Petroleum resins and their production with BF3 catalyst

Details Petroleum resins and their production with BF3 catalyst Petroleum resins and their production with BF3 catalyst

2000-07-19

2002-11-12

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Removing and recycling removed material from an ongoing...

C526S210000, C526S237000, C526S290000

Reexamination Certificate

active

06479598

ABSTRACT:

The present invention is concerned with the production of petroleum resins and with the improved resins so produced.
Petroleum resins are well known and are produced by the Friedel-Crafts polymerization of various feeds, which may be pure monomer feeds or refinery streams containing mixtures of various unsaturated materials. Typical feeds are C
4
to C
6
or C
8
to C
9
olefin and diolefin feeds and mixtures thereof and a variety of pure olefinic monomers.
The resulting hydrocarbon resins can range from viscous liquids to hard, brittle solids with colours ranging from water white to pale yellow, amber, or dark brown depending on the monomers used and the specific reaction conditions. Typically, pure monomer resins tend to be water white, C
9
monomer resins tend to be brown, and C
5
monomer resins tend to be yellow.
Hydrocarbon resins are used in adhesives, rubbers, hot-melt coatings, printing inks, paint, flooring, road marking and polymer and other applications. The resins are usually used to modify other materials.
Pure monomer hydrocarbon resins can be prepared by cationic polymerization of styrene- based monomers such as styrene, alpha-methyl styrene, vinyl toluene, and other alkyl substituted styrenes using Friedel-Crafts polymerization catalysts such as unsupported Lewis acids (e.g., boron trifluoride (BF
3
), complexes of boron trifluoride, aluminium trichloride (AlCl
3
), alkyl aluminium chlorides).
Similarly, aliphatic C
4
to C
6
hydrocarbon resins can be prepared by cationic polymerization of cracked petroleum distillates containing C
4
, C
5
and C
6
paraffins, olefins, and diolefins also referred to as “C
5
monomers”. These monomer streams are comprised of cationically polymerizable monomers such as 1,3-pentadiene which is the primary reactive component, along with butadiene, cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, isoprene, cyclopentadiene, and dicyclopentadiene. The polymerizations are catalysed using Friedel-Crafts polymerization catalysts such as unsupported Lewis acids (e.g., boron trifluoride (BF
3
), complexes of boron trifluoride, aluminium trichloride (AlCl
3
), or alkyl aluminium chlorides). In addition to the reactive components, non-polymerizable components in the feed include saturated hydrocarbons, which can be co-distilled with the unsaturated components such as pentane, cyclopentane, or 2-methyl pentane. This monomer feed can be co-polymerized with C
4
or C
5
olefins or dimers.
Aromatic C
9
hydrocarbon resins can be prepared by cationic polymerization of aromatic C8, C
9
, and/or C
10
unsaturated monomers derived from petroleum distillates resulting from naphtha cracking and are referred to as “C
9
monomers”. These monomer streams are typically comprised of mixtures of cationically polymerizable monomers such as styrene, alpha methyl styrene, beta methyl styrene, vinyl toluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl substituted derivatives of these components. In addition to the reactive components, non-polymerizable components include aromatic hydrocarbons such as xylene, ethyl benzene, cumene, ethyl toluene, indane, methylindene, naphthalene and other similar species.
Although unsupported Lewis acids are effective catalysts for cationic polymerization reactions to produce hydrocarbon resins, they have several disadvantages. Conventional unsupported Lewis acids are single use catalysts, which require processing steps to quench the reactions and neutralize the acids. Further, conventional unsupported Lewis acids also require removal of catalyst salt residues from the resulting resin products. Once the salt residues generated from the catalyst neutralization are removed, the disposal of these residues presents an environmental hazard and additional cost. Therefore, it is of particular interest to reduce the amount of catalyst residues, particularly halogen-containing species generated in these reactions.
Another problem involved in using conventional unsupported Lewis acid catalysts, such as AlCl
3
and BF
3
, is that they are hazardous materials. These conventional Lewis acid catalysts generate highly corrosive acid gases on exposure to moisture, (e.g., HF, HCl) and it has been necessary to rigorously dry the feeds prior to polymerization.
The present invention therefore seeks to overcome these problems and to provide a commercially viable process for the production of petroleum resins, particularly from C
5
to C
6
or C
8
to C
9
refinery feedstreams or mixtures thereof which can tolerate conventional impurities in the feed, reduces catalyst residues in the resin and does not require extensive spent catalyst disposal.
The invention employs a supported Friedel-Crafts catalyst. It has been suggested in PCT publication WO 95/26818 that supported Lewis acid catalysts may be used for hydrocarbon conversion reactions including the polymerization of unsaturated monomers such as piperylene. More recently, PCT publication WO 98/130587 is specifically concerned with supported metal halide catalysts useful for the preparation of hydrocarbon resins, WO 98/130587 is primarily concerned with using zinc, zirconium and aluminium halide catalysts.
We have found, however, that particular supported boron trifluoride catalysts when used with particular feeds give new resins with desirable and improved properties. Conventionally when using boron trifluoride catalysts in complexed or uncomplexed form, it has been necessary to rigorously dry the reaction feeds. We have found that when using a particular type of boron trifluoride catalyst moisture in the feed can be tolerated and can, in some instances, be beneficial.
Accordingly we have found that by using a supported boron trifluoride catalyst, which is complexed with an organic or inorganic cocatalyst, the catalyst properties can be controlled and the catalyst can be used to produce petroleum resins in high yield including certain novel petroleum resins having particularly desirable properties. The use of the boron trifluoride complex enables better control of the acid strength of the catalyst and allows catalysts of increased strength to be used. In particular we find that when petroleum resins produced in this way are used in adhesive formulations for bonding substrates to metal adhesive compositions that are highly resistant to high shear conditions may be obtained. We have also found that when used with natural rubber an adhesive with good cohesion may be obtained with a resin of lower molecular weight as compared with resins produced using other conventional catalyst systems.
The present invention therefore provides a process for the production of petroleum resins by the polymerization of C
5
to C
6
and/or C
8
to C
9
unsaturated hydrocarbon feeds wherein the feed is contacted under polymerization conditions with a supported boron trifluoride cocatalyst complex.
The preferred supported boron trifluoride catalysts are described in Chemical Communications 1998, Pages 2135 and 2136 and are the subject of PCT Patent Publication WO 00/13792.
This preferred catalyst is a novel form of a supported boron trifluoride complex that exhibits Bronsted and Lewis acid properties that can be tuned by varying the cocatalyst, the nature of the support and the calcination temperature. The catalytic activity of homogeneous boron trifluoride complexes in many organic reactions is dependent on the ability of the complex [H
+
][X:BF
3
−
] where X is the complexing agent, to act as a proton donor to olefins. The activity of the cocatalyst (HX) in homogenous systems is observed to decrease in the order.
 HF>H
2
SO
4
>H
3
PO
4
>C
6
H5OH>H
2
O>RCOOH>ROH
Silica is a preferred catalyst support. We have now found that by supporting different polarizable proton donating boron trifluoride complexes on SiO
2
, tuneable catalytic activity combined with the advantage of ease of catalyst recovery of a heterogeneous solid acid can be achieved. Subsequent thermal treatment of the catalyst also enables additional tuning of the relative amou

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