Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1997-11-18
2001-03-06
Sellers, Robert E. L. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C264S240000, C523S466000, C523S467000, C525S09200D, C525S107000, C525S108000, C525S109000, C525S111000, C525S113000, C525S122000, C525S423000, C525S438000, C525S454000, C525S463000, C525S471000, C525S476000, C525S485000, C525S486000
Reexamination Certificate
active
06197898
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a process for molding and shaping polymer blends comprising at least one thermoplastic polymers and an uncured thermosettable and/or polymerizable epoxy resin.
CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
Not applicable.
BACKGROUND OF THE INVENTION
The invention also relates to articles shaped out of a material comprising a thermoplastic phase in which cured or polymerized epoxy particles have been dispersed. Said articles can be obtained with the process of the invention
Processes for the molding and shaping of polymer blends comprising thermoplastic polymers blended with epoxy resins are known. The advantages of said processes are related to the fact that some thermoplastic polymers are difficult to mold and shape in view of their high processing temperature. By blending the polymers with uncured or low molecular weight epoxy resins it becomes possible to shape the polymers at lower temperatures. To obtain shaped products with the good properties of the used thermoplastic polymers, it is necessary to separate the epoxy resin from the thermoplastic polymer after the shaping step to obtain a continuous matrix of the thermoplastic polymer(s) with dispersed epoxy particles. Processes to make products made from material with a continuous phase of cured epoxy resins in which thermoplastic particles have been dispersed are also known. In the latter case products are obtained with the material properties of the cured epoxy resin which has been adjusted somewhat by the dispersed particles of thermoplastic resin.
U.S. Pat. No. 3,763,088 describes a process wherein a non-crystalline thermoplastic resin is blended with uncured epoxy resins. The blends can be prepared by dry blending and fusion mixing the ingredients in a melt extruder at elevated temperatures. The hot melt may be shaped by injection molding. The relative quantity of epoxy resin is chosen such that a final structure results in a continuous phase of polymer particles in which uncured epoxy resin particles have been dispersed. To obtain such a structure it is essential to use epoxy resins with a molecular weight which is sufficiently high. The examples use epoxy resins with molecular weights of 3600 to 8,000.
U.S. Pat. No. 4,623,558 describes a process wherein a thermoplastic resin is blended with an uncured epoxy resin and a thermal initiator or a photo initiator at a temperature below the curing temperature of the system. The blend after combination with glass mats is heated and cured. For polymers with high melting temperatures or high glass transition temperatures, such as polyphenylene ethers, it is however not possible to get homogeneous blends of the polymer, the epoxy resin and the initiator at temperatures below the curing temperature when the relative amount of thermoplastic resin is too high. In practice the process this patent is only suitable for the processing of blends which after curing form a continuous phase of a cured epoxy resin in which particles of the thermoplastic polymer have been dispersed.
U.S. Pat. No. 5,382,384 and its parent U.S. Pat. No. 5,250,228 describe a process wherein a thermoplastic resin, a thermosetting resin, a conductive filler and a curing agent are mixed together wherein the mixture is shaped below the curing temperature of the mixture and wherein the shaped mixture is heated quickly to the curing temperature and is cured at the curing temperature. The mixing is performed below the curing temperature of the curing agent. As described before this makes it impossible for high melting polymers like polyphenylene ether to be used in relatively large quantities.
European patent application EP-B-0 537 005 describes a process for the manufacture of prepregs wherein a polyphenylene ether polymer is blended with a liquid epoxy material, optionally with a flame retardant and a catalyst, at a temperature of 100-130° C. The blend is subsequently granulated into particulates and the particulates are combined with one or more reinforcing cloth or fiber and the thus obtained combination is cured under pressure at 210° C. to 250° C. The blending of the polyphenylene ether and the epoxy are performed at a temperature below the curing temperature of the epoxy resin. This limits the possibilities of the process considerably.
In Polymer, Vol. 35, no. 20, 1994, page 3450 has been described a process wherein solutions of an epoxy and polyphenylene ether (PPE; a thermoplastic resin) are prepared in a Brabender kneader at 175° C. by kneading for about one hour. As an alternative it has been proposed to prepare the blend by mixing for 5-10 minutes in a co-rotating twin screw extruder. Subsequently a curing agent is added to the homogeneous solution in the Brabender mixer for about two minutes, the obtained compound is compression moulded and cured by curing cycles of two hours followed by a post-cure treatment of four hours at 200° C.
Mixing of epoxy/PPE mixtures, in particular those with more than 20% by wt of PPE, at temperatures of 175° C. results in compositions which are too viscous for many commercially useful shaping processes such as injection molding.
It has now been found that even with curing agents or catalysts which are fast at the chosen melt mixing temperatures it is possible to work at high temperatures (in the case of PPE at temperatures of over 220° C.) without causing premature reaction of the epoxy resin. This can be achieved by ensuring a quick mixing. The mixing time in the second step of process of the invention may, depending upon the nature of the constituents and the required temperatures, be far below two minutes.
The present invention provides a simple but effective process for the shaping of polymer blends comprising one or more thermoplastic polymers and an uncured thermosettable and/or polymerizable epoxy resin. With the process of the present invention it is possible to use relatively fast curing and/or polymerization systems resulting in short cycle times. With the process of the invention it becomes possible to shape polymers at temperatures below their normal processing temperatures. This is of importance for the processing of thermoplastic materials which are unstable or sensitive to oxidation at their processing temperature. With the process of the present invention it also becomes possible to incorporate into polymers materials that are thermally unstable at the usual processing temperature of the polymer. With the process of the invention it is possible to shape the blend and to cure and/or polymerize the epoxy resin in the blend after the shaping step even when relatively large quantities of thermoplastic resin with a high melting point or a high glass transition temperature are used.
SUMMARY OF THE INVENTION
The present invention provides a process for preparing a polymer composition comprising: melt mixing at least one thermoplastic polymer at a temperature above the glass transition temperature or above the melting temperature of the thermoplastic polymer with one of (i) an uncured epoxy resin, or (ii) an epoxy curing agent or a catalyst to form a blend; (b) further melt mixing at a temperature above the glass transition temperature or above the melting temperature of the thermoplastic polymer the other of (i) an epoxy resin, or (ii) a epoxy curing agent or a catalyst, with the blend in (a) to form a substantially uncured but essentially curable and/or polymerizable composition; (c) optionally forming a shaped product from the composition in (b); and (d) fast curing and/or fast polymerizing the optionally formed shaped product.
REFERENCES:
patent: 3367978 (1968-02-01), White
patent: 3367990 (1968-02-01), Bremmer
patent: 3375298 (1968-03-01), Fox
patent: 3468824 (1969-09-01), Williams
patent: 3475513 (1969-10-01), Benson
patent: 3652710 (1972-03-01), Holub
patent: 3689444 (1972-09-01), Gilbert
patent: 3763088 (1973-10-01), Izawa
patent: 3812214 (1974-05-01), Markovitz
patent: 4137275 (1979-01-01), Smith et al.
patent: 4496695 (1985-01-01), Sugio et al.
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Bailly Christian Maria Emile
Caraher Joel Matthew
de Wit Gerrit
Fortuyn Johannes Everardus
Jana Sadhan C.
General Electric Company
Sellers Robert E. L.
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