Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-03-05
2004-07-13
Zalukaeva, Tatyana (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S198000, C526S197000, C526S208000, C526S230000, C526S328000, C526S329100, C564S008000, C564S009000, C428S500000, C428S515000, C428S516000, C428S520000, C428S522000
Reexamination Certificate
active
06762260
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to polymerizable compositions comprising compounds containing moieties capable of free radical polymerization, organoborane amine complex initiators capable of initiating free radical polymerization and polymerizable compounds containing ring opening heterocyclic moieties, such as oxirane or aziridine moieties. In another embodiment the invention relates to a method of polymerizing compounds containing moieties capable of free radical polymerization and moieties containing oxirane or aziridine functionality capable of ring opening polymerization. In another embodiment, the invention relates to cured compositions having regions of free radically polymerized polymer and regions of polymers derived from ring opening compounds.
In many practical situations in which compounds are subjected to polymerization, for instance where the polymerizable compounds are used as adhesives, it is desirable to have polymerizable compositions and adhesive compositions that can cure on demand, by performing an operation such as heating, shearing or contacting two or more components containing reactive materials. Cure on demand means that the polymerization can be initiated when desired. A significant problem with cure on demand compositions is the stability of the compositions. Many such compositions at, or near, ambient temperature will cure partially resulting in an increased viscosity causing difficulties in handling and reduced functionality of the polymerizable composition or adhesive composition.
Low surface energy olefins such as polyethylene, polypropylene and polytetrafluroethylene have a variety of attractive properties in a variety of uses, such as toys, automobile parts, furniture applications and the like. Because of the low surface energy of these plastic materials, it is very difficult to find adhesive compositions that bond to these materials. The commercially available adhesives that are used for these plastics require time consuming or extensive pretreatment of the surface before the adhesive will bond to the surface. Such pretreatments include corona treatment, flame treatment, the application of primers, and the like. The requirement for extensive pretreatment of the surface results in significant limitations to the designers of automobile components, toys, furniture and the like.
A series of patents issued to Skoultchi (U.S. Pat. Nos. 5,106,928; 5,143,884; 5,286,821; 5,310,835 and 5,376,746 (all incorporated herein by reference)) disclose a two-part initiator system that is useful in acrylic adhesive compositions. The first part of the two-part system includes a stable organoborane amine complex and the second part includes a destabilizer or activator such as an organic acid or an aldehyde. The organoborane compound of the complex has three ligands which can be selected from C
1-10
alkyl groups or phenyl groups. The adhesive compositions are disclosed to be useful in structural and semi-structural adhesive applications, such as speaker magnets, metal to metal bonding, automotive glass to metal bonding, glass to glass bonding, circuit board component bonding, bonding select plastics to metal, glass to wood, etc. and for electric motor magnets.
Zharov, et al. discloses in a series of U.S. Patents (U.S. Pat. Nos. 5,539,070; U.S. 5,690,780; and U.S. 5,691,065 (all incorporated herein by reference)) polymerizable acrylic compositions which are particularly useful as adhesives wherein organoborane amine complexes are used to initiate cure. It is disclosed that these complexes are good for initiating polymerization of an adhesive that bonds to low surface energy substrates.
Pocius in a series of patents (U.S. Pat No. 5,616,796; U.S. 5,621,143; U.S. 5,681,910; U.S. 5,686,544; U.S. 5,718,977; and U.S. 5,795,657 (all incorporated herein by reference)) disclose amine organoborane complexes with a variety of amines such as polyoxyalkylene polyamines and polyamines which are the reaction product of diprimary amines and compound having at least two groups which react with a primary amine. Pocius (U.S. Pat No. 5,686,544) discloses a composition comprising an organoborane polyamine complex, polyol and an isocyanate decomplexing agent.
Many of the complexes disclosed in the Zharov, Skoultchi and Pocius Patents are not stable in compositions containing olefinic unsaturation at, or near, ambient temperatures and thus the complexes disassociate and induce polymerization at, or near, ambient temperature with time. This instability at or near, ambient temperature can result in polymerization before desired and can result in compositions that are unsuitable for the desired use. Further, the compositions generally are two part compositions in which one side is a resin side and the other side is a hardener. One side (hardener) contains the organoborane complex and the other contains the decomplexing agent. In most cases the volume ratio of the two parts is significantly different, that is greater, than 4:1, often greater than 10:1. The problem is that most commercial equipment designed to dispense two part compositions utilizes ratios of 4:1 or less. In order to get these compositions to work in such equipment, resin or nonreactive ingredients are added to one side or the other to get a suitable volumetric ratio. The problem is that if resin is added to the side containing the complex, the mixture is unstable and could begin to cure at ambient temperatures and render the composition useless. If excessive inert materials are added to the hardener side, the inert ingredient can act as a plasticizer or create a weak continuous phase and negatively impact the properties of the polymerized composition.
After polymerization many of the compositions of the prior art demonstrate excellent stability, strength, and adhesion at or near ambient temperatures, but at elevated temperatures undergo significant loss of strength and adhesion at elevated temperatures. This limits the environments where substrates bonded using these adhesives can be used.
Therefore, there is a need for adhesive systems which are capable of bonding to low surface energy substrates, and initiator systems which facilitate such bonding. What are further needed are polymer compositions and adhesive systems which are thermally stable at, or near, ambient temperatures and which will undergo polymerization when the user desires. Also needed are adhesive compositions which are capable of bonding to low surface energy substrates, and bonding low surface energy substrates to other substrates, without the need for extensive or costly pretreatment. Further compositions that can be used in existing commercial equipment at mix ratios of 4:1 or less are needed. Compositions that have stability, strength and adhesion at elevated temperatures are also desired.
SUMMARY OF THE INVENTION
The invention is a two part polymerizable composition comprising in one part an organoborane amine complex and one or more compounds containing one or more ring opening heterocyclic moieties, and in a second part, compounds capable of being polymerized by free radical polymerization, a catalyst capable of polymerizing compounds containing ring opening heterocyclic moieties and optionally a component that will decomplex the organoborane amine complex. In one embodiment the invention is a two phase system comprising a first phase containing one or more polymers prepared from the compounds which polymerize by free radical polymerization and a second phase comprising polymerized or partially polymerized compounds derived from one or more compounds containing ring opening heterocyclic moieties. In one embodiment the polymer prepared from the compounds containing heterocyclic ring opening moieties is not miscible with the polymer prepared by free radical polymerization and thus the resulting polymerized composition has at least two regions each rich in one of the two polymers formed. In another embodiment the polymerizable compositions of the invention can be formulated into adhesive compositions. Adhesive compositions of the pres
Harrington Daniel D.
Sonnenschein Mark F.
Webb Steven P.
Wendt Benjamin L.
Dow Global Technologies Inc.
Sims Norman L.
Zalukaeva Tatyana
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