Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-03-02
2002-06-11
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S602000, C524S607000, C526S317100, C526S318000, C526S318100
Reexamination Certificate
active
06403698
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to amide-type polymers, for example polyamide and polyesteramide polymers, and methods for making such polymers. The amide-type polymers are produced by introducing a polymer colloid system using a diol and/or water based polymer colloid system into an amide-type polymerization reaction. The polymer colloid system may comprise a water component, a diol component, or a mixture thereof, and optionally, one or more co-solvents. An amide-type polymer/first polymer blend is also provided. The amide-type polymers produced according to the methods of the invention are heterophase materials.
BACKGROUND OF THE INVENTION
Latex polymers are utilized in a variety of products due to the unique features of the polymer delivery system. Latex polymers, by nature, have lower viscosities than their solution counterparts. This lower viscosity allows for higher polymer concentrations to be delivered in an application without encountering the numerous problems associated with high viscosity fluids. The reason for the unique viscosity behavior of latex polymers results from the heterogeneity of the system. The fact that the latex polymers are dispersed, rather than dissolved, in a continuous low viscosity media reduces the influence of the latex polymer on the viscosity of the medium. Therefore, the continuous phase or solvent of the latex is the dominant component affecting the viscosity of the system.
Typically, the continuous phase of most commercial latexes is water. This is beneficial in that water has low toxicity and is not flammable. Water is a good choice when the continuous phase is to be used as a delivery system for the polymer. In some circumstances, however, water may be detrimental to the substrate, or it may be necessary to change the drying characteristics of the latex.
Solvents other than water may be used in the continuous phase. For example, the addition of diol solvents in minor amounts is known. Japanese Patent No. 04335002 discloses the addition of alcohol(s) as an antifreeze agent for the production of vinyl ester emulsions at low temperatures. The amount of the diol solvent disclosed is below 50 wt. %. Japanese Patent No. 63186703 discloses the addition of film forming agents and plasticizers in an amount up to 10 wt % of the solid component to effect film formation properties of the resulting emulsion. Japanese Patent No. 06184217 discloses the addition of polyols and water-soluble inorganic salts to vinyl chloride suspension polymerization reactions to produce vinyl chloride polymers that have good powder fluidity. EP 255137 discloses the use of water soluble alcohol in a water/alcohol level of 100/0 to 50/50 for producing polyvinylester with a high degree of polymerization.
U.S. Pat. No. 3,779,969 describes the use of propylene diol or diethylene diol in amounts of 10-50 wt. % of the emulsion. The ethylene diol is added to impart improved wetting properties of the emulsion.
U.S. Pat. No. 4,458,050 describes a process for the manufacturing of polymer dispersions in diol chain extenders. The patent relates to the production of polymers which have low viscosity for the preparation of polyurethanes. The '050 patent does not disclose compositions which lead to stabilized latexes in diol solvents. The patent also discloses large amounts of polymeric stabilizers to produce the dispersion polymer. Japanese Patent Nos. 60040182 and 64001786 disclose compositions for wateroil repellency for fabric treatment. The compositions are aimed at producing fluoropolymer emulsions in a mixture of diol solvents. Such fluoropolymers are not the subject of this invention.
U.S. Pat. No. 4,810,763 discloses suspension polymerization in an organic medium for the preparation of pressure sensitive adhesives. The compositions described in the '763 patent are specifically aimed at producing large particle size dispersions. This patent does not disclose compositions which produce particle size latexes having a particle size below 1000 nm. This reference also does not disclose emulsion polymerization.
U.S. Pat. No. 4,885,350 and U.S. Pat. No. 5,061,766 disclose the dispersion polymerization of vinyl monomers in hydrophilic organic liquids. To produce the dispersion polymer, large amounts of polymeric dispersion stabilizers are disclosed.
It is known to modify polyamide polymers by blending the polyamide polymer with another polymer in an extruder. To improve the impact properties of a polyamide, a low Tg elastomer is typically added to the polymer in a twin-screw extruder. For example,
Polymer Engineering and Science
, Vol. 23, 7, Page 380 (1983) discloses the use of maleated LDPE blended into nylon 6,6 in a torque rheometer. The effects of polyamide blend component properties and final blend morphology on properties are shown in
Adv. Chem. Ser
. (1993), 233 (Toughened Plastics 1), 70-104. The use of epoxy, carboxylic acid, and imide functionality in polyamide/core-shell rubber blends is disclosed in Japanese Patent No. 04175370. Using anhydride and epoxy functionality in polyamide blends with rubbery ethylene copolymers is disclosed in WO 9522570. The size of the dispersed phase is critical in attaining good properties as taught in
J. Appl. Polym. Sci
. (1994), 54(3), pg 339-54. However, these previously disclosed methods of modifying polyamide polymers each require a separate blending step. Such blending processes are energy intensive, sometimes resulting in the reduction of the physical properties of the polymer, in particular the molecular weight, and it requires a blending step, which utilizes more resources and more time.
There exists a need for a process for producing a polymer blend by more economical methods. Such a need has been solved by the present invention, which can achieve such a blend in a polymerization reactor, wherein the physical properties of the polyamide polymer are maintained or improved.
SUMMARY OF THE INVENTION
In one aspect, the invention herein provides a method of making an amide-type polymer/first polymer blend comprising the steps of:
a. preparing a polymer colloid system comprising a first polymer dispersed in a liquid continuous phase;
b. introducing the polymer colloid system into an amide-type polymerization reaction medium prior to or during the reaction, wherein the reaction medium comprises 1) a diacid component and a diamine component, an oligomer of a diacid and a diamine component, or a mixture thereof; and
c. polymerizing the components of b)1, thereby providing an amide-type polymer/first polymer blend.
In a further aspect, the invention provides an amide-type polymer/first polymer blend comprising:
a. a polymer colloid system comprising a first polymer comprising a non-core shell polymer; and
b. an amide polymer.
In yet a further aspect, the invention provides a method of making a amide-type polymer/first polymer blend comprising the steps of:
a. preparing a polymer colloid system comprising a liquid continuous phase;
b. introducing the polymer colloid system into an amide-type polymer; and
c. extruding the polymer colloid system and the amide-type polymer, thereby providing an amide-type polymer/first polymer blend.
DETAILED DESCRIPTION OF THE INVENTION
The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.
Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
In this specification and in the claims that follow, reference will be made to a number of terms which shall be defined to have the following meanings:
The singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise.
“Optional” or “optio
Darnell William R.
Hale Wesley R.
Jones Allan Scott
Murray David Logan
Carrier, Esq. Michael K.
Cheung William K
Eastman Chemical Company
Graves, Jr. Esq. Bernard J.
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