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United States Patent 3,264,272 IONIC HYDROCARBON POLYMERS Richard Watkin Rees, Wilmington, DeL, assignor to E. I. du Pont de Nemours and Company, Wilmington, Del, a corporation of Delaware N0 Drawing. Filed Apr. 8, 1963, Ser. No. 271,477 35 Claims. (Cl. 260-585) This application is a continuation-in-part of my application Serial No. 135,147, filed August 31, 1961, now abandoned.
The present invention relates to novel hydrocarbon polymers, and, more particularly, to hydrocarbon polymers which contain ionic crosslinks.
The crosslinking of hydrocarbon polymers is well known in the art. Thus, polymeric hydrocarbon elastomers, such as natural rubber, are crosslinked or vulcanized by the use of sulfur, which reacts with the carbon of the unsaturated bonds in polymer molecules to form a bridge between two molecules so that one polymer molecule is covalently bonded to a second polymer molecule. If sufiicient crosslinks of this type occur in the polymeric hydrocarbon, all molecules are joined in a single giant molecule. The characteristic property of a crosslinked polymer is its intractibility above the softening point or melting point normally observed in the uncrosslinked base polymer. Thus, whereas the nncrosslinked polymer has a marked softening point or melting point above which the polymer is fluid and deformable, the crosslinked polymer retains its shape and will tend to return that shape when deformed at all temperatures at which the polymer is stable and can not be permanently deformed. Although once crosslinked the polymer is no longer fabricable, except possibly by machining, crosslinked polymers have found wide utility because of the significant improvement in the physical properties obtained by crosslinking. Thus, by vulcanizing rubber elasticity, impact resistance, flexibility, thermal stability and many other properties are either introduced or improved. The crosslinking of non-elastomeric polymers increases the toughness, abrasion resistance and, particularly, the upper use temperatures of the material.
In addition to the vulcanization of diene hydrocarbon polymers using sulfur, other methods of crosslinking hydrocarbon polymers which do not require a double bond and which do not use sulfur have been developed. Thus, saturated hydrocarbon polymers and, in particular, polyethylene, are crosslinked by reactions resulting from the addition of a peroxide to the polymer at elevated temperatures. Peroxides decompose to form free radicals which in turn attack the polymer chain to form crosslinking sites which then react to form crosslinks. Irradiation of polyethylene also results in a crosslinked product by substantially the same mechanism except that the free radicals are generated by decomposition of the polymer itself. By either method, however, a product is obtained which is intractible and can not be further fabricated by techniques normally used in the fabrication of polyethylene, such as melt extrusion or injection molding. The improvement obtained in the solid state properties of a hydrocarbon polymer by crosslinking have, therefore, been always combined with a loss in fabricability as a result of which crosslinked hydrocarbon polymers, with the exception of elastomeric hydrocarbon polymers, have found little commercial success as compared to the uncrosslinked hydrocarbon polymers. Furthermore, crosslinking reduces the crystallinity of saturated hydrocarbon polymers, thereby decreasing the stiffness and rigidity of the product.
It is an object of the present invention to provide a new class of hydrocarbon polymers. It is a further object of the present invention to provide a new class ice of hydrocarbon polymers of greatly improved solid state properties. It is a further object to provide hydrocarbon polymers which combine desirable solid state properties of crosslinked hydrocarbon polymers with melt flow properties of uncrosslinked hydrocarbon polymers. Other objects will become apparent hereinafter.
The objects of the present invention are accomplished by ionic copolymers comprising a polymer of an a-olefin having the general formula RCH CH where R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms, the olefin content of said polymer being at least 50 mol percent based on the polymer, and an a,B-ethylenically unsaturated carboxylic acid having 1 or 2 carboxyl-ic acid groups, the acid monomer content of said polymer being from 0 .2 to 25 mol percent based on the polymer, said carboxylic acid-containing polymer containing uniformly distributed throughout the polymer, one or more metal ions having ionized valences of 1 to 3 inclusive where the acid comonomer is monocarboxylic, and an ionized valence of one where the acid comonomer is dicarboxylic, the quantity of the metal ion being sufficient to neutralize at least 10 percent of the said carboxylic acid.
The u-olefin polymers employed in the formation of the ionic copolymers of the present invention are c0- polymers of ix-olefins with ethylenically unsaturated acids. As indicated, the u-olefins employed in the copolymer are a-olefins which have the general formula RCH CH Where R is either a hydrogen or an alkyl group having preferably from 1 to 8 carbon atoms. Thus, suitable olefins include ethylene, propylene, butene-l, pentene-l, hexene-l, heptene-l, 3-methylbutene-1, 4-methylpentene-l, etc. Although polymers of olefins having higher carbon numbers can be employed in the present invention, they are not materials which are readily obtained or available. The concentration of the a-olefin is at least 50 mol percent in the copolymer, and is preferably greater than mol percent.
The second essential component of the base copolymer comprises an a,p-ethylenically unsaturated carboxylic acid group containing monomer having preferably from 3 to 8 carbon atoms. Examples of such monomers are acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, monoesters of said dicarboxylic acids, such as methyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogen fumarate and maleic anhydride. Although maleic anhydride is not a carboxylic acid in that it has no hydrogen attached to the carboxyl groups, it can be considered an acid for the purposes of the present invention because of its chemical reactivity being that of an acid. Similarly, other 0:,{3- monoethylenically unsaturated anhydrides of carboxylic acids can be employed. As indicated, the concentration of acidic monomer in the copolymer is from 0.2 mol percent to 25 mol percent, and, preferably, from 1 to 10 mol percent.
The base copolymers employed in forming the ionic copolymers of the present invention may be prepared in several ways. Thus, the copolymers may be obtained by the copolymerization of a mixture of the olefin and the carboxylic acid monomer. This method is preferred for the copolymers of ethylene employed in the present invention. Methods employed for the preparation of ethylene tcarboxylic acid copolymers have been described in the literature. However, as pointed out further hereinafter, the preferred products are those obtained from base copolymers in which the carboxylic acid groups are randomly distributed over all of the copolymer molecules. Such distribution is obtained using the technique described in detail in coassigned application Serial No. 119,265 filed June 26, 1961, now abandoned. In brief, that technique requires carrying out the copolymerizasesame tion of the ot-olefin and the carboxylic acid monomers in a single phase environment, i.e. one in which the monomers are soluble, e.g. benzene or ethylene, which may be in liquid or vaporized form. Preferably, and especially when relatively small amounts of the carboxylic acid component are desired in the base copolymer, the process is continuous, the monomers being fed to the reactor in the ratio of their relative polymer-forming reactivities and the residence time in the reactor being limited so that from about 320% of the ethylenemo-nomer feed is converted to polymer. In a preferred process, a mixture of the two monomers is introduced into a polymerization environment maintained at high pres sures, 50 to 3000 atmospheres, and elevated temperatures, 150 to 300 C., together with a free radical polymerization initiator such as a peroxide.
Copolymers of a-olefins with carboxylic acids may also be prepared by copolymerization of the olefin with an a,fl-ethylenically unsaturated carboxylic acid derivative which subsequently or during copolymerization is reacted either completely or in part to form the free acid. Thus, hydrolysis, saponifieation or pyrolysis may be employed to form an acid copolymer from an ester copolymer.
Although ionic crossl-inks can also be formed with copolymers obtained by grafting an a e-ethylenically unsaturated carboxylic acid monomer to a polyolefin base, such copolymers do not show the degree of improvement obtained with copolymers formed by direct copolymerization, i.e., direct copolymers. To insure uniform ionic crosslinking throughout :the copolymer, it is essential to employ a copolymer containing the oarboxylic acid groups randomly distributed over all molecules. Such random distribution is best obtained by direct copolymerization. Graft copolymers which contain a third non-reactive monomer grafted to the carboxylic acid copolymer are, of course, satisfactory.
The copolymers employed to form ionic copolymers which are useful as plastics are preferably of high molecular weight in order to achieve the outstanding combination of solid state properties of crosslinked polyolefins with the melt fabricability of uncrosslinked polyolefins. Although the mechanical properties of a low molecular weight copolymer are improved by the process of the present invention, the resulting product does not exhibit such mechanical properties as are markedly superior to the same unmodified copolymer, when of high molecular weight. The molecular Weight of the copolymers useful as base resins is most suitably defined by melt index, a measure of viscosity, described in detail in ASTMD- 1238-57T. The melt index of copolymers employed in the formation of ionic copolymers which are useful as plastics is preferably in the range of 0.1 to 1000 g./ min, and, more particularly, in the range of 1.0 to 100 g./ 10 min. However, it should be pointed out that low molecular weight copolymers result in ionic copolymers which, although not suitable as plastics, are outstanding adhesives and laminating resins.
The copolymer base need not necessarily comprise a two component polymer. Thus, although the olefin content of the copolymer should be at least 50 mol percent, more than one olefin can be employed to provide the hydrocarbon nature of the copolymer base. Additionally, other copolymerizable monoethylenically unsaturated monomers, illustrative members of which are mentioned below in this paragraph, can be employed in combination with the olefin and the carboxylic acid comonomer. The scope of base copolymers suitable for use in the present invention is illustrated by the following examples: Ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers, ethylene/itaconic acid copolymers, ethylene/ methyl hydrogen maleate copolymers, ethylene/maleic acid copolymers, ethylene/ acrylic acid/methyl methacrylate copolymers, ethylene/methacrylic acid/ethyl acrylate copolymers, ethyl-ene/itaconic acid/methyl methacrylate copolymers, ethylene/methyl hydrogen maleate/ ethyl acrylate copolymers, ethylene/methacrylic acid/ vinyl acetate copolymers, ethylene/ acrylic acid/vinyl alcohol copolymers, ethylene/propylene/acrylic acid copolymers, ethylene/ styrene/ acrylic acid copolymers, ethylene/methacrylic acid/acrylonitrile copolymers, ethylene/ fumaric acid/vinyl methyl ether copolymers, ethylene/ vinyl chloride/acrylic acid copolymers, ethylene/vinylidene chloride/acrylic acid copolymers, ethylene/vinyl fiuor-ide/methacrylic acid copolymers, and ethylene/chlorotrifiuoroethylene/inethacrylic acid copolymers.
The copolymers may also, after polymerization but prior to ionic crosslinking, be further modified by various reactions to result in polymer modifications which do not interfere with the ionic crosslinking. Halogenation of an olefin acid copolymer is an example of such polymer modification.
The preferred base copolymers, however, are those obtained by the direct copolymerization of ethylene with a monocarboxylic acid comonomer.
The ionic copolymers of the present invention are obtained by the reaction of the described copolymer base with an ionizable metal compound. This reaction is referred to herein as neutralization. The reaction mechanism involved in the formation of the ionic copolymers and the exact structure of the copolymers are at the present time not completely understood. However, a comparison of the infrared spectrum of the copolymer base with that of the ionic copolymer shows the appearance of an absorption band at about 6.4 micron which is characteristic of the ionized oarboxyl group, COO, a decrease in the crystallinity band at 13.7 micron and a substantial decrease, depending on the degree of neutralization, of a band at 10.6 micron, characteristic of the unionized carboxyl group, COOH. It is consequently deduced that the surprising properties of ionic copolymers are the result of an ionic attraction between the metal ion and one or more ionized carboxylic acid groups.
This ionic attraction results in a form of crosslinking which occurs in the solid state. However, when molten and subjected to the shear stresses which occur during melt fabrication, the ionic crosslinks of these polymers are ruptured and the polymers exhibit melt fabricability essentially the same as that of the linear base copolymer. On cooling of the melt and in the absence of the shear stress occurring during fabrication, the crosslinks, because of their ionic nature, are reformed and the solidified copolymer again exhibits the properties of a crosslinked material.
The change in properties resulting from the neutralization of the base copolymer to the ionic copolymer is greatly influenced by the degree of neutralization and, therefore, the number of ionic crosslinks and the nature of the crosslink involved. Although an improvement in solid state properties is obtained with even a small percentage of the acid groups neutralized, in general, a noticeable improvement is observed only after 10 percent of the acid groups have been neutralized. However, to obtain the optimum solid state properties which are derivable from ionic copolymers, the number of crosslinks should be sufiicient to form an infinite network of crosslinked polymer chains. This, of course, not only depends on the degree of neutralization, but also on the number of crosslinking sites and the molecular weight of the base copolymer. In general, it was found that base copolymers having molecular weights as measured by melt index of 1 to 5 g./ 10 min. and a monocarboxylic acid concentration of 5 to 10 percent show optimum solid state properties upon 50 to percent neutralization. The degree of neutralization can be decreased as the molecular Weight of the copolymer base is increased or as the acid content of the copolymer base is increased without significantly changing the solid state properties. In general, no substantial further improvement in solid state properties is observed if the cross linking is continued beyond the point at which an in finite network is formed. However, the shear stress necessary to break the ionic crosslinks and, thus, make the copolymer melt fabricable is steadily increased with an increasing number of crosslinks beyond that necessary to achieve an infinite network.
The melt fabricability of the ionic copolymer is affected not only by the number of crosslinks, but to a much greater degree, is affected by the nature of the crosslink. The combination of certain types of acid copolymers with certain metal ions results in intractible materials which do not lend themselves to melt fabrication. Thus, it was found that base copolymers with dicarboxylic acid comonomers, even those in which one acid radical has been esterified, when neutralized with metal ions which have two or more ionized valences, result in intractible ionic copolymers at the level of neutralization essential to obtain significant improvement in solid state properties. Similarly, base copolymers with monocarboxylic acid comonomers result in intractible ionic copolymers when neutralized to the indicated degree with metal ions which have four or more ionized valences. It is believed that the nature of the ionic bond in these instances is too strong to be suitable for the formation of ionic copolymers which exhibit solid state properties of crosslinked resins and melt properties of uncrosslinked resins.
Metal ions which are suitable in forming the ionic copolymers of the present invention can be divided into two categories, uncomplexed metal ions and complexed metal ions. In the uncomplexed metal ions the valence of the ion corresponds to the valence of the metal. These metal ions are obtained from the commonly known and used metal salts. The complexed metal ions are those in which the metal is bonded to more than one type of salt group, at least one of which is ionized and at least one of which is not. Since the formation of the ionic copolymers requires only one ionized valence state, it will be apparent that such complexed metal ions are equally well suited in the present invention. The term metal ion having one or more ionized valence states means a metal ion having the general formula Me' X where n is the ionic charge and is at least one, X is a nonionized group and n+m equal the valence of the metal. The utility of complexed metal ions employed in the formation of ionic copolymers corresponds in their ionized valences to those of the uncomplexed metal ions. The monovalent metals are, of course, excluded but higher valent metals may be included depending on how many metal valences are complexed and how many can be ionized. The preferred complexed metal ions are those in which all but one metal valences are complexed and one is readily ionized. Such compounds are in particular the mixed salts of very weak acids, such as oleic and stearic acid, with ionizable acids, such as formic and acetic acid.
The uncomplexed metal ions which are suitable in forming the ionic copolymers of the present invention, therefore comprise for the aolefin-monocarboxylic acid copolymers, mono-, diand trivalent ions of metals in Groups, I, II, III, IV-A and VIII of the Periodic Table of Elements (see page 392, Handbook of Chemistry and Physics, Chemical Rubber Publishing Co., 37th ed.). Uncomplexed monovalent metal ions of the metals in the stated groups are also suitable in forming the ionic copolymers of the present invention with copolymers of olefins and ethylenically unsaturated dicarboxylic acids. Suitable monovalent metal ions are Na+, K Li+ Cs+, Ag Hg+ and Gu Suitable divalent metal ions are Be, +2 C -I-Z +2 B +2 +2 +2 +2 +2 p +2 Fe, Co, NH and Zn+ Suitable trivalent metal ions are Al+ Sc, Pe+ and Y+ The preferred metals, regardless of the nature of the base copolymer are the alkali metals. These metals are preferred because they result in ionic copolymers having the best combination of improvement in solid state prop- 6 erties with retention of melt fabricability. It is not essential that only one metal .ion be employed in the formation of the ionic copolymers and more than one metal ion may be preferred in certain applications.
The quantity of ions employed or the degree of neutralization will differ with the degree of solid property change and the degree of melt property change desired. In general, it was found that the concentration of the metal ion should be at least such that the metal ion neutralizes at least 10 percent of the carboxylic acid groups in order to obtain a significant change in properties. As explained above, the degree of neutralization for optimum properties will vary with the acid concentration and the molecular weight of the copolymer. However, it is generally desirable to neutralize at least 50 percent of the acid groups. The degree of neutralization may be measured by several techniques. Thus, infrared analysis may be employed and the degree of neutralization calculated from the changes resulting in the absorption bands. Another method comprises the titration of a solution of the ionic copolymer with a strong base. In general, it was found that the added metal ion reacts stoichiometrically with the carboxylic acid in the polymer up to percent neutralizations. Small excess quantities of the crosslinking agent are necessary to carry the neutralization to completion. However, large excess quantities of the crosslinking agent do not add to the properties of the ionic copolymer of the present invention, since once all carboxylic acid groups have been ionically crosslinked, no further crosslinks are formed.
The crosslinking of the ionic copolymer is carried out by the addition of a metal compound to the base copolymer. The metal compound which is employed must have at least one of its valences satisfied by a group which is substantially ionized in water. The necessary ionization is determined by the water solubility of the metal when bonded solely to the ionizable salt group. A compound is considered water-soluble for the purposes of the present invention if it is soluble in water at room temperature to the extent of 2 Weight percent. This requirement is explained as separating those ionic compounds which are capable of exchanging a metal ion for the hydrogen ion of the carboxylic acidgroup in the copolymer from those which do not interact with the acid. The second requirement of the metal compound employed to give rise to the ionic crosslink is that the salt radical reacting with the hydrogen of the carboxylic acid group must form a compound which is removable from the copolymer at the reaction conditions. This requirement is essential to obtain the carboxylic acid group of the copolymer in ionic form and, furthermore, to remove the salt radical fromthe copolymer so that the attraction between the ionized carboxylic acid group of the copolymer and the metal ion is not overshadowed by the attraction of the metal ion and its original salt radical. With these two parameters it is, therefore, possible to determine those metal compounds which form metal ions having the required ionic valences. Although the foregoing limits delineate metal compounds suitable in forming metal ions in the acid copolymers which result in ionic crosslinks, certain types of compounds are preferred because of their ready availability and ease of reaction. Preferred metal salts include formates, acetates, hydroxides of sufiicient solubility, methoxides, ethoxides, nitrates, carbonates and bicarbonates. Metal compounds which are generally not suitable in resulting in ionic crosslinks include in particular metal oxides because of their lack of solubility and the fact that such compounds form intractible compositions, metal salts of fatty acids which either are not sufficiently soluble or form compounds with the hydrogen of the acid which can not be removed and metal coordination compounds which lack the necessary ionic character.
As set forth hereinabove, in addition to uncomplexed metal ions,co1 nplexed metal ions which contain the necessary ionic valences bonded to groups meeting the aforesaid requirements can be employed. In such cases the group which does not ionize or is not removed has no effect on the ability of the ionizing group to be removed and the resulting metal ion to cause the ionic crosslinking. Thus, whereas zinc distearate or calcium dioleate are ineffective to cause ionic crosslinking such mixed metal salts as zinc stearate-acetate or calcium oleate-acetate are effective crosslinking agents.
It is not essential that the metal compound be added as such, but it is possible to form the metal compound in situ from components which react with each other in the desired manner in the polymer environment. Thus, it is possible to add a metal oxide to the base copolymer then add an acid such as acetic acid in the proper proportion and form the ionic compound, i.e., the metal acetate, while the polymer is milled.
The crossinking reaction is carried out under conditions which allow for a homogeneous uniform distribution of the crosslinking agent in the base copolymer. No particular reaction conditions are essential except that the conditions should permit the removal of the hydrogensalt radical reaction product which is preferably accomplished by volatilization. Since the homogeneous distribution of the crosslinking agent and the necessary volatilizaton of the hydrogen-salt radical reaction product is difficult at room temperature, elevated temperatures are generally employed. More specifically, the crosslinking reaction is carried out either by melt blending the polymer with the crosslinking metal compound, which prefera'bly is employed in solution, or by adding the crosslinking agent, directly or in solution, to a solution of the copolymer base and then, on reaction, precipitating and separating the resulting polymer. Of these techniques, the first is greatly preferred because of its relative simplicity. It is to be understood, however, that the specific technique employed is not critical as long as it meets the specific requirements set forth above. The course of the neutralization, i.e., the degree to which the metal ion is ionically linked with the carboxylate ion and the carboxylate hydrogen has reacted with the metal compound anion and has been removed, can be readily followed by infrared spectroscopy through measurement of the nonionized and ionized carboxylate groups.
The following examples further illustrate the methods employed in forming the ionic copolymers of the present invention. Neutralization as used in the examples is based on the percentage of carboxylate ions as compared to carboxylic acid groups.
EXAMPLE I A 500 g. sample of an ethylene/methacrylic acid copolymer, containing 10 weight percent of methacrylic acid and having a melt index of 5.8 g./l min. (ASTM- D-1238-57T) was banded on a 6 inch rubber mill at 150 C. After the copolymer had attained the mill temperature, 24 g. of sodium met-hoxide dissolved in 100 ml. of methanol was added to the copolymer over a period of minutes as working of the copolymer on the mill was continued. Melt blending 01f the composition was continued for an additional 15 minutes during which time the initially soft, fluid melt became stiff and rubbery on the mill. However, the polymer could still be readily handled on the mill. The resulting product was found to have a melt index of less than 0.1 g./ minutes and resulted in transparent, as compared to opaque for the copolymer base, moldings of greatly improved tensile properties.
EXAMPLE II To a solution of 50 g. of an ethylene/methacrylic acid copolymer containing 10 weight percent of methacrylic acid and having a melt index of 5.8 g./ 10 minutes in 250 ml. of xylene maintained at a temperature of 100 C. was added 3 g. of strontium hydroxide dissolved in 50 ml. of water. Gelation followed immediately. The product was recovered by precipitation with methanol and washed thoroughly with water and acetone. The final dry product was found to have a melt index of 0.19 g./ 10 minutes and resulted in glass clear moldings.
EXAMPLE III To 50 g. of an ethylene/methacrylic acid copolymer containing 10 Weight percent of methacrylic acid and having a melt index of 5.8 g./ 10 minutes milled at a temperature of to C. on a 6 inch rubber mill was added gradually 6.3 g. of magnesium acetate (x i-H O) in 25 ml. of water. Milling was continued for 15 minutes at which time the evolution of acetic acid had ceased. The product had a melt index of 0.12 g./l0 minutes and resulted in clear, resilient moldings.
EXAMPLE IV To 50 g. of an ethylene/itaconic acid copolymer having a melt index of 9 g./10= minutes and containing 3 percent by weight of the copolymer of itaconic acid was gradually added 3 g. of sodium hydroxide in 2.0 ml. of water while the polymer was being worked on a 6 inch rubber mill at a temperature of C. Upon addition of the hydroxide, the polymer melt became stiff, transparent and elastomeric.
EXAMPLE V To 50 g. of a copolymer of ethylene and maleic anhydride, containing 7 weight percent of copolymerized maleic anhydride and having a melt index of 8.5 g./ 10 minutes, being milled on a rubber mill at a temperature of 135 C., is added 22.8 g. of zinc monoacetate monostearate. After 15 minutes on the mill a transparent, tough resilient polymer product is obtained having sufficient melt flow for fabrication into film by standard melt extrusion. Repeating the experimental procedure with zinc acetate an intractible resin is formed within 10 minutes of milling, preventing further milling. The resin could not be extruded into a film using standard melt extrusion.
EXAMPLE VI To 50 g. of a copolymer of ethylene and methacrylic acid, containing 10 weight percent of copolymerized methacrylic acid and having a melt index of 5.8 g./l0 minutes, being milled on a rubber mill at 130 C. are added the following components in the order indicated: (a) 3.25 g. zinc oxide, (in) 11.7 g. stearic acid, and (c) 2.5 g. of acetic acid. Only after the addition of the acetic acid does the melt become clear and an increase in viscosity is observed. After 10 minutes of further milling the copolymer is removed. Although the melt index is reduced, the resulting ionic copolymer is suitable for melt fabrication.
EXAMPLE VII An ethylene/methacrylic acid copolymer containing 10 percent methacrylic acid was banded on a two roll mill at C. and 3.6 weight percent of powdered sodium hydroxide was added over a period of 2 minutes. Milling was continued over a period of 10 minutes to ensure homogeneity. The ionic copolymer obtained was reduced more than tenfold in melt index and was glass clear and resilient. When extruded as a melt, the ionic copolymer could be drawn into fibers having pronounced elastic recovery.
Specific examples of the ionic copolymers of the present invention and their properties are shown in the following tables.
Table I shows physical properties of ionic copolymers obtained from an ethylene/methacrylic acid copolymer with monovalent, divalent and trivalent metal ions. The ethylene/methacrylic acid copolymer employed contained 10 weight percent of the acid and had a melt index of 5.8 g./l0 minutes. In addition to the improvements shown in the table, all these ionic copolymers exhibited excellent bend recovery which was not exhibited by the 9 copolymer base. The tests were carried out on compression molded sheets of the ionic copolymer.
ionic copolymer are compared and contrasted against the How number which corresponds to the melt index, except Table I Metal Cation Na+ Li Sr' Mg++ Zn++ Al+++ Metal Anion CI-I O- OH" 011- 011 0- CH30O 0- 01-1 000- Weight percent of Cross linking Agent 4. 8 2. 8 9. 6 8. 4 12. 8 14 Melt Index, g./
min 5.8 0. 03 0. l2 0. 19 0. 12 0. 09 0. Yield Point 1 in p.s.i 890 1, 920 1,906 1, 954 2, 176 1, 920 1, 035 Elongation l in percent 553 330 317 370 326 313 347 Ult. Tens. St. in
p.s.i 3, 400 5, 200 4, 920 4, 900 5, 862 4, 315 3, 200 Stifiness 10, 000 27, 600 30, 000 32, 400 23, 800 30, 170 15, 000 Transparency (visual) Hazy Clear Clear Clear Clear Clear Clear Table II shows the effect of varying concentrations of crosslinking agent and varying concentrations or carboxylic acid groups on the solid state properties of an ethylene methacrylic acid copolymer employing sodium methoxide as the crosslinking agent. The term stoichiometric as employed in the table indicates such quantities of the metal ion as are necessary to form ionic links with all of the polymer carboxylate groups.
that a temperature of 250 C. and a weight of 5000 g. is employed. Polyethylene which is crosslinked by peroxides or by ionizing radiation shows no flow for the conditions employed to measure the flow number. As can be seen from the table, at low shear stresses, i.e., under conditions at which melt index is measured, the ionic copolymers have low melt indices as compared to the base copolymers. However, at higher temperatures Table 11 Percent Methacrylic Acid 5 10 10 10.. 10 16, Percent Sodium Added Excess of Stoi- 70% 0f Stoi- 90% 0f Sto1- Sto1chiom Excess of stoi. E e of st i.
chiom. chiom. chiom. chiom. chiorn. copolymer Base Melt Index in 5 5.8 5.8. 5.8. 5.8 25.
g./10 min. Melt Index of Crosslinked Poly- 0.34
mer in g./10 min. Yield Point 1 1,300 Elongation 273 Ult. Tens. Str. 1 3,550 Stilfness 1 14,200 Transparency Slight Hazo 1 ASTM-D-412-51T. 7 ASTM-D-747-58T.
Table III illustrates the ionic crosslinking of ethylene/ dicarboXy-li-c acid copolymers using sodium acetate as the crosslinking agent. The table also illustrates that the crosslinking is more efiective with high molecular weight copolymers than with low molecular weight copolymers, although with both a significant decrease of melt flow is obtained in the melt indexer.
and under higher shear stresses the ionic copolymers show greatly improved flow.
Table IV further illustrates some of the requirements which must be met to obtain the ionic copolymers of the present invention. Thus, the use of zinc metal (Product No. 7) which is not ionized, does not result in any ionic crosslinking. Zinc oxide, which is ionic when dissolved Table III Percent Melt Index Yield Ult. Tens. Elongation St'fincss 2 Copolymer Sodium in g. /10 mm. Strength 1 Strength in percent 1 in p.s.i. Transparency Hydroxide in p.s.i. in p.s.i.
Ethylene/3 wt. percent maleic anhydride copolymer 1, 000 18 180 200 18, 000 Opaque. D 1. 2 0. 1 1, 300 2,100 290 17, 400 Hazy. Ethylene/2-3 wt. percent 6. 8 250 00 520 19, 000 Opaque.
methyl hydrogen maleate copolymer Do 1. 8 0.1 1, 350 3,100 380 23, 500 Hazy Ethy1ene/2-3 wt. percent malcic acid copolymer 4 5 1, 420 80 450 24, 600 Opaque. Do 6 N0 flow 1', 440 3, 000 260 17,000 Hazy. Ethylene/6 wt. percent itaconic acid copolymer 320 8 33 15, 800 Opaque. Do 2. 0 11 528 1, 900 180 3,000 Hazy.
Table IV shows the surprising melt properties of the ionic copolymers. The ionic copolymers illustrated were obtained by reacting aqueous or methanolic solutions of the crosslinking agents indicated in the table with the copolymers indicated on a two roll mill at temperatures of 150 to 200 C. until homogeneous compositions were obtained. In each instance sufiicient quantities of the crosslinking agent were added to neutralize all of the acid in water and when employed as a crosslinking agent (Product No. 8), results in only a partial ionic copolymer because zinc oxide does not dissolve sufficiently in water or other polar solvents. Zinc stearate is not efiective as a crosslinking agent (Product No. 9) to give rise to an ionic copolymer because the stearate radical remains in the polymer. As can be seen from the combination of a monocarboxylic acid with a trivalent metal (Product groups. The melt index of the copolymer base and the No. 6) a borderline improvement in the melt flow properties is obtained at higher shear stresses which is explained by the greater ionic attraction between the metal ion in a higher valence state and the carboxylic acid group. The inoperability of divalent metal ions and dicarboxylic acid groups (Products 21 and 17) to result in ionic copolymers of the present invention is also illustrated. These polymers are believed to have such strong ionic bonds that they in effect act like regularly crosslinked polyolefins. The table further illustrates the wide variety of metal ions which are suitable crosslinking agents. Additionally, the table also shows that the presence of a third monomer does not interfere in the formation of the ionic copolymers of the present invention.
12 EXAMPLE X Table IV Comonomer Copolyrner Ionic Copol- Flow Product No. Oon1onomcr(s) Cone. Crosslinking Reagent Base M.I., ymer MI. in Number in g./l min. g./l0 min. g./l0 min.
10. 0 Sodium Hydroxide 6. 3 0.03 4. 9 10.0 do 5.8 No flow 5.5 10. 0 Lithium Hydroxide 5. 8 0.12 6. 5 10. 0 Zinc Acetate 5. 8 0. 13 7. 0 10. 0 Magnesium Acetate. 5. 8 0. 107 6. 5 10. 0 Aluminum Hydroxide 5. 8 0. 2 0. 5 10. 0 Zinc Metal 5. 8 6.5 10. 0 Zinc Oxide 5. 8 0. 98 10. 0 Zinc Stearate. 5.8 4. 8 10. 0 Nickel Acetate 5.8 0. 25 10. 0 Cobalt Acetate 5. 8 0.13 10. 0 Sodium Carbonate 5. 8 0.05 10. 0 Tin Acetate 5. 8 0. 17 10. 0 Sodium Methoxide 5. 8 0.03 10. 0 Sodium Formats.. 5. 8 0.08 6 Sodium Hydroxide 9.0 0.11 6 Strontium I-Iydroxide 9. 0 No flow 6 Zinc Oxide 9. 0 No flow 3 Sodium Hydroxide 300 No flow 3 Lithium Hydr0xide 300 0.008 1% Zinc Acetate 300 N o flow 22 plus }Sodium Hydroxide 5. 5 0. 45
Methacrylic Acid 5 Vinyl Acetate A 3 plus Magnesium Acetate 5. 5 0.12 5. 8
Methacrylic Acid 5 Methyl Methacrylate l 4 D1118 Sodium Hydroxide 3.6 0.16 6. 2
Methacrylic Acid 5 Styrene 15 25 plus do 6.0 0.13 7. 5
Methacrylie Acid 5 EXAMPLE VIII EXAMPLE XI An ethylene/methacrylic acid copolymer containing 10 percent of methacrylic acid was ionically crosslinked with sodium hydroxide until 76 percent of the carboxyl groups had been neutralized. The melt index of the resulting polymer was 0.65 g./1O minutes. This resin was extruded through a one inch extruder equipped with a tubular film die and take-oiI. The ionic copolymer was extruded into 0.5 mil film using a 225 C. temperature for the extruder barrel and a 250 C. temperature for the die. The resulting film was completely haze-free and transparent. Dart drop test gave a value of 375 g. at 0.5 mil thickness. Comparable values for polyethylene =0.92. g./cc.) are 50 g. Pneumatic impact was 7.4 kg.-cm./mil; a polyterephthalate ester film has a value of 6.5 kg.-cm./mil. In addition to its excellent impact resistance, this film displayed marked shrinkage when immersed in boiling water making it ideal for many packaging applications. X-ray examination showed the film to be biaxially oriented.
EXAMPLE IX Using the ionic copolymer of Example VIII, a mil wire coating was produced on #14 copper wire. A three and one-quarter inch Davis-Standard wire coater fitted with an 0.124 inch tapered pressure die was employed. Extrusion was carried out at 450 ft./minute using temperature settings of 475 F. on the barrel and 490 F. on the die and quench temperatures of 200 F. to 72 F. A very smooth, glassy, coating was obtained displaying excellent toughness and electrical properties. Polyethylene having the same melt index could not be extruded into a continuous smooth wire coating under these conditions.
Using the ionic copolymer of Example VIII, four ounce Boston Round bottles were prepared. The resin was extruded through a two-inch ext-ruder fitted with a crosshead tubing die (0D. inch, I.D. inch) and blown into a bottle using a 4 ounce Boston Round bottle mold. The resin was heated to C. in the extruder. T-he extrusion screw speed was 25 rpm. The bottles obtained were stiff, transparent and directly printable.
The foregoing examples and experimental data have demonstrated the surprising combination of improvement in solid state properties and retention of melt properties obtained by the compositions of the present invention. One of the more apparent improvements obtained is that of transparency. Hydrocarbon polymers are generally not transparent in all but exceptionally thin forms and even there special techniques such as quenching and drawing must be employed to obtain a measure of transparency. The copolymers of the present invention, however, can be made to be transparent even in thick molded sections. Another solid state property which is markedly improved by ionic crosslinking is the resilience or bend recovery of the copolymer. In contrast to hydrocarbon polymers which have a slow and incomplete recovery from bend, the copolymers of the present invention snap back when deformed and assume their original shape. The improvement obtained in tensile properties and stiffness is apparent from the data presented in the tables. In this respect the copolymers of the present invention exhibit greatly surprising properties. In contrast to peroxide-crosslinked polyethylene where the stiifness is decreased by crosslinking, the ionic copolymers exhibit even greater stiffness and rigidity than the unmodified base polymer. Other solid state properties improved by ionic crosslinking are toughness and stress-crack resistance. The impact strength of thin films made from ionic copolymers is equal to and better than that of polyterephthalate films which are considered the toughest plastic films commercially available. Tests designed to measure stress-crack resistance of hydrocarbon polymers using detergents commonly used in such tests failed to result in failures and, thus, the ionic copolymers are considered to be free from stress-cracking.
The ionic copolymers of the present invention also exhibit highly surprising rheological properties. Thus, al though having extremely low melt indices, which would indicate that the ionic copolymers are not metal 'fiabricable, the opposite is true in that the ionic copolymers can be melt extruded, injection molded and compression molded with ease. This is explained, of course, by the difference in shear stress exerted on the melt in a melt indexer and in an extruder, for example. At low shear stresses the high melt strength of the polymer results in low melt flow. However, once this is overcome by a higher shear stress, the ionic copolymers flow readily. The combination of high melt strength at low shear stresses and good melt fiow at high shear stresses is highly desirable in all applications requiring forming of the melt subsequent to extrusion such as in bottle blowing in which an extruded parison is blown into a bottle and in thermoforming in which molten sheet is forced against a mold by means of a vacuum. In both these fabrication techniques, the polymer melt becomes unsupported during some part of the fabrication cycle and it is, therefore, highly desirable that the polymer melt have a high melt strength and a good retention of shape. Similarly, the ionic copolymers of the present invention are extremely useful for the preparation of foams in that they overcome the extremely low strength of the foamed but not yet solidified polymer which has been a major problem in foam extrusion and which frequently has caused the collapse of the foam.
An additional advantage that can be obtained in the copolymers of the present invention is coloration. By proper choice of metal ions and combinations of metal ions many colors can be produced in the ionic copolymers. This method coloration has advantages over polymer dyeing in that dyes have a tendency to exude from hydrocarbon polymer-s and frequently are not compatible therewith. It also has an advantage over coloration by pigmentation in that the coloration is more uniform and even, particularly in light colors. Furthermore, colored compositions can be made transparent.
The ionic copolymers may be modified, if desired, by the addition of antioxidants, stabilizers, fillers and other additives commonly employed in hydrocarbon polymers. The ionic copolymers can be blended with each other and all hydrocarbon polymers in general to achieve improvement in properties of those polymers with which the ionic copolymers are blended. It is generally preferred to employ additives which do not interfere with the ionic crosslinks, i.e., compounds which do not meet the requirement of crosslinking compounds set forth above or if ionic in nature to employ such metal ions as would complement the metal ions used in the crosslinking. Generally, however, additives do not interfere with the ionic crosslinks since they are not of the type which would result in metal ions and, furthermore, are employed in very small quantities. If desirable, the copolymers of the present invention can be blended with other hydrocarbon polymers to meet particular needs of an application. In order to realize the surprising prop erties obtained in ionic copolymers, it is essential that the ionic copolymers do not contain any significant number of covalent crosslinks, since the latter would obscure and overshadow the ionic crosslinking.
The high molecular weight ionic copolymers of the present invention can be extruded into films of excellent clarity, fibers of outstanding elasticity and resilience, pipes with superior stress-crack resistance, wire coatings with improved cut-through resistance and good dielectric properties despite the presence of metal ions, and foamed sheets; they can be further injection molded into intricate shapes and closely retain the dimension of the mold; they can be vacuum formed, blow molded and compression molded with greater ease and better properties than linear hydrocarbon polymers. Ionic copolymers can, furthermore, be drawn and uniaxially or biaxially oriented. Ionic copolymer surfaces, are printable and adhere well to adhesives commercially available. Thus, they can be laminated to paper, metal foil and other plastic surfaces. The adhesion of the ionic copolymer is so good that they themselves can be employed as adhesives. Low molecular weight ionic copolymers, particularly are useful for such purposes. Many other uses and modifications of the ionic copolymers of the present invention will be apparent from the foregoing description and it is not intended to exclude such from the scope of this invention.
I claim:
1. Ionic copolymers of a-olefins having the formula RCH=CH Where R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms, and u,13-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, said copolymers having from 10% to 90% of the carboxylic acid groups ionized by neutralization with metalions uniformly distributed throughout the copolymer, said copolymer being a direct copolymer of the a-olefins and the unsaturated carboxylic acid in which the carboxylic acid groups are randomly distributed over all molecules and in which (1) the a-olefin content of the copolymer is at least 50 mol percent, based on the a-olefin-acid copolymer, (2) the unsaturated carboxylic acid content of the copolymer is from 0.2 to 25 mol percent, based on the a-olefin-acid copolymer, and (3) any other monomer component optionally copolymerized in said copolymer is monoethylenically unsaturated, and said metal ions having an ionized valence of from one to three inclusive when the unsaturated acid is a monocarboxylic acid and an ionized valence of one when the unsaturated acid is a dicarboxylic acid and said metal ions being selected from the group consisting of uncomplexed and complexed metal ions, said ionic copolymers having solid state properties characteristic of crosslinked polymers and melt-fabricability properties characteristic of uncrosslinked, thermoplastic polymers.
2. Ionic copolymers of ethylene and an a,/8-unsaturated monocarboxylic acid having from 3 to 8 carbon atoms, said copolymers having from 50% to of the carboxylic acid groups ionized by neutralization with metal ions having an ionized valence of from one to three inclusive uniformly distributed throughout the copolymer, said metal ions being selected from the group consisting of uncomplexed and complexed metal ions, said copolymer being a direct copolymer of ethylene and the unsaturated monocarboxylic acid in which the carboxylic acid groups are randomly distributed over all molecules and in which the ethylene content of the copolymer is from to 99 mol percent, based on the ethylene-acid copolymer, and the unsaturated monocarboxylic acid content of the copolymer is a complementary amount from 10 to 1 mol percent, based on the ethylene-acid copolymer, said ionic copolymers having solid state properties characteristic of cross-linked polymers and meIt-fabricability properties characteristic of uncrosslinked, thermoplastic polymers.
3. Ionic copolymers of claim 1 in which the c p-ethylenically unsaturated carboxylic acid is monocarboxylic.
4. Ionic copolymers of claim l in which the a-olefin of formula R-CH:CH is ethylene and the a,fl-ethylenically unsaturatd carboxylic acid is monocarboxylic.
5. Ionic copolymers of claim 1 in which the ot-olefin of formula RCH CH is ethylene and the o fl-et hylenically unsaturated carboxylic acid is a dicarboxylic acid naving from 4-8 carbon atoms.
6. The ionic copolymer set forth in claim 5 wherein the metal ions are complexed metal ions selected from the group consisting of complexed metal ions of metals in Groups II, III, IV-A and VIII of the Periodic Table of Elements.
7. The ionic copolymer set forth in claim 3 wherein the metal ion is an ion of a metal in Group I of the Periodic Table of Elements.
8. The ionic copolymer set forth in claim 7 wherein the metal ion is an ion of an alkali metal.
9. The ionic copolymer set forth in claim 3 wherein the metal ion is an ion of a metal in Group II of the Period Table of Elements.
10. The ionic copolymer set forth in claim 9 wherein the metal ions are magnesium ions.
11. The ionic copolymer of claim 3 wherein from 50 to 80 percent of the said 0a,,B-UI1S21t11I21'ECd carboxylic acid is neutralized by the said metal ions.
12. The ionic copolymer set forth in claim 4 wherein the u,B-unsaturated monocarboxylic acid is acrylic acid.
13. The ionic copolymer set forth in claim 4 wherein the c o-unsaturated monocarboxylic acid is methacrylic acid.
14. The ionic copolymer set forth in claim 2 wherein the metal ions are alkali metal ions.
15. The ionic copolymer set forth in claim 14 wherein the metal ions are sodium ions.
16. The ionic copolymer set forth in claim 2 wherein the metal ions are ions of a metal of Group II of the Periodic Table of Elements.
17. The ionic copolymer set forth in claim 16 wherein the metal ions are zinc ions.
18. The ionic copolymer set forth in claim 4 wherein the copolymer is an interpolymer of ethylene, methacrylic acid and a third copolymerizable monomer.
19. The ionic copolymer set forth in claim 18 wherein the third copolymerizable monomer is vinyl acetate.
20. The ionic copolymer set forth in claim 18 wherein the third copolymerizable monomer is methyl methacrylate.
21. The ionic copolymer of claim 3 wherein the aolefin is a mixture of ethylene and propylene.
22. The ionic copolymer of claim 3 wherein the metal ions are complexed metal ions selected from the group consisting of complexed metal ions of metals in Groups II, III, IV-A and VIII of the Periodic Table of Elements.
23. The ionic copolymer set forth in claim 5 wherein the metal ions are alkali metal ions.
24. The ionic copolymer set forth-in claim 5 wherein the a,B-unsaturated dicarboxylic acid is maleic acid.
25. The ionic copolymer set forth in claim 4 wherein the u,B-unsaturated monocarboxylic acid is methyl hydrogen maleate.
26. The ionic copolymer set forth in claim 5 wherein the a e-unsaturated dicarboxylic acid is fumaric acid.
27. The ionic copolymer set forth in claim 5 wherein the ot,,8-unsaturated dicarboxylic acid is itaconic acid.
28. The ionic copolymer set forth in claim 5 wherein from to percent of said carboxylic acid groups are ionized by neutralization with metal ions.
29. The ionic copolymer of claim 28 wherein the metal ions are sodium ions.
30. The product of claim 4 in film form.
. The product of claim 4 in foamed form.
. The product of claim 4 in funicular form.
. The product of claim 4 in tubular form.
. The product of claim 4 in the form of a coating. The product of claim 30 in biaxially oriented form.
References Cited by the Examiner UNITED STATES PATENTS 2,599,123 6/1952 Pinkney 260-78.5 2,646,425 7/1953 Barry 260-88.1 2,798,053 7/1957 Brown 260-881 2,854,357 9/1958 Johnson et al. 260-785 3,132,120 5/1964 Graham 260---86.7
JOSEPH L. SCHOFER, Primary Examiner. L. WOLF, Assistant Examiner.
Patent Citations
Referenced by
Original Image


text:
Topic: Brann vs Rosenborg
Brann won 3-1 in their previous meeting at Lerkendal on November 9th, and are still undefeated in the Royal League, but have not managed to win a home match yet. Memelli is suspended for this match.
Rosenborg have struggled so far in the Royal League, and does not seem to care about the competition at all.
Brann to win and the match to end with more than 2.5 goals.

subset: commoncrawl


text: Media Contact: Jhodi Redlich, 401-874-4500KINGSTON, R.I., Feb. 12, 2014 – The University of Rhode Island is offering a chance to learn from the ultimate networker. If you're looking for a job or want to create a new one, you won't want to miss a chance to meet the energetic author Daniel Seddiqui on March 19. Free and open to the public, this networking event will be held at 7 p.m. in Swan Hall, 60 Upper College Rd. on the Kingston campus.


text:
LAS CRUCES, N.M. (Oct. 24)-The New Mexico State men's basketball team was voted to win the WAC title in the WAC Coaches' Preseason poll and second in the media poll. Senior forward Tyrone Watson and sophomore guard Daniel Mullings earned Preseason All-WAC honors.
The 10 head coaches selected the Aggies to finish first with five first-place votes and 77 points. Utah State captured second place with five first-place votes and 76 points. Denver took third place with 65 points. With 54 points, Louisiana Tech secured the fourth spot. UT Arlington (48) and Idaho (45) followed closely behind in fifth and sixth place, respectively. UTSA was picked seventh with 31 points, while Seattle was selected eighth with 22 points. San Jose State (18) and Texas State (14) were selected ninth and tenth, respectively.
Utah State junior guard Preston Medlin was tabbed as the league's preseason player of the year. Mullings earned a first-team nod along with Denver junior forward Chris Udofia, Idaho center Kyle Barone and Louisiana Tech sophomore guard Raheem Appleby. Second-team selections include Kevin Butler (UT Arlington), Jeromie Hill (UTSA), James Kinney (San Jose State), Kyisean Reed (Utah State) and Watson.
The conference media poll selected Utah State as this year's favorite. Utah State received 232 points and 15 first-place votes. New Mexico State was picked second with 223 points and eight first-place votes. Denver garnered 181 points and one first-place vote for third place followed by Louisiana Tech with 162 points. Idaho was fifth with 144 points followed by UT Arlington with 137 points and one first-place vote. UTSA was seventh with 104 points, followed by Seattle (77) in eighth, San Jose State (61) in ninth and Texas State (54) in tenth.
Medlin was named the preseason player of the year, and Utah State junior forward/center Jarred Shaw, a transfer from Oklahoma State, was picked as the preseason newcomer of the year. The All-WAC team included Medlin, Appleby, Barone, Mullings and Udofia.
2012-13 Preseason Men's Basketball Coaches Poll
Rank Teams (1st Place Votes) Points
1. New Mexico State (5) 77
2. Utah State (5) 76
3. Denver 65
4. Louisiana Tech 54
5. UT Arlington 48
6. Idaho 45
8. Seattle U 22
9. San Jose State 18
10. Texas State 14
Preseason All-WAC Teams
First Team
Raheem Appleby, So., G, Louisiana Tech
Kyle Barone, Sr., C, Idaho
Preston Medlin, Jr., G, Utah State
Daniel Mullings, So., G, New Mexico State
Chris Udofia, Jr., F, Denver
Second Team
Kevin Butler, Sr., F, UT Arlington
Jeromie Hill, Jr., F, UTSA
James Kinney, Sr., G, San Jose State
Kyisean Reed, Sr., F, Utah State
Tyrone Watson, Sr., F, New Mexico State
Player of the Year: Preston Medlin, Utah State
2012-13 Preseason Men's Basketball Media Poll
Rank Teams (1st Place Votes) Points
1. Utah State (15) 232
2. New Mexico State (8) 223
3. Denver (1) 181
4. Louisiana Tech 162
5. Idaho 144
6. UT Arlington (1) 137
8. Seattle U 77
9. San Jose State 61
10. Texas State 54
Preseason All-WAC Media Team
Raheem Appleby, So., G, Louisiana Tech
Kyle Barone, Sr., C, Idaho
Preston Medlin, Jr., G, Utah State
Daniel Mullings, So., G, New Mexico State
Chris Udofia, Jr., F, Denver
Preseason Player of the Year: Preston Medlin, Jr., G, Utah State
Newcomer of the Year: Jarred Shaw, Jr., F/C, Utah State


text:
The great video game experiment
You won't find Kokoromi on your Xbox
BY Kevin Gillich
Photography by Richmond Lam
In Montreal, independent artists are as common as poutine and potholes. But Kokoromi, a collective of artists and video game developers, has sidestepped the Converse-wearing, indie-rock-loving crowd by working with an underused artistic medium: video games.
"To me, video games are the medium with the most potential," says collective member Phil Fish. "Games can be moving art, they can be social tools used for change—you name it." Video games have come a long way since the early days; some explore concepts as complicated as city planning and human relationships, but the majority of them are still developed by large gaming studios. That's why last winter Fish and friends Heather Kelley and Damien Di Fede decided to start Kokoromi (Japanese for experiment).
Fish and Kelley met while working at Ubisoft, an international game developer with offices in Montreal. The group wanted to create experimental and artistic video games and to nurture a more independent local video-game scene. "Right now, the gaming scene in Montreal is a bunch of high-powered executives networking," says Fish. Major video-game developers such as Ubisoft, A2M and Electronics Arts have studios here. All three are known for mainstream games based on movie and TV franchises or sports.
Last November, Kokoromi held its first event, Gamma 01, which attracted six other games, including one from Toronto and two from Pittsburgh. The collective's entry, Glee, featured game play that was generated by ambient noise: think what Space Invaders might be like if the alien ships moved in time with whatever song happened to be piping out of your stereo as you played.
The event also served as a contrast to last November's Arcadia video game festival, also held in Montreal, an event flush with advertising dollars from big video game names like Nintendo and Xbox.
The success of their event convinced Kokoromi that the scene in Montreal is worth nurturing. Interested participants are mostly people who work for the big developers but crave a more creative outlet. The group aims to help people develop their talents outside the nine-to-five world.
Kokoromi also knows they have to convince others that video games are a medium worth working in. "It's still a young art form," says Di Fede. "There isn't the same sort of understood language [as other art forms]. Film, for example, is a little more readily understood by people because they watch a lot of movies and they've been exposed to it their entire lives."
"I think our goal will have been reached when there is a YouTube of games, when it is as popular as something like making videos," says Kelley.


text:
Hey guys,
I recently completed this website in Drupal. It's my first time using Drupal, and although it's a long learning curve, I survived. As you can tell it's a pretty simple website design with the main purpose of getting email subscribers.
Carter Cutlery: http://www.cartercutlery.com/
Let me know what you think.
All in all it's quite nice. One thing to check – in Firefox 3.5 on the front page there, the text is sitting up in the knife. So you can't read the first sentence. Seems to be positioned with IE all right. I'm also noticing some positioning issues with the right side when you are viewing/buying items in the cart. May be related.
Just curious what spurred the decision to go with Drupal? Was the cart a drupal cart that the customer wanted to use?
Thanks xheathen,
Strange… The text looks fine over here in 3.5. Are you on a mac per chance? I haven't check that.
I'm glad IE is working for you. I've got some bug over here where IE is not loading the CSS at all. Makes it difficult to test…
Yea, about Drupal: Client had a very crappy coldfusion site (which was only static HTML) and a Godaddy shopping cart; both ugly. He didn't care about what program was used.
I have done a lot of work with WordPress, and just a touch of work with Joomla. I wanted to learn enough about the largest OS website projects to be able to use the best programs for the different website proposals I get. I heard the "If you have a hammer, everything's a nail" quote, which really struck home for me since I had fallen in love with WordPress. I didn't want to be a "Oh yea, I could make that in WordPress" Developer. :geek: I wanted to be a "I've tried everything, and WordPress is the best for that" Developer. :ugeek: Only 50% serious on that one. Drupal is a huge program that does a lot automagically. I'm very impressed with Ubercart so far though- well worth making the site in Drupal.
Drupal is intense! I really enjoyed working with it, but I had a team and I really felt I needed it…seemed like a lot to learn just on my own. The idea of nodes/blocks/views is amazing though and I can see the potential. Even whitehouse.gov is using Drupal now!
As far as the site, its nice…although try turning on CSS Compression (under performance) so IE doesn't choke on the massive number of stylesheets.
I just completed this site in drupal:
We wanted to integrate Ubercart eventually but its on hold for quite some time.
Anyway, as far as your site goes, the one thing that really peeves me of the automatic start of the audio…for surfers like me who love their music loud, it makes me want to click away really quickly when a site does that. Otherwise, the site is very professional and I love the huge banner pictures with the opaque red background. The one other thing I would do is see if the navigation could stand out a bit more, for some reason the top links just don't seem like links…perhaps even center it?
Oh and the text does the same for me. I changed the #mission { bottom:20px } to bottom:6px and that fixed it.
Yea, it is definitely intense. Great for huge sites, way to much for small sites IMO. I may come across another site that needs it… we'll see.
oooooh, that could definitely be the problem in IE. I was afraid of doing that because it totally broke another dev website I was working on in Drupal… *crosses fingers* *flips switch* *success* Good point. It works in IE again. Yeay.
Cool. I like the design. The logo is hiding behind the nav in my FF 3.5, though.
Yea… I have two clients now with that. (At least it's only on the home page…)
Yea. That was intentional to try to send most people to the four main sections (which are those four icons all over the place).
Thnx. I wanted to keep the 20px spacing everywhere so I brought the font-size down 1px. Looks better over here. How's it look now?
Thanks for the tips and ideas, guys.
yea… no idea. I have a feeling my FF has morphed into it's very own version of FF… I call it v3.strange :?
Huh… I can't seem to duplicate the issue any more. I've looked at it on the same computer and it's fine. Maybe there were some problems with not bringing in the CSS you mentioned with IE? In any case, one of these days I'll have to try and dig into Drupal. I've dabbled in Joomla enough to hate it, and by far my favorite no-Wordpress CMS is CMS Made Simple (although the support kind of sucks, but the overall implementation for clients is easy and almost as easy for them to understand how to use it out of the box), but I haven't even tried to stab at Drupal yet :)
Good. The CSS/Javascript optimization must have fixed it.
Yea, it's a great system with an equally epic learning curve. I've also haven't been able to create an easy-to-use admin area for "handing off to clients." Thankfully this client has a nerd working for him who can handle the interface.
I've seen that CMS before, and wish I had time to look into it (and all the other good ones…)
Not too bad, not too bad at all.
Here's my annoyances:
1)Seems like everything is cramped, it would really nice to have some whitespace (place where there's nothing but blank page, no images, no text) to let the design breathe, that way the users don't get overwhelmed with too much text.
2)The sound is okay, just don't make it play automatically. People don't expect websites to speak so often it's sort of annoying when they decide to every time you refresh the page (1st time okay, 2nd, 3rd, 100th, not so cool)
3)Along the lines of 1) use some line spacing, it makes it much more readable.
4)You might ant to style your fields and buttons so they match everything else.
5)The shopping cart is kind of hard to find which seems like it would be a pretty important part of the site.
That's my advice, I haven't been web developing half as long as you have, take it for what it's worth.
You must be logged in to reply to this topic.


text:
Tribeca Film has acquired North American rights to Toronto-bound "The Fitzgerald Family Christmas," a domestic drama written, directed and starring Edward Burns. On this Irish-American working class family comedy, Burns brings back old pals Connie Britton and Michael McGlone, who co-starred in Burns...Read More »
If you missed it, catch the replay of my live internet chat with writer/director Ed Burns about his film Newlyweds, just released on VOD and iTunes. It's a charming, wry romantic comedy about a couple whose in-laws invade their marriage, and it offers a fascinating, fresh model for how to m...Read More »
Edward Burns' latest film, Newlyweds, is a delightfully witty, sharply observed romance that comes with its own amazing origin story. Although you wouldn't guess it from the film's clear, bright look, it was shot for a pittance -- around $9,000, yes that's thousand &nda...Read More »


text:
Presented by Jeremiah Conway, Author and Professor
Date: Tuesday, May 14, 2013
Time: 4:00pm-6:00pm
Location: 301 Bailey Hall, USM Gorham Campus
Cost: FREE!
Credit: 0.2 CEUs ($20 processing fee required)
Registration: Please contact Christen Stande, 207-780-5055 or
firstname.lastname@example.com to register. Space is limited, pre-registration is required.
What leads people into teaching and what sustains this motivation? For many it is the possibility of making a difference in people's lives. This innate motivation is fragile and needs to be cultivated and nurtured. Without this care, it can easily end up lost, forgotten, or buried under countless duties and responsibilities.
Join us for a presentation by Professor Jeremiah Conway, author of the recent book—The Alchemy of Teaching. The Transformation of Lives—invites us to consider and reflect on the often messy, wondrous, sometimes chaotic struggle for human change that occurs in classrooms.
His book, which has received glowing national reviews, offers educators a literary glimpse into the heart of a teacher and classroom. Through his stories we are given a gentle, yet potent, reminder that teaching matters, it's a privilege and lives are at stake in it.
Presented by Jeremiah Conway
Professor Conway (Ph.D. Yale) is a professor of philosophy at the University of Southern Maine. He has received the University's Outstanding Teaching Award several times, as well as other prestigious awards. He has written over 40 published articles on philosophy, teaching, and his interactions with students.
Click here to download a copy of the poster (pdf).


text:
And then there were two.
The Blockbuster Video store at 3141 W. Colorado Ave. on the west side of Colorado Springs began a liquidation sale this week and is scheduled to close in May. That leaves two Blockbuster stores in the Springs — 3790 E. Woodmen Road and 6530 S. Academy Blvd. A spokesperson for Blockbuster said Thursday there are no plans to close those stores.


text:
Monday, September 14, 2009
13 months!!
Today Riley is thirteen months old. I have two newsy bits regarding him to tell you before we get to the usual stats; first of all, yesterday he tried to climb our neighbour kid's bike and it fell over on him and he busted up his toe. The toenail was all black and hanging off, and the toe was red and swollen, and he wouldn't/couldn't walk on it yesterday evening. Poor baby! Today at boot camp he was visibly limping. Then at some point, I noticed the blood that was trapped under the toenail came out, and he seemed MUCH more comfortable, so maybe the pressure was the main problem. He still complains if it gets bumped, but he was running around at Ayden's soccer practice with no limp, so that is good! It was VERY cute this morning; I was showing my friend Rowenna his toe and he pointed at it, looked all sad and pathetic, and said "goo-woo, ba ba" in this very pathetic voice (obviously to elicit sympathy, which worked). SO CUUUUUTE!!!
The other bit of news is that tonight Riley did some sign language for the first time totally unprompted! He heard an airplane, looked at the sky, and moved his fist in the correct way for 'airplane,' while making the sound of a motor with his mouth. I LOVE this stage, where they use sign language to initiate conversation about things they notice or are interested in. It is awesome to see him communicate what he's interested in. We did baby sign language with our other two kids too, and found it very helpful in reducing frustration surrounding communication for that developmental period where they understand much more than they can say. And it is fun to be able to 'talk' before they can talk!
blackberry picking by the river
So. Today Riley is thirteen months old.
Weight, STILL 20.5 lbs (I wish he would hit 22 lbs already, so we could turn his carseat around!)
Height, 2 feet 5 inches
his brothers
momma milk
small dogs
other babies
hockey sticks
pine cones
sushi, including the seaweed
(I told you this kid loves food)
opening the shower door while you are in it
hot tubs
running water in sinks and tubs
creek water
dog's water dish
tickle monster
dropping food on the floor for the dog
climbing on the oven drawer to get to the stovetop
pulling hair
scratching people
diaper changes
getting dressed (except for his shoes and socks, which he loves)
lying down on his back in the water
carseat, though he is getting better at longer trips
large dogs
being put in the stroller
kisses from mommy (too busy for that business!)
feeling left behind
now can walk down stairs if holding someone's hand
communicates with sign language
makes proper car, truck, and airplane noises
uses ride on toys
can operate screw off/on tops if loose
climbs like an orangutan
can hit a ball with a hockey stick
remembers where he hid objects even a few days later (sometimes)
has invented a whole new level of 'switch nursing'--he prefers to breastfeed by having both breasts available and switching from side to side every 3 or 4 sucks, which helps me to develop better flexibility in my back ;)
can balance on one foot for 3 or 4 seconds
can walk backwards
can run forwards
dances any time he hears music
blows to cool down his food
learning to use a fork
knows how to use a spoon
waves 'bye bye' and 'hello'
sleeps well between 8:30 pm and 4:30 am--wakes to nurse about two or three times between 4:30 and 7:00, on average
orients his entire existence around trying to escape out the front or back door and running out onto the street. Where he's going, nobody knows, but he's determined to get there. Maybe he figures God sent him to the wrong family? THESE PEOPLE ARE KOOKS, YOU CAN'T BE SERIOUS?! I'M NOT STAYING HERE ANOTHER MINUTE!
We love, love, LOVE you, baby Einstein!
I'm so glad you're mine.
2 comments:
- Louise and Gary Chapman said...
He's acting like a 2 year old! Wow. What a cutie. Guess I should get on the signing...I was def. a little more on it with Kai.
- September 14, 2009 at 10:04 PM
- Dana said...
What an accomplished little boy!! Not to mention adorable. Hugs and kisses.
- September 15, 2009 at 6:51 AM
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David Cochard (Artist)
Key Largo
imported edition
$57.00 Friday July 22, 1899, 9:27. The heavy diving helmet has just been closed again on the head of Pablo, the diver whom you recruited yesterday at the Siren Bar. In a few minutes, he will be at work and you already dream of grandiose wealth! Under the...


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We are live at the Fox Cities Performing Arts Center in Appleton to learn about the big milestone they are celebrating, as well as to hear some more about Flashdance: The Musical.
Fox Cities PAC Homepage
Fox Cities PAC Homepage
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On Sale
This striking lamp adapts the best of mid-century modern design with a contemporary flair. The translucent crystal rectangular lamp body has a clean, impressive look. The crisp linen shade complements the linear form. This lamp displays modern elegance. Crystal glass body. Linen shade. From the Vienna Full Spectrum crystal lighting collection.
Look to Vienna Full Spectrum to deliver innovative, European inspired designs that complement today's home décor. From chandeliers to sconces to pendants and even clocks, Vienna Full Spectrum has its finger on the pulse of the new millennium. We welcome you to discover the perfect complement for your home's décor by browsing our collection of beautiful Vienna Full Spectrum lighting fixtures.
Shipping and Delivery Information - For item EU31305 if ordered by 1 pm Pacific Time


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One of the main points low-power FM advocate Prometheus Radio Project has made to the FCC as the agency crafts expanded service rules for LPFMs concerns second-adjacent waivers.
Prometheus representatives say a second-adjacent frequency waiver standard modeled after the FM translator rules is appropriate. Current second-adjacent frequency restrictions keep LPFM stations out of urban areas because of lack of frequency space, according to the advocacy group.
NAB opposes any relaxation of the second-adjacent channel spacing requirements. NAB executives have reiterated to FCC officials that the broadcast lobby interprets the Local Community Radio Act as prohibiting the commission from reducing the minimum second-adjacent channel distance separation requirements between low-power and full-service FM stations, but permits waivers under certain circumstances.
NAB believes such waivers should be considered only in "truly exceptional circumstances," according to a summary of their conversation.
NPR too urged the agency to only issue such waivers under limited circumstances "as Congress intended so that newly constructed LPFM stations are not forced to ameliorate interference problems, including terminating service," the broadcaster wrote in a summary of a lobbying visit.
NPR cautioned the FCC to be careful not to upset the balance of interests as it facilitates additional LPFM service yet also protects primary and existing secondary broadcast service from interference.
LPFM advocates Prometheus Radio project and the Amherst Alliance support the concept of the commission approving second-adjacent channel spacing waivers more routinely.
NPR also raised concerns about "significant alterations" to the LPFM service rules, in particular authorizing 250 watt LPFMs, which would depart from the LPFM service Congress envisioned when it authorized the service, according to NPR. LPFM advocates want their stations to have more power.
The Local Community Radio Act says that LPFM and translators should be treated equally. Ultimately, only way to do that is to treat them identically. Translators are not a source of interference, because there is no area where people could be that a 2nd or 3rd adjacent interfering signal can be strong enough to interfere with the signal being protected. The same rule should apply to LPFMs.
I'm wondering why does NAB and NPR always oppose anything about LPFMs?
What are they scare about!? In LPFM new talents and programming could evolve, to make FM/AM-radio exiting to listen, not like todays auto-jock-computerized-boring-radio.
LPFM isn't a competitor to NAB and NPR. The competitor are services like Pandora, Spotify and the listeners own music on his/her smartphone.
I program a 100 watt LP-FM. With good propagation, it gets about 10-12 miles. With bad propagation, it gets about 5 miles. An LP-FM should be able to be heard consistently 10 miles around its transmitter site. The NAB is advocating for the big broadcasters, yet their charge is to promote all of broadcasting. LP-FMs should be allowed 250 watts, where stations will fit. It's not unreasonable.
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Now that the schedule is set and the draft is over, it's time to take a closer look at each of the Ravens 2013 opponents. Next up: The Cleveland Browns.
Weeks 2, 9: Cleveland Browns
Sunday, Sept. 15, 1 p.m., M&T Bank Stadium
Sunday, Nov. 3, 4:24 p.m., Cleveland Browns Stadium
2012 Record: 5-11
Key offseason losses: WR-KR Josh Cribbs; K Phil Dawson (to San Francisco); DE Frostee Rucker (to Arizona); TE Ben Watson (to Saints);
Key additions: WR Davone Bess (trade with Dolphins), DT Desmond Bryant (from Oakland), QB Jason Campbell (from Chicago), OLB Quentin Groves (from Arizona), OLB Paul Kruger (from Baltimore), WR David Nelson (from Buffalo)
Top 5 draft picks: DE Barkevious Mingo (LSU, 1st round), CB Leon McFadden (San Diego State, 3rd round), S Jamoris Slaughter (Notre Dame, 6th round), DE Armonty Bryant (East Central (OK), 7th round), OT Garret Gilkey (Chadron State, 7th round)
Overview: The Browns could look dramatically different in 2013, beginning with the coaching staff. Rob Chudzinski, the Panthers' offensive coordinator the past two years, takes the helm for his first job as an NFL head coach. He's brought in Norv Turner as the offensive coordinator and Ray Horton as the defensive coordinator.
The Browns worked to upgrade their 23rd-ranked defense via free agency, signing former Ravens linebacker Paul Kruger, linebacker Quentin Groves and defensive tackle Desmond Bryant.
The Browns also went defensive in the draft, taking LSU defensive end Barkevious Mingo with their first pick. Overall, though, it was a thin draft for the Browns, who had only two picks in the first five rounds. They had no second-round pick after grabbing Josh Gordon in the supplemental draft last year, and then sent their fifth-round pick to the Dolphins in the trade for wide receiver Davone Bess. They also traded two other mid-round picks for higher picks next year.
Bess, who had 61 catches with the Dolphins last year, should help upgrade a passing attack. No one on the Browns had more than 53 receptions, and Browns receivers had huge problems with dropped passes.
Who, exactly, will lead the offense remains a question. Second-year quarterback Brandon Weeden is the incumbent, but the Browns brought in veteran Jason Campbell to compete for the job, and the jury is still out on whether either is the answer.


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MMA News
Vinny Magalhaes Should Be Signed By The UFC
by Jamie McAllister:
Chugging along with as much focus and determination as the #RallyForMarkHunt train is also a campaign on Twitter by the dedicated followers of Vinny Magalhaes to get the BBJ specialist back to where he belongs in the UFC via numerous tweets to the UFC brass!
The BJJ specialist who was a finalist on the Ultimate Fighter show losing via knockout to Ryan Bader in the first round. After this loss Magalhaes lost his next bout in the UFC and was promptly cut. Ever since then Magalhaes has won 7 of 8 fights and achieved a finish in all of his wins via submission as well as some TKO and in his last bout scored an impressive head kick knockout over Mikhail Zayats defending his M1 Light Heavyweight Championship just in case you have not seen it here is the fight video (I advanced it to the knockout but feel free to watch the full fight)
Also he is the current ADCC Champion earning a gold medal in the Heavyweight Division beating Fabricio Werdum in the finals. And to top that all off he has an unbreakable arm !
On a more serious note I personally do not think there is anyone more deserving of a UFC recall than Vinny Magalhaes his recent record speaks for itself in terms of finishing winning 7 of 8 in conjunction with the style he has finished some of the fights in !
14 Responses to "Vinny Magalhaes Should Be Signed By The UFC"
Well that is all true but they forgot the BIGGEST point! He is under contract with M-1! People write up some of the dumbest articles without clearly thinking before writing.. Always saying this guy should be in the UFC.. Well maybe he should be its prolly cause he is under a contract of a different promotion so he cant be apart of the UFC!
Hey Scotty,
I think I read somewhere that the last fight in M1 was the last on his contract. But I believe its still one of those things where they can match any other offer and keep him if they decide too……….read that somewhere after the owner thru a fit when Vinny won his last fight
but then again I could be completely wrong. lol butttttttt im not getting mad bout it HA
no, not anymore. is now a free agent
Vinny deserves to be in UFC and if he isn't signed it will be because USUAL bullshit Dana White politics.
He was released weeks ago !
My own arm hurts after watching that!
he definitely will be back
I agree on merit. The guy is just such a jackass that I couldn't careless.
That dude is JACKED! ALL NATURAL or yer a FAGGET!
The Guy already was in the UFC, he lost twice in a roll against Bader & Eliott Marshall so they let him out. But maybe he's improved? I didn't really follow him that much.
I believe UFC said he had to improve reason they released him.. But he has been pretty dominate since he left.. All his wins have been either by submission or KO and on a 5 fight win streak.. I think he should get another shot!
Think he would do well now ! Possible title run ?
He has sick BJJ, probably the best in the LHW division and his stand up has improved so I agree if his contract is up he deserves to be signed by the UFC.
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February 23, 2015 by Tim Letcher
The Ole Miss Rebels were in the mix for the SEC West title last season. Read More
February 10, 2015 by Tyler Brett
Chad Kelly is an incredibly talented quarterback who has derailed his career with off-field incidents. Can he turn things around at Ole Miss? Read More
February 3, 2015 by Alexander Christian
Since landing at Ole Miss, Hugh Freeze has proven to be one of the nation's best recruiters. But as National Signing Day is upon us, the Rebels are treading water with a number of top recruits. Read More
December 31, 2014 by RantSports Staff
The TCU Horned Frogs showed their worth against the Ole Miss Rebels in the Peach Bowl. Read More
December 30, 2014 by Michael Terrill
These are the top five NFL Draft prospects in the Peach Bowl played by the TCU Horned Frogs and Ole Miss Rebels. Read More
December 17, 2014 by Alexander Christian
Atlanta will play host to the most intriguing matchup of the bowl season outside of the playoff games when the No. 9 Ole Miss Rebels, take on the No. 6 TCU Horned Frogs. Read More
December 16, 2014 by Alexander Christian
Outside of the playoff matchups, no bowl game is getting as much attention as the Peach Bowl. Here are five bold predictions for what is arguably the most intriguing matchup of the bowl season. Read More
December 9, 2014 by Ryan Ratty
In a battle of two of the best teams not in the College Football Playoff, TCU will try to take its anger out on Ole Miss. Read More
December 8, 2014 by Sam Mattfolk
Both TCU and Ole Miss have had their share of disappointment this season, but his has also been historic seasons for each. The Big 12 and SEC will do battle in the Peach Bowl in Atlanta. Read More
December 7, 2014 by Tim Letcher
The TCU Horned Frogs will face the Ole Miss Rebels in the Chick-fil-A Peach Bowl, it was announced on Sunday. Read More
November 30, 2014 by Rick Stavig
Which bowl game will the Ole Miss Rebels play in? Here's some possible scenarios. Read More
November 25, 2014 by Connor Muldowney
Mississippi State will travel to Ole Miss to take on the Rebels in week 14. Who will come out on top? Read More
July 16, 2015 by Seth Lassen
The Ole Miss head coach has a strong opinion on a very polarizing issue. Read More
July 14, 2015 by Barrett Pfeiffer
Ole Miss' offseason battle at the QB spot will be won by none other than Chad Kelly. Read More
June 13, 2015 by levidunagan
The Ole Miss Rebels enter the 2015 season with a wealth of talent at both wide receiver and tight end. The Rebels return four key players, including Evan Engram and Laquon Treadwell. Read More
May 18, 2015 by Brian Kalchik
These are the five must-watch games for the Ole Miss Rebels in 2015. Read More
March 21, 2015 by Tim Letcher
The Ole Miss Rebels had a truly special season in 2014. Read More
March 19, 2015 by levidunagan
The Ole Miss Rebels return their most experienced and talented team in 2015. The Rebels need to manage expectations to reach the SEC Championship game for the first time. Read More


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When the Arab awakening swept through the Middle East last year, with waves of democratic protesters swallowing tyrants in Tunisia, Egypt, and Libya, no one could confidently predict what kind of political order would emerge from the ruins. Certainly the stability of the old order of autocracies was shattered, hopefully along with their characteristic corruption and stagnation. In the long term, there is still reason to hope for a democratic transformation similar to the one that eventually emerged in Eastern Europe at the end of the Cold War.
The danger that most concerned many U.S. policy analysts at the time, however, was a repeat of the Iranian revolution of 1979, which was hijacked by Islamic theocrats. The anti-American protests that targeted U.S. embassies throughout the Middle East last week suggest that at least in the near term, the greater peril may come from the model of Lebanon: a weak democracy with inadequate institutions and security forces that are unable or unwilling to confront the Islamic extremists in their midst. In the case of Lebanese Hezbollah, the extremists exploited that weakness to form a shadow state that has become too powerful to uproot.
Of course, the common thread that runs through the anti-American protests in Egypt, Libya, and Yemen is an anti-Islamic film made in California that went viral on the Internet. Events of the Arab Spring have also driven home the point that each of these countries is distinct, with different cultures and ethnic tapestries.
Yet there are similarities that have emerged in the past year in the fledgling democracies of the Arab Spring. In Libya, for instance, the newly-elected government has been unable to enforce its authority over as many as 200 private, well-armed militias. These bands, which have no shortage of weapons looted from Muammar el-Qaddafi's arsenals, range from ordinary Libyans to virulently anti-Western Salafists to hard-core supporters of al-Qaida (such as the shadowy Islamic extremist group Ansar al-Sharia, which some experts suspect in the death of U.S. Ambassador Chris Stevens and three other Americans).
"This [attack] didn't come out of the blue," said Barak Barfi, a research fellow at the New America Foundation who spent six months in Libya during the revolution. There were earlier attacks in the country this summer, he noted, including a rocket-propelled grenade fired at the British ambassador's convoy and a bomb attack at the gates of the U.S. consulate. If Libya doesn't move to integrate its militias and create national security services that can deal with these fomenting threats, Barfi said in a phone call from Turkey, "there are going to be long-term problems with these Islamist groups because they're going to be able to grow, create an infrastructure, draft more people. Then we're not going to be looking at a couple hundred people ... but thousands."
While the assault on the American Embassy in Cairo appears to have been spontaneous in reaction to the anti-Muslim video posted on YouTube, the attacks there also highlight the security void that has developed since last year's revolution. Egypt's security services, deeply unpopular after violently suppressing protesters, have been largely marginalized—and jihadists have responded by ramping up their presence in the Sinai and carrying out attacks like last August's deadly cross-border assault on southern Israel.
The U.S. Embassy was also overrun in Yemen, another Arab Spring country and home to al-Qaida's most active branch. Because security forces have been focused on unrest in the capital for much of the past year, al-Qaida has been able to seize significant territory in the south. Until the new president, Abed Rabbo Mansour Hadi, directed a successful offensive there, militants actually governed several major cities. Since the government's offensive, the group is suspected of a string of attacks, including a recent assassination attempt that nearly killed the country's defense minister in his convoy.
The only magnet more alluring to Islamic extremists than weak central governments and security forces is outright conflict and organized violence, especially conflicts that break down along the region's ethnic fault lines, whether between Sunni and Shiite Muslims, or Muslims and religious minorities. For instance, unrest coupled with the sectarian divide in Syria, between Sunni Muslims and Syrian President Bashar al-Assad's minority Alawite clan that runs the country, has given al-Qaida and other groups that share its ideology a "golden opportunity," according to Bruce Hoffman, director of the Center for Security Studies at Georgetown University. The Syrian rebel group Jabhat al-Nusra, suspected of links to al-Qaida, is gaining prominence as it brings more-experienced foreign fighters to the front lines, making it "far more active in recent months and far more consequential," Hoffman said.
The fight against Assad affords jihadists a rallying point against what they consider an Alawite infidel, according to a recent op-ed by Ed Husain, a senior fellow at the Council on Foreign Relations. "In the event of Assad's falling, al-Qaeda will probably gain de facto control of parts of Syria to serve as a new strategic base for jihadis in the Middle East, or at least enjoy tribal protection in the broader regions with Iraq and Jordan," Husain wrote in National Review. "A new government in Syria not only will be indebted to these fighters, but also will be in need of their cooperation to minimize the potential of militias fighting each other."
Of course, the first Arab tyranny to recently attempt the transition to democracy is Iraq, where political paralysis in the Shiite-led government has breathed new life into Sunni Al Qaeda in Iraq, which has launched a string of devastating bombings this year responsible for hundreds of Iraqi deaths. As if any more evidence was needed, Iraq's experience suggests that the transition to democracy in the Arab world will continue to be contested violently by Islamic extremists who sense opportunity in weakness.