Hydrocarbon resins from aryl norbornene derivatives

Details Hydrocarbon resins from aryl norbornene derivatives Hydrocarbon resins from aryl norbornene derivatives

2001-09-20

2002-08-06

Teskin, Fred (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S237000, C526S308000, C526S347000, C525S333300, C525S338000, C524S553000

Reexamination Certificate

active

06429272

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to novel mixed aliphatic/aromatic hydrocarbon resins, particularly useful for tackifying purposes. Also, this invention relates to a novel process for preparing the hyrdrocarbon resins wherein 5-aryl-2-norbornene is polymerized, optionally with other alkenes, in the presence of a Friedel-Crafts catalyst. Products resulting from hydrogenation of the hydrocarbon resins are also included within the invention.
BACKGROUND OF THE INVENTION
Polymers produced from norbornene derivatives are well known in the art, and there are many processes known for the preparation of the polymers. Also known is the use of norbornene, and derivatives thereof, as monomers and comonomers in preparing polymeric materials. In general, norbornene, and derivatives thereof, can be polymerized by ring opening metathesis polymerization method (ROMP), or by catalysis method using metallocene or Ziegler-Natta catalysts. Polymers prepared by the ROMP method have unsaturated backbones, and the process involves opening of the strained, unsaturated and bridged 5-member ring of norbornene. Polymers prepared using Ziegler-Natta catalysts are addition polymers that preserve the norbornene structure. Ziegler-Natta catalysts are typically based on titanium compounds, in combination with an organoaluminum co-catalyst such as triethylaluminum.
Copolymers of norbornene, or substituted norbornene, with ethylene, are commercially available, and are primarily used for optical applications such as compact discs. A problem associated with norbornene-ethylene copolymers is that the copolymers are brittle below the glass transition temperature of the copolymers. It is known that the use of 5-aryl-substituted norbornene, such as 5-phenyl-2-norbornene overcomes the problem of brittleness associated with use of norbornene. It is also known that aryl-substituted norbornene, such as 5-phenyl-2-norbornene, can be copolymerized, using either metathesis catalysts such as tungsten halides or metallocene catalysts such as zirconocene, with other cyclic alkenes or ethylene, to provide interpolymers that exhibit satisfactory modulus, optical, impact-resistant and strength properties.
The polymeric products that are known and commercially available are generally high molecular weight polymers, having a M
n
molecular weight exceeding 4000, and as such, are not suitable for use as tackifiers. It is generally acknowledged that tackifying resins have number average molecular weights (M
n
) in the range of about 100 to about 1500.
SUMMARY OF THE INVENTION
The present invention relates to certain mixed aliphatic/aromatic hydrocarbon resins, that are particularly suitable for use as tackifiers. The hydrocarbon resins are homopolymers of 5-aryl-2-norbornene, or interpolymers of 5-aryl-2-norbornene with at least one, or more, other cyclic or acyclic alkene. The aryl group of the 5-aryl-2-norbornene is any aromatic group or substituent having at least 5 carbon atoms preferably from 5 to about 20 carbon atoms. Exemplary aromatic groups or substituents include phenyl, substituted phenyl, indenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl, n-butylphenyl, trimethylphenyl, t-butylphenyl, substituted indenyl, substituted naphthyl, and the like. The novel hydrocarbon resins are characterized by having, in combination, (a) a softening point ranging from about 50° C. to about 150° C., (b) a number average molecular weight (M
n
) ranging from about 120 to about 1000, (c) a weight average molecular weight (M
w
) ranging from about 150 to about 2000, (d) a z-average molecular weight (M
z
) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen determined by
1
H NMR.
The novel 5-aryl-2-norbornene homopolymers and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene, may be hydrogenated to produce novel hydrogenated hydrocarbon resins. The hydrogenated resins have all the above-recited characteristics, (a) through (e), of the 5-aryl-2-norbornene homopolymers and interpolymers described above, and are further characterized by having (f) a mixed methylcyclohexane aniline cloud point (MMAP) ranging from about 15° C. to about 65° C.
The homopolymers of 5-aryl-2 norbornene, and the interpolymers thereof, with at least one, or more, other cyclic or acyclic alkene, and the resins resulting from the hydrogenation of the homopolymers and interpolymers of the 5-aryl-2-norbornene, are useful as tackifiers for non-woven, hot-melt and pressure sensitive adhesive formulations.
The novel process of the invention for producing the novel homopolymers of 5-aryl-2-norbornene, and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene(s), described herein, is comprised as follows. A 5-aryl-2-norbornene, with a cyclic or acyclic alkene where an interpolymer is desired, is polymerized in the presence of a Friedel-Crafts catalyst, such as, for example, aluminum chloride and boron trifluoride, under suitable polymerization conditions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to certain mixed aliphatic/aromatic hydrocarbon resins, that are particularly suitable for use as tackifiers. The hydrocarbon resins are homopolymers of 5-aryl-2-norbornene, or interpolymers of 5-aryl-2-norbornene with at least one, or more, other cyclic or acyclic alkene. The aryl group of the 5-aryl-2-norbornene is any aromatic group or substituent having at least 5 carbon atoms preferably from 5 to about 20 carbon atoms. Exemplary aromatic groups or substituents include phenyl, substituted phenyl, indenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl, n-butylphenyl, trimethylphenyl, t-butylphenyl, substituted indenyl, substituted naphthyl, and the like. The novel hydrocarbon resins are characterized by having, in combination, (a) a softening point ranging from about 50° C. to about 150° C., (b) a number average molecular weight (M
n
) ranging from about 120 to about 1000, (c) a weight average molecular weight (M
w
) ranging from about 150 to about 2000, (d) a z-average molecular weight (M
z
) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen determined by
1
H NMR.
The novel 5-aryl-2-norbornene homopolymers and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene, may be hydrogenated to produce novel hydrogenated hydrocarbon resins. The hydrogenated resins have all the above-recited characteristics, (a) through (e), of the 5-aryl-2-norbornene homopolymers and interpolymers described above, and are further characterized by having (f) a mixed methylcyclohexane aniline cloud point (MMAP) ranging from about 150° C. to about 65° C.
The homopolymers of 5-aryl-2 norbornene, and the interpolymers thereof, with at least one, or more, other cyclic or acyclic alkene, and the resins resulting from the hydrogenation of the homopolymers and interpolymers of the 5-aryl-2-norbornene, are useful as tackifiers for non-woven, hot-melt and pressure sensitive adhesive formulations.
The novel process of the invention for producing the novel homopolymers of 5-aryl-2-norbornene, and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene(s), described herein, is comprised as follows. A 5-aryl-2-norbornene, with a cyclic or acyclic alkene where an interpolymer is desired, is polymerized in the presence of a Friedel-Crafts catalyst, such as, for example, aluminum chloride and boron trifluoride, under suitable polymerization conditions.
In further detail, the polymerization process may be operated either in a continuous manner, or, in a batch manner, utilizing a nitrogen-flushed, oven-dried round bottom flask equipped with an overhead stirrer and an additional funnel. In the batch process, the flask is charged with the 5-aryl-2-norbornene, and, optionally, the at least one, or more, other cyclic or acyclic alkene, and the desired Friede

Affiliated with

Also associated with

Rating

Hydrocarbon resins from aryl norbornene derivatives does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Hydrocarbon resins from aryl norbornene derivatives, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Hydrocarbon resins from aryl norbornene derivatives will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2887696