 2. Table 6 shows that the resins produced according to the present invention exhibit excellent tackifying properties for both natural and thermoplastic block copolymers such as Shell Cariflex (Registered Trade Mark) TR 1107. The composition of A -3 Carene is shorn in Table 7. Example 4 In this example the piperylene rich stream is replaced by a conventional C5 petroleum resin feed containing both isoprene and piperylene (composition described in Table 8) and the relative effect of spiking such a feed with Limonene is compared with those of commerci- ally available streams like dipentene, d and k -Pinene, (composition shown in Table 9). Resins properties are described in Table 10. Since B-pinene is the main component in the manufacturing process of polyterpene resins its use is shown for comparative purpose. Its impact on resin softening point is very pronounced but it leads to higher molecular weight than limonene and Carene. TABLE 1 Composition of C5 - C8 U.O.P. Olefin Additives Gas Chromatography Analysis (after hydrogenation) < C5' 3.39 12.67 11.03 C5's: 4.73 6.94 12.34 C6's: 25.70 37.61 32.55 C7's: 24.78 29.71 20,60 C8's: 35.50 12.48 23.02 Cg's 0.78 0.78 0.41 C9 's and higher 4.34 0.46 REID Vapor Pressure (ASTM d 323) at 20 C 0.39 bar 0.55 bar 0.57 bar at 33 C 0.75 bar 1.08 1.07 Bromine number Br/100 g 125 84 74 Sulfur (ppm) 6 10 5 Mercaptans (ppm) 1 TABLE l(Cont'd) Ultra-Violet Flouresence Indicator Analysis Olefins vol.% 80 56 40 Paraffins vol.% 20 44 60 Paraffins Content (wt.%) After olefin absorption with mercuric perchlorate 43.7 52.3 TABLE 2 Gas Chromatographic Analysis of Fluid Catalytic Cracked Olefin Fraction Overall Composition (wt.%) Total Paraffins 33.90 35 07 35.33 Total Diolefins 0.33 0.32 0.90 Total Olefins 58.40 56.43 59.13 Total Aromatics 0.11 0.50 2.31 Unidentified 7.26 7.68 2.33 Specified gravity at 15 C 0.6457 0.6614 0.6801 Olefin Fraction Boiling Range C 25-50 25-70 25-100 c4ls 16.09 11.04 7.09 C5,s 38.25 28.33 19.78 C6 5 5.37 20.18 32.01 TABLE 3 Feed Composition Limonene Concentrate (wt.%) 40 33 26 33 Solvent (wt.%) 30 35 35 17 Benzene (wt.%) 30 Pentadiene 1: :3 concentrate (wt.%) 32 39 32 Fluid cat cracker olefine (wt.%) - - 18 Limonene in Total Feed (wt.%) 29.7 24.1 19.3 24.5 Pentadiene in Total Feed (wt.%) 23.0 28.1 23.0 Pentadiene on combined Pentadiene + Limonene (based on exact concentration in feed) 4 & 8 59.3 LS.4 Product Resin (wt.%) 6.2 43.6 42.6 47.8 Liquid Oligomers (wt.%) 13.2 8.6 5.6 11.6 Unreacted Compounds (wt.%) 80.6 47.8 51.8 40.6 Product Properties Resin softening point ASTM E-28 (OC) 115 144 146 124 Gardner Colour ASTM D-1544 11 2+ 3- 3 Heat stability (colour after 16 hrs at 1500C) 13.5 10 7 Wax cloud point OC Wax!resin/EVA* 50:25:25 70 250+ 250+ Molecular wt. G.P.C. Mn 1735 1370 Mw 10920 4330 Mw/Mn 6.23 3.16 Pressure Sensitive Adhesive Properties (Resin: Natural Rubber = 50:50 wt.) 1800 Peel Strength (PSTC-1**) llbs/inch) 390 2.6 2.1 2.8 TABLE 3 (Cont'd) Polyken Tack (grams) ASTM D-2979 1100 300 300 1050 Tack Rolling Ball (cm) PSTC-S 2 30+ 30+ 4.5 1780 Holding Power PSTC-7 (hours to failure) 27 500 500 131 * Ethylene/vinyl Acetate copolymer containing 28 wt. vinyl acetate and or Melt Index 12-18 * Wax having a melting point of 65 C. ** Pressure sensitive Tape Council Test Method. TABLE 4 Feed Composition Limonene concentrate (wt.%) - - 20 20 3?. Solvent (wt.%) 30 - - - 17 F.C.C. olefins (wt.%) 41 58 40 48 18 Pentadiene 1,3 concentrate (wt.%) 29 42 40 32 32 Limonene in Total Feed (wt.%) - - 14.9 14.9 24.3 Pentadiene in Total Feed (wt.%) 19.4 28.0 28.8 23.0 23.0 Product Resin (wt.%) 27.8 40.0 49.4 42.0 47.4 Liquid Oligomers (wt.%) 5.2 6. 11.2 15.4 11.6 Unreacted Compounds (wt.%) 67.0 53.7 39.4 36.6 40.0 Product Properties Sovto ing Point 100 93 112 113 124 Cardner Colour 4- 3+ 3.5 3.5 3 Heat Stability 14 13.5 13.5 12- 12+ Molecular Wt Mn 1350 1295 1420 1370 Mw 2990 2350 4205 4330 Mw/Mn 2.21 1.81 2.96 3.16 Wax Cloud Point C 50:25: :25 72 70 76 69 1800 Peel Strength (1b/inch) 2.1 2.2 2.3 2.3 2.8 Polyken Tack (grams) 950 870 950 1000 1050 Tack Rolling Ball (cm) 2 1 2.5 2.5 1780 Holding Power 62 27 123 53 131 TABLE 5 Comparison of Carene and Limonene Feed Composition Carene Concentrate (wt.%) 20 25 Solvent (wt.%) 40 37.5 37.5 Limonene (wt.%) - - 25 Pentadiene 1; ;3 concentrate (wt.) 20 25 25 Fluid cat cracker olefine (wt.%) 20 12.5 12.5 Carene in Total Feed (wt.%) 16.8 20.9 1.2 Limonene in Total Feed (wt.%) - - 19.7 Pentadiene in Total Feed (wt.%) 14.4 18.0 18.0 Product Resin (wt.%) 27.2 33.4 35.2 Liquid oligomers (wt.%) 10.4 11.8 10.8 Unreacted Compounds (wt.%) 62.4 54.8 54.0 Product Properties Resin softening point ASTM E-28 C 112 112 108 Gardner colour ASTM D-1544 3.5 3.5 4.5 Heat stability (colour after 16 hrs at 150 C) 12.5 11 12.5 Wax cloud point C Wax/resin/EVA* 50:25:25 68 68 68 40:40:20 86 84 80 Molecular wt. G.P.C. Mn 1190 Mw 2265 Mw/Mn 1.907 TABLE i (Cont'd) Pressure Sensitive Adhesive Properties (resin: Natural Rubber = 50:50 wt) 1800 Peel Strength (PSTC-1** llbs/inch) 2.95 3.10 2.85 Polyken Tack (grams) ASTM D-2979 1150 1300 1100 Tack Rolling Ball (cm) PSTC-6 1.5 1.5 2 1780 Holding Power PSTC-7 (hours to failure) 23 18 49 * Rthylene/vinyl Acetate copolymer containing 28 wt.% vinyl acetate and of Melt Index 12-18. * Wax having a melting point of -650C. ** Pressure sensitive Tape Council Test Method. TABLE 6 Comparison of Limonene and A -3 Carene Feed Composition Limonene concentrate (wit.) 12.5 Carene concentrate (wt.%) - 12.5 F.C.C. olefines (wit.) 51.0 51.0 Pentadiene 1,3 concentrate (wt.%) 36.5 36.5 Limonene in Total Feed (wit.) 9.8 0.9 Carene in Total Feed (wit.) 0.6 10.5 Pentadiene in Total Feed (wt.%) 24.4 24.4 Product Resin (wit.) 41.2 39.8 Liquid oligomers (wit.) 10.4 10.0 Unreacted compounds (wt.%) 48.4 60.2 Product Properties Softening Point 98 100 Gardner Colour . 4- 4 Heat Stability 14 14.5 Molecular Wt. Mn 1145 1285 Mw 2150 2400 Mw-/M 1.87 1.86 Wax Cloud Point C 50:25:25 68 < 68 40:40: :20 75 88 Pressure Sensitive Adhesive Properties (Resin/Rubber ratio 50/50 wt.%) Rubber Type NR(1) TR 1107(2) NR(1) TR 1107(2) 1800 Peel Strength lb/inch) 2.65 5.5 2.45 6.0 Polyken Tack (grams) 1100 1600 1150 1600 Tack Rolling Ball (cm) 1.5 2 1.5 1780 Holding Power 46 500 64 500+ (1) Natural Rubber 65 Mooney Viscosity (2) Shell block copolymer TR 1107 (styrene - isoprene - styrene) TABLE 7 # -3 Carene Concentrate (Typical) by Gas Chromatography t- Pinene 1.8 4- 3 Carene 83.9 c(- Terpinene 0.5 - Cymene 1.7 Limonene 7.4 Terpinolene 0.6 Unidentified Difference to 100.0 TABLE 8 Typical Composition of a Steam Cracked Petroleum Feedstock Boiling Point C (25-70) By Gas Chromatography Overall Composition Paraffins 2.1 C5 to C6 conjugated diolefins 50.0 C5 to C6 olefins 43.8 Benzene 3.4 Typical C Diolefins Isoprene 23.7 EMI22.1 <tb> Pentadiene <SEP> 1,3 <SEP> trans <SEP> 11.8 <SEP> <tb> <SEP> # <SEP> 19.7 <tb> Pentadiene <SEP> 1,3 <SEP> cis <SEP> 7.9 <tb> Cyclopentadiene 1.8 Typical C Olefins 2 Methyl butene 1 2 Methyl butene 2 Pentene 1 7.4 Cyclopentene 4.8 TABLE 9 Typical Composition of Commercial Dipentene and Terpenes Stream By Gas Chromatography Product Dipentene A Dipentene B &alpha; -Pinene ss-Pinene Dipentene Source EMI23.1 Sulfate Turpentine EMI23.2 Gum Turpentine &alpha; ; -Pinene 0.10 3.9 95.6 1.5 1.7 Camphene 6.7 2.9 1.6 0.5 6.2 Pinene 0.6 2.0 92.4 0.1 Carene 0.2 0.E 1.0 l.l i- Terpinene 7.0 6.4 18.7 p- Cymene 1.4 13.8 0.1 1.9 Limonene 41.6 29.6 0.7 22,1 t¯ Terpinene 6.5 2.2 9.7 Terpinolene 28.4 22.7 29.4 2-3,8 Menthadiene 3.1 1.3 5.8 Carbonyl number (ppm) 360 770 54 115 186 TABLE 10 Composition of Ter?enes as Petroleum Resin Feed Additives Feed Composition (wt.%) Steam Cracker Feed (IBP-700C cut) 40 40 40 40 40 40 Paraffinic Solvent L.V.N. 30 30 30 30 30 30 F.C.C. Olefins (IBP-1000C cut) 30 20 20 20 20 20 Carene - 10 " Limonene 10 - - Dipentene A 10 - &alpha;- Pinene 10 ss- Pinene 10 Pentadiene 1,3 in Total Feed 7.9 7.9 7.9 7.9 7.9 7.9 Isoprene in Total Feed 9.5 9.5 9.5 9.5 9.5 9,5 Carene in Total Feed - 8.4 0,5 - Linonene in Total Feed - 0.7 7.9 4.2 &alpha; ;- Pinene in Feed 9.6 0.1 -Pinene in Feed 9.2 TABLE 10 (Cont'd) Resin Properties Product Resin (wt.) 23.6 29.0 31.0 29.1 27.2 36.4 Liquid oligomers (wt.%) 6.0 8.7 9.0 9.9 7.7 5.9 Unreacted Compounds (wt.%) 70.4 61.6 60.0 61.0 65.1 57.7 Product Properties Softening Point 93 97 99 95 93 103 Gardner Colour 3 2.5 4 3.5 3.5 3.5 eat Stability 13+ 13- 13- 12.5 13 13+ Molecular Wt Mn 1435 1345 1300 1900 1470 Mw 3010 3585 3170 2535 4805 Mw/Mn 2.19 2.66 2.48 2.13 3.26 Wax Cloud Point C 50:25:25 80 76 73 68 105 124 40:40: :20 120 115 84 142 1800 Peel Strength (Ib/inch) 2.35 2.45 2.55 2.30 2.2' 2.9 Polyken Tack (grams) 850 1000 1100 950 1000 1050 Tack Rolling Ball (cm) 4 1.5 3 1.5 3 9 1780 Holding Power 35 36 14 16 95

Claims: What We Claim Is:- A. 1. A process comprising copolymerissing using a Friedel Crafts catalyst (1) a petroleum resin feed comprising C5 olefins and iolefins, C6 olefins and diolefins or a mixture of C5 and C6 olefins and di olefins said feed being obtained from the cracking of petroleum feedstock and (2) Limonene in the absence of carvestrene. 2. A process comprising copolymerising using a Friedel Crafts catalyst (1) a petroleum diolefins C olefins and diolefins or a mixture of C5 and C6 and di olefins said feed being obtained from the cracking of petroleum feedstock and (2) limonene the petroleum resin feed comprising at least 40 wt.% of the combined weight of limonene and resin feed. 3. A process according to 91 aims 1 or claim 2 wherein the polymerr isation feed also contains branched olefins, substituted aromatics, and/or tertiary hydrocarbon.halideS for resin molecular weight contribution control. 4. A process according to anyone of the preceding claims wherein'the feed also contains unsaturated C8-C1O aromatics such as styrene, methyl styrene, vinyl toluepe, indene. 5. A process according to any of the preceding claims in which frost 50.1 to 99 wt.% of piperylepe and/or isoprene based on the combined weight of C5 conjugated diolefines and limonene is used. 6. A process according to any of the preceding claims in which other unsaturated cyclic monomers are included in the copolymerisation 7. A resin whenever prepared by a process according to any of the preceding claims. 8. A petroleum resin having a softening point in the range 60 C to 1400C comprising a copolymer of from 50.1 to 99 wt.% piperylene and from 49.9 to 1 wt.% limcnene

Inventors: LEPERT, ANDRE
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1979
Main classification: C08F240
IPC codes: C08F240