text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 6, 1982
|Filing date
|Jun 16, 1980
|Priority date
|Dec 22, 1978
|Also published as
|Publication number
|Adolf Heslinga, Pieter J. Greidanus
|Original Assignee
|Nederlandse Centrale Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Referenced by (53), Classifications (32), Legal Events (1)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation-in-part of copending U.S. application Ser. No. 105,750 filed Dec. 20, 1979.
The invention relates to a method for preparing a polymer mixture; formed products obtained therefrom, such as granules, fibres, foils, foam; and a polymer alloy.
It has already been proposed to prepare moisture-absorbent and extensively swellable polymers of unsaturated carboxyl compounds, such as maleic anhydride, by polymerizing the carboxyl monomer with a crosslinking agent, such as a polyethylenically unsaturated compound, according to the method specified in U.S. Pat. No. 2,798,053. Such polymers are used as synthetic gums in the preparation of sticky or gel-like aqueous mixtures.
It is also known from British Pat. No. 1,200,106 that certain weakly crosslinked polymers with a large numer of hydrophilic units can be advantageously used as absorbing and binding liquids. As described in U.S. Pat. No. 4,192,727, such polymers, which are slightly crosslinked, partly hydrolyzed polyacrylamides, have been recommended as components of the filling material for disposable diapers and beds and of other similar sanitary products because of their ability to retain appreciably more aqueous liquid under pressure than an equal amount of fluffy cellulose or similar material. In some application of such extensively water-swellable polymers, however, difficulties have been encountered in containing the polymer after it has been saturated with the aqueous liquid.
It is desirable to have an extensively water-swellable, water-insoluble polymer in fibrous form, such as has been described in more detail in U.S. Pat. No. 3,983,095. Further, it is in general desirable to have polymers with an adjustable capacity of moisture absorption.
Furthermore, U.S. Pat. Nos. 4,160,754 and 3,939,123 have described water-swellable and water-absorbent materials obtained by other cross-linking reactions, such as between polyisocyanates and polyols. Moreover, many moisture-sensitive or swellable plastics have been developed on the basis of water-soluble polymers, such as polyacrylic acid, polyacrylamide and derivatives thereof, alone or combined with naturally occurring hydrophilic polymers, such as starch, cellulose and derivatives. These materials are known as synthetic hydrogels. In many cases they are manufactured in the form of powders, fibres, granulates, foils, etc. They are used for, among other things, medical and sanitary purposes. In this context, cf. Encyclopedia of Polymer Science and Technology, 15, 273-291.
These as well as the many other water-soluble or water-degradable packaging materials which are now available have major drawbacks. Specifically, processibility at high temperatures (such as 120� to 200� C.), which are customarily used in the processing of thermoplastics, is often very poor. This is particularly so when polymers having side groups are activated at elevated temperatures. Crosslinking reactions often cause the initially thermoplastic characteristics to be lost, so that continuous processing at high temperatures becomes very difficult or impossible to implement.
On the other hand, many hydrophilic polymers, such as polyvinyl alcohol, cellulose, starch and derivatives thereof, have very high melting or softening ranges, or do not melt or soften at all. In such cases, too, the conventional thermoplastic processing techniques cannot be used or are very difficult to operate. In addition, crosslinking reactions or dehydration may take place, causing the original properties of the structures to be irreversibly changed.
Accordingly, there is a need for synthetic polymers having hydrophilic properties comparable to starch, proteins and cellulose which can be prepared and processed according to the available technology for thermoplastics (e.g., extrusion, injection molding, foil extrusion and calendering) without causing untimely irreversible changes or reactions in the polymers.
The invention aims at providing a method of preparing hydrophilic synthetic polymers which eliminates the drawbacks of the prior art preparation methods.
To this end, the method according to the invention is characterized in that a polymer alloy is prepared which is stable and homogeneous up to high temperatures, initially made mainly from component (a) which is one or more polymers of high molecular weight having anhydride groups and component (b) which is one or more polymers of high molecular weight with groups which have the ability to interact with hydrogen atoms to form hydrogen bonds. The term "polymer alloy" is well known in the art. Note particularly the article entitled "Polymer Alloys," Polymer Science and Technology, Plenum Press, New York, Vol. 10 (1977).
To prepare the polymer alloy, a solution of component (a) is first prepared in an organic solvent, to which solution component (b) is added. Component (a) in the dissolved state is protolyzed in whole or in part prior to or after the addition of component (b) under the action of protolyzing agents. Thereafter, the solvent is removed. Components (a) and (b) each have molecular weights of at least 104.
In general, component (a) has highly polar characteristics, but is nevertheless insoluble in water. Under the influence of water, however, at certain pH and temperature conditions, it may be converted into a water-soluble polymer by the formation of free carboxyl groups or carboxylate ions. The solubility in water is a function of pH.
A major aspect of the invention is the discovery that a homogeneous polymer alloy can be prepared. Generally speaking, substances of high molecular weight which are made up of different chemical structures are not or only slightly homogeneously miscible in all proportions (cf. among others, Encyclopedia of Polymer Science and Technology, 20, 694-697). The preparation of homogeneous polymer alloys was generally considered impossible or very difficult.
Surprisingly, it has now been discovered that a polymer alloy may be prepared from a component (a) which is a high molecular weight polymer of an alkene-unsaturated monomer and a component (b) which is a polymer having an ester side chain.
Component (a) may be at least one high molecular weight polymeric material having an appendant anhydride group and a molecular weight of at least 10,000. Most preferably, this component is made by reacting an alkene-unsaturated monomer with maleic anhydride. The alkene-unsaturated monomer may be of the styrene type having the formula: ##STR1## wherein R is hydrogen, an alkyl group having from 1 to 6 carbon atoms, or a halo atom; the benzene ring may be substituted with low molecular weight alkyl, hydroxy, nitro or halo groups. The most preferred compound of this class is styrene, though alpha-methyl styrene, para-alpha-methyl styrene, and para-t-butyl styrene may also be used. In addition to styrene-type monomers, another alkene-unsaturated monomer which is preferred in preparing component (a) is methyl vinyl ether. This monomer, when reacted with maleic anhydride, forms a copolymer sold under the trademark Gantrez AN-169, a trademark of GAF Corporation. The component (a) which is a copolymer of styrene and maleic anhydride is referred to hereinafter as (SMA).
Component (b) must be at least one polymeric material having a molecular weight of at least 10,000, which is reactive with hydrogen ions. Examples of such compounds include polymers based on acrylic esters, nitriles and amides, e.g., acrylonitrile, methylmethacrylate, cyclohexylmethacrylate; vinyl and vinylidene halides, e.g., vinyl chloride, vinylidene chloride; vinyl carboxylates, e.g., vinyl acetate, vinyl trimethylacetate, vinyl formate. Furthermore, as polymeric materials, polyesters and nylon may be used. The most preferred are vinyl, cellulose, acrylic and methacrylic esters. Specific examples are: poly(vinyl acetate) (PVAc), cellulose triacetate (CTA), cellulose aceto-butyrate (CAB), poly(ethyl acrylate) (PEtAcr) or poly(methyl metacrylate) (PMMA).
These components (a) and (b) are miscible in all proportions below certain temperatures because of a slight interaction between the polymer species. At a specific temperature, however, segregation or phase separation will take place. This temperature is called the critical temperature, Tc. Tc is a function of the molecular weights of the components and the mutual weight ratio.
Furthermore, it has been found that miscibility at high temperatures (100�-200� C.) can be adjusted by increasing the physical interaction (association) of the polymer components. This increased interaction is brought about by partial hydrolysis (generally protolysis) of component (a), before or after the addition of component (b). The protolysis introduces carboxyl groups along component (a), which furnish hydrogen bonds for the association between components (a) and (b).
By a "partial protolysis" is meant that only a portion of the anhydride groups is opened by use of the protolyzing agent. Generally from 5 to 80% of the anhydride groups are protolyzed, preferably from 10 to 15%. The materials used for protolysis may be water, alcohols, and amines. As a practical matter, these latter compounds have from 1 to 10 carbon atoms.
The preferred degree of protolyzing of component (a) and the ratio between component (a) and component (b) is dependent on a variety of factors and generalizations are difficult. However, the degree of interaction between component (a) and component (b) is directly related to Tc. The higher the Tc, the stronger the interaction between component (a) and component (b).
It is of major importance to conduct the protolyzing of component (a) after component (a) has been dissolved in an organic solvent to get a homogeneous reaction.
The manner of evaporation of the solvent or drying is an important part of the present invention. Specifically, it should be carried out so that the aforementioned increased interaction is maintained. An instructive example of polymer alloys according to the invention consists of (a) a copolymer of styrene and maleic anhydride and (b) poly(vinyl acetate). With this alloy the principal effect of the invention, hereinafter referred to as "solvent alloying", is shown.
In order to further illustrate the invention, the following figures are attached:
FIG. 1 shows the relationship of protolysis time and critical temperature, Tc, for solutions of polymer alloys containing various amounts of water.
FIG. 2 shows the relationship of protolysis time and critical temperature for solutions of polymer alloys containing copolymers of styrene-maleic anhydride and, respectively, poly(vinyl acetate) cellulose triacetate, cellulose acetobutyrate and poly(ethyl acrylate).
FIG. 3 shows the degree of swelling in water of hydrogels in relation to the ratio of the components (a) and (b).
FIG. 4, entitled "Reaction Equations", shows, in Equation 1, the dehydration reaction of the hydrated or hydrolyzed copolymers in a dry atmosphere and Equation 2 shows the formation of a semi-ester during the protolysis reaction.
An example of the preparation is as follows:
A mixture of polymers SMA and PVAc is prepared by forming a solution in, for example, butanone. The copolymer (SMA) may be prepared separately by the solution polymerization of styrene and maleic anhydride or a previously prepared polymer may be dissolved. Following the completed polymerization up to the desired molecular weight, partial protolysis of the SMA is effected by adding, for example, water or alcohol to the polymer solution. Heating and catalysts will accelerate the protolysis. Consequently, continued heating of the solution of SMA increases the Tc. The increase of Tc can be expressed as a function of time, concentration and temperature (FIG. 1).
After the protolysis, the PVAc is added to SMA solution, either in solid form or likewise as a solution in butanone, whereupon the polymers are mixed.
Although the concentration of the solution is not critical, a solution of about 20% polymer content is generally used for practical reasons. The dissolving technique is of major importance for obtaining an optimum degree of homogenization. Association of the two components (a) an (b) in the solvent allows the alloying effect to be attained in a short time to a maximum and effective extent. The degree of association of components (a) and (b) is increased by partial hydrolysis (protolysis) of the copolymer as described.
The solid homogeneous polymer alloy may thereafter be obtained by a drying process in which the solvent is evaporated (distilled) in a closed system at temperatures ranging from 100� to 200� C. (generally, from 130� to 160� C.). The distillation or drying process can be accelerated by working under reduced pressure (for example, 10 to 500 mm Hg).
The drying process is performed in a closed system to facilitate solvent recovery and to insure that the atmosphere has a certain degree of humidity. Preferably, the humidity should be from 0.1 to 0.5% by weight. A fully "dry" environment should be avoided. The reason for this is to avoid the dehydration of the hydrated or hydrolyzed copolymers having anhydride groups into the cyclic anhydride configuration (the reversal of the reaction). (In this connection, cf. reaction equation 1 on FIG. 4.) If dehydration occurs, the association is reduced and phase segregation will take place. The drying process should therefore take place in highly specific conditions. It has surprisingly been found that in certain conditions during drying association is not decreased but, rather, increased. Furthermore, in a closed system the drying process can also be combined with the hydration or hydrolysis reaction.
With the rapid rise of temperature during the drying process, a rapid conversion from anhydride groups to COOH groups occurs in the closed system. As the drying takes place, because the butanone distills off more rapidly, the water content in the solution increases. This, too, accelerates the conversion process.
The relation between the temperature and the state of the resin takes the following course in the drying apparatus: ##STR2##
The Tc rises as a result of fast protolysis by H2 O beyond 100� C.
It is evident that many added substances with reactive functions, such as alcohols, can be chemically bonded to the residual anhydride groups during the drying process. In this connection, cf. the reaction equation 2 on FIG. 4, where a rapid protolysis reaction takes place in the apparatus at an elevated temperature during the drying process to form a semi-ester.
It naturally is also possible to add the widest variety of substances before the drying process: plasticizers, stabilizers, modifiers, adjuvants, fillers, pigments and dyes, lubricants, biologically active substances, etc.
The preferred polymer alloys of the invention at issue have the following properties: thermoplastic; clear; density about 1.2 to 1.3 g/cm3 ; softening the processing temperatures from 100� to 200� C.; excellent resistance to aliphatic hydrocarbons, oils and fats; soluble in lower alcohols and ketones; and capable of swelling in aromatic hydrocarbons.
The mechanical properties of these polymer alloys are a function of the molecular weights of the components and of the ratio of the two components. For example, a high PVAc content lowers the modulus of elasticity or raises the elongation at break. This is shown in Table A below:
TABLE A__________________________________________________________________________TENSILE TESTING OF FOIL SAMPLES (POLYMER ALLOY OF SMA ANDPVAc) STRIPS (1.5 cm WIDE) LENGTHWISE FROM SAMPLESFIXED LENGTH 10 cm; DRAWING RATE 3cm/min; THICKNESS ca. 0.1 mm Yield Ultimate Elastic ElongationFoil Stress, Stress, Modulus, at Break,Composition kgf/cm.sup.2 kgf/cm.sup.2 kgf/cm.sup.2 percenta/b-SMA/PVAc Aver. S.A.* Aver. S.A.* Aver. S.A.* Aver. S.A.*__________________________________________________________________________CopolymerNo. 1010/90 138 9 113 8 7,000 2,000 250 4020/80 211 8 139 5 11,000 1,200 90 4030/70 425 15 410 80 17,000 2,500 6 3.040/60 -- -- 487 4 15,000 3,000 2.3 0.2CopolymerNo. 910/90 97.0 3.0 101 3 6,500 2,000 294 820/80 185 9 134.5 1.5 10,500 1,300 220 2530/70 343 9 201 10 16,500 2,000 35 940/60 -- -- 470 40 20,800 1,200 2.6 0.3__________________________________________________________________________ *S.A. = standard deviation
The modulus (or the rigidity) can be further lowered by adding plasticizers and/or other modifiers. This is shown in Table B below:
TABLE B______________________________________EFFECT OF PLASTICIZERS: POLYMER RATIO, ca. 1:1(50/50) PLASTICIZER CONTENT, ca. 30 percentPlasticizer Ultimate Yield Elastic ElongationCode Stress Stress Modulus at Break______________________________________PPA 135 71 3000 220%SPA 133 152 5000 59%PolyethyleneComparisonMaterial 150 120 2400 400%______________________________________ PPA = pentaerythritol SPA = sorbitol triacetatetripropionate-
The new type of polymer alloys of the invention can be processed by using the customary techniques for extrusion from melts and apparatus or techniques for casting from organic solvents. Foils can be fabricated according to known foil blowing techniques. Extrudates and granulates may be obtained by standard extrusion techniques.
Fibres can be manufactured according to the usual techniques; monofilaments, for example, from the melts by dry or wet spinning techniques on the basis of direct coagulation from organic solvents in water or aqueous solutions.
The new compositions of the invention posses the advantage of being extrudable from a melt, either as such or in combination with suitable plasticizers. Suitable plasticizers are here defined as those substances which are adequately compatible with the polymer mixtures and do not give rise to undesired exudation, phase segregation, reactions, etc. Examples are the phthalate type, e.g., dibutyl phthalate and dioctyl phthalate, and the ester type, e.g., glycerine triacetate, glycerol ester and citric acid ester.
The polymer alloys have both hydrophobic and hydrophilic groups. This manifests itself in a typical characteristic, e.g., swellability, particularly in water (see FIG. 3). Swellability of polymer mixtures is evidence of the interaction of the polymer components on a molecular scale (alloying) and also the strong interaction between the different polymer species.
The polymer alloy also has the properties of polyanhydride resins; the presence of residual anhydride group causes the alloy to be reactive even in solid form, so that secondary chemical reactions are possible. Secondary reactions are possible, for instance, with water, alcohols, ammonia, amines and epoxy compounds. (In this connection, cf. the reaction equation 2 of the formula sheet.) These reactions are used in order to improve the processability of the alloys during processing (e.g., extrusion).
A few percents, i.e., 1 to 5 wt. %, of fatty alcohol such as stearyl alcohol may be added to the polymer solution before drying. The formed stearyl esters act during processing as internal, nonexuding lubricants. Clearly, very many modifications, both with regard to chemical and to physical properties, are possible in this manner by means of secondary reactions. The hydrophilic as well as the hydrophobic characteristics can thus be increased and decreased.
The polymer alloys are stable in dry conditions and when stored at normal atmospheric conditions with respect to temperature and relative humidity (50 to 60 percent). However, upon prolonged exposure to air of high humidity or in direct contact with water, a gradual conversion takes place from the anhydride group to the free dicarboxylic acid. The polarity (hydrophilic character) thus increases while the modulus (brittleness), measured in dry conditions, rises simultaneously. As a result of the conversion of the polyanhydride to polyacid or polyelectrolyte, the material assumes the properties of a stable hydrogel. The degree of swelling in water is a function of the degree of ionization of the composition of the polymer alloy, the polymer ratio and of the pH of the aqueous medium. Maximum swelling takes place at, for example, a pH of from 6 to 8, and minimum swelling at a pH of from 2 to 3 (in buffered solution). This phenomenon is reversible and is comparable with the familiar behaviour in water of proteins, such as gelatin and keratin.
The hydrogel accordingly possesses the characteristic properties of a polyelectrolyte and can also function, for example, in hydrogel form, as an ion exchanger by binding multivalent metal ions such as Ca, Cu, Zn and Cd. The hydrogels and xerogels fabricated by hydrolysis from the polymer alloys are stable because of the extensive interaction of component (b) with the hydrolyzed or ionized component (a).
The polyanhydride-polymer alloy can be rapidly converted into a hydrogel polyelectrolyte by reaction with strong organic or inorganic bases such as NaOH and KOH, and especially by ammonia, ammonia-in-water solutions, and organic amines. Crosslinking takes place in reactions with bi- or polyfunctional compounds, such as glycols (preferably, lower aliphatic glycols), di- and polyamines. The degree of swelling of the hydrogels can thus be varied as a result of reactions with both mono- and polyfunctional reactive compounds.
The polymer alloys according to the invention can be used for manufacturing synthetic products having a variety of properties.
The material can be in the form of granules, fibres, foils, powders and other forms known in the processing technology of polymeric materials. Of particular importance is the conversion by water into substances having hydrogel properties (or polyelectrolyte properties).
Especially important is the use of fibrous or powdery material in the form of a polyelectrolyte or salt for moisture absorption. Also possible is the use of hydrogels, formed in secondary reactions, as ion exchangers.
As a result, the polymer alloys are particularly suitable for manufacturing polymer compositions for the controlled release of active constituents, specifically, under the action of water. Both the speed and the degree of swelling affect the delivery rate of the active constituents. The delivery rate naturally is also a function of form and size of the polymer mixtures (granules, powders, foils, fibres, etc.). Active substances may comprise such products as insecticides, fungicides, herbicides, biocides, feromones, repellents for the control of pests, plant diseases or the attack on plants by insects and/or other harmful organisms. Another application is for the controlled delivery of pharmacologically active substances.
If the polymer alloys are prepared in fibrous form, they can be converted by secondary reaction with strong bases into fibres having a high swelling capacity or moisture absorbency in water.
The completed, water-insoluble and water-swellable fibres are suitable for many purposes. These fibres can primarily be used in the manufacture of absorbent layers for sanitary products.
The above application can likewise be implemented by forming the polymer alloys into foils, films of thin sheets or strips. The swellability or absorbency is primarily a function of the ratio of the two polymers in the polymer alloy. Elevated concentrations of component (a) increase the swellability after secondary hydrolysis or ionization to form the hydrogel structures.
Furthermore, the polymer alloy according to the invention may comprise an additional component, such as the active materials noted above, a reactive component for modification of the polymer alloy during its preparation, or a foaming agent for forming a porous structure. As additional material, a filler, such as carbon black, chalk, fibres, can be added after or during the preparation of the polymer alloy.
In a vessel having a capacity of about 50 l, 30 l (25 kg) of methylethyl ketone (MEK), 3120 g of styrene, 3000 g of maleic anhydride, and 7.5 g of azo-bis-isobutyronitrile (catalyst) were successively mixed. The vessel was equipped with a heating jacket, a stirrer, a thermometer and a thermal safety device. The contents were heated while being stirred continuously. Initially, the contents were heated to 60� C. over a period of one hour and thereafter held at 60� C. for 2 hours; at 70� C. for 1 hour; and at 80� C. for 3 hours. The total polymerizing time was about 7 hours. The product had a viscosity of about 450 centipoises, a solids content of about 20% by weight, and a critical segregation temperature, Tc, of 41� C. measured with PVAc solution. (See Example II and FIG. 1.)
It will be understood that the degree of polymerization can be varied by altering the catalyst concentration and the reaction temperature.
By measurements of the intrinsic viscosity, the molecular weight was determined to be about 10,000 to 100,000 (J. of Applied Polymer Science 20: 1619 [1976]).
The solid polymer can be obtained by evaporation of the solvent or by precipation in excess methanol.
Upon completion of the polymerization of SMA as described in Example I, to 20% samples of the SMA solution MEK, sufficient water was added, with vigorous stirring, to prepare separate samples having water contents of about 0.1, 0.5, 1 and 2%, respectively. These water-containing solutions were heated for about 20 to 30 hours at 75� C. During heating the critical segregation temperature, Tc, was determined for the mixtures of the samples and poly(vinyl acetate) (PVAc) solution. FIG. 1 shows the rise of Tc for the PVAc/SMA mixture (the extent of protolysis) as a function of the water concentration and the protolysis time at 75� C.
The effect of temperature and water content on the rise of Tc was illustrated by the finding that the Tc of a PVAc/SMA mixture in MEK containing 1% water rose to 100� C. after 40 days of storage at 20� C., while a comparable mixture containing 2% water when heated to 75� C. obtained a Tc value of 100� C. after only 8 hours.
A series of samples were prepared by mixing approximately equal parts of the copolymer solution (20% SMA in MEK) and, respectively, a poly(vinyl acetate) solution, PVAc (M70, Hoechst); a cellulose triacetate solution, CTA (Tenite I, Eastman Kodak); a cellulose aceto-butyrate solution, CAB (Tenite II, Eastman Kodak); and a poly(ethylacrylate), PEtAcr, all of the latter in a 20% MEK solution. To the foregoing solution 1% water was added and the solutions were heated to 75� C. for differing protolysis times.
FIG. 2 shows the rise of Tc as a function of protolysis time at 75� C. At Tc the mixtures suddenly turned turbid as a result of segregation.
10 kg of the 20% copolymer solution of Example I was protolyzed with 10 g water at about 75� to 80� C. for about 16 hours. The Tc rose from 100� to 110� C. This protolyzed copolymer solution, in a vessel (boiler) having a capacity of 50 l, was mixed with 19.6 kg of MEK and 4.66 kg of solid PVAc. The PVAc was Mowilith-70, a suspension or bead polymerizate of Hoechst (Frankfort, Germany). The SMA/PVAc mixing proportion was 30:70. The solid PVAc was dissolved with slow stirring at a temperature of about 15� to 20� C. until a clear solution had been formed. The total solution of the polymer blend was 34.30 kg having a solid matter content of 20%.
Naturally it is possible to carry out the mixing operation with a PVAc solution in MEK. Predissolved PVAc has the advantage of rapid mixing with copolymer solution. Clearly, any desired polymer proportions can be rapidly obtained according to the above procedure.
In the drying process about 1000 kg of the polymer blend were dried with air in an industrial dryer (Luwa Filmtruder). Before drying, about 2 kg of stearyl alcohol (internal, non-exuding lubricant; C18 H37 OH) were stirred into this solution, in order to improve the processability of the solid alloy during processing. Use may naturally be made of other similar dryers as well.
Solid polymer alloy prepared following Example III has a density of from 1.2 to 1.3 g/cm3, and a modulus of elasticity, depending on moisture content and mixture ratio, of from 2,000 to 10,000 kgf/cm2 (viscous to hard).
The granulate can be processed in standard degassing extruders (double-screw), allowing the residual moisture content or solvent to be even further reduced.
Thermal stability tests show a slight increase in viscosity after 1 to 2 hours at 150� C., and some crosslinking after 1 hour at 190� C. The colour remains light yellow. Moisture absorption at high humidity (100 percent relative humidity) is about 5 percent for 30:70 polymer alloy; in boiling water, after 1 hour, about 10 percent. Under normal conditions, the material is stable and permanently thermoplastic.
Using the Luwa Filmtruder and the polymer alloy mentioned in Example III, the following drying tests were carried out:
______________________________________ Appear- Wall Yield of solid ance ofTest Input, temp., Vacuum polymer blend polymerNo. kg/h �C. mm of Hg kg/h blend______________________________________1 75 ca. 160 300 17 turbid2 60 ca. 160 400 14 slightly turbid3 60 ca. 180 400 15 clear4 50 ca. 180 500 12 clear5 75 ca. 180 200 18 slightly turbid______________________________________
The solid matter content of the extrudate formed from the above dried product was about 98 percent. The original Tc was about 100� C.
An additional 1 percent of water was added to about 1000 kg of resin mixture of Example III, followed by 2 hours of stirring and heating at 70� to 80� C. As a result, the critical temperature, Tc, rises to above 140� C.
______________________________________ Appear- In- Wall Yield of solid ance ofTest put, temp., Vacuum polymer blend polymerNo. kg/h �C. mm of Hg kg/h blend______________________________________6 75 ca. 160 300 16 clear[optimum]7 60 ca. 190 200 15 slightly turbid______________________________________
Test no. 6 shows the optimum drying, while in test no. 7 the drying was carried too far and the Tc dropped again.
These examples clearly indicate that the clear homogeneous polymer alloy is only obtained under specific conditions.
Starting from the solution of polymer alloys of Example III, drying tests have also been carried out with a small laboratory closed roller dryer, set up horizontaly and having two rollers with a screw. The input was about 7 kg/h (20 percent solution); the wall temperature from 140� to 150� C.; and the vacuum, 300 to 400 mm of Hg. The yield of polymer alloy was about 1.5 kg/hr. Its appearance was slightly turbid.
The resultant polymer alloy formed a continuous extrudate having a solid matter content of about 98 to 99 percent. The residual moisture content was 0.5 to 1 percent. The extrudate can be granulated immediately upon cooling.
The dryer of Example V was charged with a polymer alloy solution prepared from the copolymer solution according to Example I and PVAc (Mowilith-70) in the proportion of 30:70. Drying was carried out in the conditions of test no. 5 in Example IV. The extrudate was now fully white, opaque and of heterogeneous composition. The appearance was the result of phase segregation of the polymer components. In contrast with clear extrudates, the extrudates of Example VI did not swell.
Two percent of water was added to the copolymer solution of Example I (percentage of total substance), and the mixture was heated for 8 hours at about 80� C. Tc was now about 90� C. This was followed by mixing with PVAc and MEK so that the proportion of polymers was 50:50.
Drying in the apparatus of Example V was carried out at an input of 5 kg/hr, a temperature of 150� C., and under a vacuum of 400 mm Hg. The yield was 1 kg/hr and the product was colourless to light yellow and clear.
This example shows tests with poly(methyl vinyl ether/maleic anhydride) (Gantrez AN-169) as component (a) ##STR3## and cellulose aceto butyrate (Tenite II) and polyvinyl acetate (M70) as component (b).
The copolymer is dried for about 5 hours at a temperature of 130�-140� C. in order to obtain the pure anhydride form of the copolymer. The dried copolymer is dissolved in dry MEK to obtain a 20% solution. The resultant solution of component (a) is mixed with a 20% MEK solution of Tenite II. The Tc is about 5�-10� C. The copolymer is then hydrolyzed by the addition of 1-2% water at a temperature of about 20� C. After 1 week the Tc=50�-60� C.; after 2 weeks it is greater than 100� C.
The same test is carried out with poly(methyl vinyl ether/maleic anhydride) as component (a) and polyvinyl acetate as component (b), both as 20% solution in MEK. The mix ratio of component (a) to component (b) is about 50:50. The initial Tc=70� C. After 1 week with 2% H2 O at 20� C., it increases to 120�-130� C. The increase of Tc�50�-60� C. is because of partial hydrolysis. After swelling at a pH of 7 a stable hydrogel is obtained.
A solution of polymer alloy was prepared according to the method described and was composed of 50/50 SMA/PVAc polymer (1:1). Tc of the solution of polymer alloy exceeds 120� C. About 10 percent (related to dry matter content) of glycerin triacetate were added prior to desiccation. Following drying according to Example V, granulate was obtained from which blown foil was prepared by extrusion from a ring-shaped slit mold.
Properties of Foil: Thickness of foil, 50 to 60 u; clear; modulus of elasticity, 2,000 to 3,000 kgf/cm2 ; elongation, 200 to 250 percent; ultimate stress, about 100 kgf/cm2.
The elasticity of the foils of polymer alloys is largely a function of the moisture content of the material and the environment. Sensitivity to moisture can be controlled by the methods described on the basis of the nature of the plasticizers, modifiers, etc.
A polymer alloy was prepared as described in Example IX except the proportion of polymers was 30:70 and the plasticizer was 5% dibutyl phthalate (on polymer basis). The foils had properties similar to that in Example IX.
A solution of polymer alloy was prepared in MEK having a solid matter content of about 40 percent. The viscosity of the solution was 35,000 to 40,000 cps.
Using prior-art techniques and methods, the solution of polymer alloy was spun as a spinning liquid by wet-state injection into water as a coagulating bath of about 20� C. The spinnerette had 15 apertures with a diameter of 0.05 mm. The solution ejected formed fibres in the form of monofilaments, which could be continuously wound.
The resultant strand had about 5 to 8 dtex (gr/10,000/m) after conditioning at a 65% relative humidity, and the moisture content was 2 to 3 percent at 20� C. (dtex is a measure for filament thickness).
From the granulate obtained according to Example VII a fibrous polymer alloy was produced by known melt-spinning techniques in conventional apparatus. The fibres are ionized by post-treatment with ammonia or organic amines (obtaining then electrolytic properties), as a result of which a high water absorbency is obtained, the degree depending on the proportion of the polymers. The swelling capacity (/V) may range from 10 to 100 grammes water/grammes polymer alloy in deionized water.
In the polyelectrolyte form (being in the form of polyions), the fibers have properties of ion exchangers.
To 20% of solution of a polymer alloy in MEK according to Example III was added 10% of Chlorfenvinphos (Birlane concentrate Shell insecticide) based on the solid polymer content. The mixture was dried under the conditions described in Example IV, Test No. 3. The result consisted of 1.6 kg of dry extrudate, which was subsequently granulated. Part of the granules were ground to powder. The granules as well as the powder were used as a control agent for a soil insecticide. The delivery rate of the active substance can be regulated by partial or complete ionization of the polymer alloy, for example by water, ammonia, bases or other protolytic substances. The delivery rate can also be regulated by adjusting the releasing surface area (cf. powder and granules).
As has been shown in Examples V and VI, as well as in Examples II, III, IV and VII, homogeneous blending, i.e., alloying, is possible only if the drying process has been carried out at temperatures below the critical segregation temperature, Tc, of the polymer mixture. The homogeneity of the solid blend can be determined by conversion of the blend into a hydrogel by ionization in water with pH 7.0-7.5. (In homogeneous blends it will not swell.)
(a) The material of the invention prepared according to Example IV (Test Nos. 3, 4 or 6) can be converted by dilute (1%) ammonia or other bases into a solid hydrogel. This is shown by immersing about 4 grammes of extrudate (platelet, ca. 4�2�0.5 cm) for about 24 hours in an amount of a 1% ammonia solution sufficient to cause swelling. After the preliminary swelling for ca. 24 hr., swelling was continued in neutral water. The water was replenished until maximum swelling had been attained (final pH=7.0 to 7.5).
A stable hydrogel was formed having maximum swelling in neutral water of about 25 to 30 times the original dry weight. The water content of the hydrogel was about 96 to 97 percent. (30:70 polymer alloy.)
(b) A second polymer alloy was prepared as follows: Solutions in MEK of PVAc (M70, Hoechst), cellulose triacetate (Tenite I, Eastman Kodak), cellulose aceto-butyrate (Tenite II, Eastman Kodak), polyethyl acrylate, PEtAcr (synthesized in the laboratory) and poly(methylmetacrylate), PPMA (Plexiglas, Rohm and Haas and Lucite, Dupont), component (b) (total amount ca. 20 percent), were mixed with SMA, component (a), solutions in MEK according to Example I, being respectively partly protolyzed to Tc values beyond 100� C. In FIG. 3 this protolyzed compound is indicated by SMAp (p=protolyzed). The solid polymer alloys were prepared by drying the respective polymer mixture solutions at about 70� to 80� C. All solid samples were clear; no segregation occurred. From these solid polymer alloys samples (films about 0.5 mm thick) hydrogels were prepared by the technique described in Example XIII a). The equilibrium take-up of water or degree of swelling (Δ/V) in water of pH ca. 7.0-7.5 was measured as function of component ratio (a:b). The results are given in FIG. 3.
The volume increase (Δ/V) is shown to be a function of the a:b ratio as well of the whole molecular structure, i.e., physicalchemical properties of component (b). It is also clearly demonstrated that the hydrophility, i.e., moisture absorbing capability of the various polymer alloys, can be adjusted by mixing more or less component (a) in the polymer alloy.
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|May 18, 1976
|Nederlandse Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek Ten Behoeve
|Degradable plastics comprising a mixture of a styrene-maleic anhydride copolymer, polyvinyl acetate and an ester of a hemiformal
|Feb 12, 1973
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|Oct 18, 1988
|Nederlandse Centrale Organisatie Voor Toegepast- Natuurweten- Schappelijk Onderzoek
|Composition for the preservation of wood
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|Arco Chemical Technology, Inc.
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|Chemie Linz Gesellschaft M.B.H.
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|Apr 1, 1991
|Jan 7, 1992
|Arco Chemical Technology, Inc.
|Polymer compositions and absorbent fibers produced therefrom
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|Sep 29, 1992
|Arco Chemical Technology, L.P.
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|Aug 20, 1996
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|Mar 18, 1997
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|Nov 1, 2000
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|Method of binding binder treated particles to fibers
|Mar 18, 2002
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|Method of enhancing blood absorbence by superabsorbent material
|May 7, 2003
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|Method of binding binder treated particles to fibers
|Aug 26, 1999
|Apr 11, 2006
|Pvaxx Research And Development Limited
|PVA-containing compositions
|Aug 15, 2000
|Dec 5, 2006
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|Method of binding particles to binder treated fibers
|Mar 1, 2001
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|Method and apparatus for blowmoding capsules of polyvinylalcohol and blowmolded polyvinylalcohol capsules
|Dec 18, 2008
|Jun 4, 2013
|Philip Morris Usa Inc.
|Hollow/porous fibers and applications thereof
|Apr 16, 2013
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|Philip Morris Usa Inc.
|Hollow/porous fibers and applications thereof
|Mar 1, 2001
|Aug 14, 2003
|Stevens Henry Guy
|Method and apparatus for blowmoding capsules of polyvinylalcohol and blowmolded polyvinylalcohol capsules
|May 7, 2003
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|Oct 30, 2003
|Stevens Henry Guy
|Polymer processing method and tablet-forming apparatus
|Sep 19, 2002
|Mar 25, 2004
|Hansen Michael R.
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|Aug 5, 2003
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|Polyvinyl alcohol alloys and their preparation
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|Bic Soc
|Fuel compositions for fuel cells and gas generators utilizing same
|U.S. Classification
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|International Classification
|Cooperative Classification
|European Classification
|Jun 1, 1981
Owner name: NEDERLANDSE CENTRALE ORGANISATIE VOOR TOEGEPAST-NA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:NEDERLANDSE ORGANISATIE VOOR TOEGEPAST-NATUURWETENSCHAPPELIJK ONDERZOEK T.B.V., NIJVERHEID, HANDEL EN VERKEER;REEL/FRAME:003855/0315
Effective date: 19810424


text:
Last Sacrifice by Richelle Mead
Release Date: December 7th, 2010
Razorbill, 594 Pages
Sub-genre: Paranormal
Source: Gifted from Sash
Age Group: Young Adult
Series: Vampire Academy #6
They come first.
My vision was growing dimmer, the blackness and ghosts closing in. I swore it was like I could hear Robert whispering in my ear: The world of the dead won't give you up a second time. Just before the light completely vanished, I saw Dimitri's face join Lissa's. I wanted to smile. I decided then that if the two people I loved most were safe, I could leave this world.
The dead could finally have me.
Rose Hathaway has always played by her own rules. She broke the law when she ran away from St. Vladimir's Academy with her best friend and last surviving Dragomir princess, Lissa. She broke the law when she fell in love with her gorgeous, off-limits instructor, Dimitri. And she dared to defy Queen Tatiana, leader of the Moroi world, risking her life and reputation to protect generations of dhampir guardians to come.
Now the law has finally caught up with Rose – for a crime she didn't even commit. She's in prison for the highest offense imaginable: the assassination of a monarch. She'll need help from both Dimitri and Adrian to find the one living person who can stall her execution and force the Moroi elite to acknowledge a shocking new candidate for the royal throne: Vasilisa Dragomir.
But the clock on Rose's life is running out. Rose knows in her heart the world of the dead wants her back…and this time she is truly out of second chances. The big question is, when your whole life is about saving others, who will save you?
It took me a while to stop smiling like an idiot at the last page of the book. One word: INCREDIBLE.
The characters:
You love some and you hate some but sometimes you can't help but feel a little of both towards others. Adrian is endearing because he is so dedicated to Rose even though she puts him through the gauntlet of a love triangle, but there is only one person that Rose will ever really love – and that's Dimitri. Lissa becomes an unbelievably strong character and her boyfriend Christian takes the snarkiness down many, many notches and becomes Lissa's rock, especially when Rose is up to no good. There are many other supporting characters that I cannot say enough positive things about. But if there's one thing for sure, it's the camaraderie that these young adults feel towards each other. The all-entrusting love that they offer truly rivals the crew from Harry Potter. [Yeah, I said it.]
The Setting:
Everywhere the characters went, there was never a lack of detail in the description of the scenes on the author's part. I could easily see the images of their surroundings play through my head like I was watching a movie in high-definition. Whether it was Russia, Alaska, Montana, or Las Vegas, the details and beautiful descriptions were not something I was at a loss for.
The Plot:
From start to finish–the author SERIOUSLY had an ingenious and creative way for our lovably adventurous troublemakers [insert: rebels] to get into and out of trouble. The love of Dimitri and Rose was too strong to be stopped by spirit, death, or worse, un-death. Setting out to kill the love of your life that was unwillingly turned Strigoi is no small feat, but finding a way to bring him back to you–regardless of the consequences, is truly amazing. With the support and help of many friends, Rose attempts the unthinkable…the impossible. But how is she supposed to win when Dimitri's demons and guilt for what he did while he was Strigoi threatens to destroy their relationship? The only thing she CAN do…love him unconditionally.
The Ending:
Wow – just..*sigh*. I could NOT have been happier about the way that Mead decided to wrap up the series. I will try not to spoil it but pretty much everyone ends up happy and the Moroi-dhampir world will never be the same – for the better. I could have not hoped for a better way to sum up all of the trials and hardships that the characters endured, but when I asked – at what cost? Well the cost was great, but the result was far greater than anyone [except the author, of course] could have imagined.
I know a lot of people that read YA love the teen angst [I am among them], but to see a YA series that shows the meaning of true, unconditional, unstoppable love is something that I find to be the main reason that I enjoyed this series so much. So to any of you that are tired of the campy, angsty, shallow tales of starcrossed vampire/non-vampire lovers make sure you pick up this series so you can experience a whole new world of vampires, love, and traditions that will redefine the vampiric society we have all become too accustomed to.

subset: commoncrawl


text:
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Made of heavy duty cast aluminum, the Tamperproof Window Lock securely locks your window in a closed or ventilating position. Utilizing a hex security screw and wrench, the lock is unable to be accidentally opened by children. The lock is easy to install. Simply place it in the window rail and attach. The aluminum finish matches your window frame. The hex wrench has a large key ring for hanging safely away from the window.
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Take a look at the range of quality 2 panel display boards that we have available from Panel Warehouse. We specialise in providing you with an entire collection of panelled display boards and stock a selection of panel amounts so you can choose the perfect display board for you. If you want to display some work or information clearly then why not try one of our 2 panel display boards that we have to offer here at Panel Warehouse. You will not be disappointed with the range of panels and boards that we have to offer.
We also feature a selection of 3 panel display boards and 5 panel display boards for you to buy online.
Panel Warehouse Display Boards are ideally suited for any use, be it in the school, office or at a trade show exhibition,. We offer Lightweight Folding Display Boards, Jumbo Display Stands, a range of Clip and Pole Exhibition Kits as well as Desktop models – all offered with Free UK Mainland Delivery on orders over £100 + VAT– we have something to suit your requirements.
Purchase Orders accepted from Local Authorities, Schools, Colleges, Universities and the NHS.


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England pace spearhead James Anderson faces a battle to be fit for the opening test against South Africa in July after scans confirmed he had suffered a tear to his right groin when playing for Lancashire in the county championship.
Anderson, England's leading test wicket-taker, limped off midway through his sixth over on Friday against Yorkshire at Old Trafford and did not bowl again in the match.
The 34-year-old will miss Lancashire's return fixture against Yorkshire starting June 2 as he will be assessed by England's medical team to understand the extend of the injury.
Anderson, who missed four of England's last 10 tests with a shoulder injury, could still feature in three county matches in June to prove his fitness ahead of the international season.
England host South Africa in first of four tests starting on July 6 at Lord's before welcoming West Indies in a three-match series to wrap up the test summer in August and September.


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"I did try coke, and I loved it. I started to do cocaine in 1980, right after I graduated college. By 1989, I could press my cheek and blood would come out of my nose. I was so sick that it really did bring me to my knees. I said to God, on my knees, hysterical crying, 'Either kill me or please, please help me get well. I cannot live like this for one second longer.'"
On how Snapple helped her sobriety:
"What most people don't know about me [is] Snapple was much more than a job. It was a lifeline and it was a way for me to stay sober. And it was a vehicle to do wonderful, nice things for other people,"People just loved me and I remember crying, literally, like, 'What did I do to myself? What did I do to myself for all these years?' So, the addiction was great because, in a way, it made me really look at myself and re-evaluate everything."
On landing the commercial:
"It was definitely controversial. There were fights in the main office. 'How are you going to take the fat girl from the order department and put her on national TV?!'"
On her fame:
"How do you separate when everybody says, 'Oh my God, it's the Snapple Lady'? I didn't even have a brand, so I'm the Snapple Lady without being the Snapple Lady. I had to embrace that the personal part of me was far greater than the Snapple persona and that it was time to move on."


text:
Creditors Take Over Reston Contractor's Subsidiary — The company, STC Group Inc., received formal notice earlier this month of the default, which cited the company's failure to comply with financial covenants of an $81.2 million credit agreement from two years ago, according to the report. Top executives resigned as a result. [Washington Business Journal]
Stolen Garage Door Openers Lead to Local Burglaries — According to WTOP, police in Fairfax County are investigating a series of burglaries that happened this week involving stolen garage door openers. The incidents occurred at four homes, two of which are in Reston. In three cases, homeowners said they spotted the suspect, whom they described as a black man in his late teens to early 20s. [WTOP]
Comstock Holding Companies Inc Reports Third Quarter Results — The Reston-based company reported a net los of around $1.5 million as compared to the third quarter of last year, during with a net loss of $1.1 million was reported. [NB Herard]
Farmer-owned Restaurant Coming to Reston Soon — The North Dakota Farmers Union, Agraria LLC and the Farmers Restaurant Group are considering a plan to open their seventh farmer-owned restaurant on the East Coast in Reston. [Bismarck Tribune]
Nando's PERi-PERi restaurant opened today at 11 a.m. on 12120 Sunset Hills Road in Reston Town Center. The Portuguese restaurant will host a grand opening on Saturday to support music programs at South Lakes High School and Herndon High School.
All sales on Saturday will be donated to the schools, according to a press release. The funds will be directed to help fund Herndon High School's marching band as the team goes to Normandy, France to represent the United States at the 75th commemoration of D-Day in 2019. South Lakes High School will use the donations to send their band to Hawaii to perform at the Pearl Harbor Memorial Parade this year and other program needs.
According to the SLHS Parent Teacher Association, raffle prizes will be up for grabs at noon, 2 p.m., 5 p.m. and 8 p.m.
"This is all about being good neighbors, and Nando's looks forward to becoming an integral part of the Reston community," said Sepanta Bagherpour, the restaurant's vice president of marketing. "We are proud to support musical programs at two of the most impressive public high schools in Virginia."
Nando's has 40 locations in the country and nine in Virginia. The chain made its U.S. debut in 2008 with its first location in the Chinatown neighborhood of Washington, D.C. According to promotional information, the chain has about 1,200 restaurants in 23 countries on five continents. It was founded in 1987 in South Africa. Other area restaurants include at One Loudoun and in the Mosaic District.
Photos courtesy of Seven Oaks Media. For more photos, visit the online album.
The Belgian bakery and restaurant Le Pain Quotidien will celebrate its opening at the Reston Town Center this Thursday, Nov. 2.
The European cafe will serve different offerings for breakfast, brunch, lunch and dinner, and will be open from 7 a.m. to 9 p.m. every day, RTC staff said today.
"A morning at the bakery begins with Daily Blend smoothies, organic skillet eggs and egg dishes, in addition to a range of organic breads, pastries, yogurt, coffee and teas," LPQ representatives said in a press release.
For brunch, lunch and dinner, the bakery will offer their signature "tartines" open-faced sandwiches, alongside savory soups, salads and quiches, and in the evening, LPQ plans to serve organic wine.
The bakery will also offer special seasonal items throughout the year. For the fall, they plan to offer treats such as a turmeric latte, spiced apple cider, Turkey Bánh Mì, a roasted pear and spinach salad, chicken "zoodle" soup and "Speculoos Tiramisu," which LPQ describes as "a Belgian twist on the classic Italian treat."
Le Pain Quotidien will be located at 11909 Democracy Drive in the Reston Town Center. For more information, visit their website.
Image of menu items courtesy of Le Pain Quotidien
Management has begun hiring for all positions as Nando's Peri-Peri (12120 Sunset Hills Road) as the Portuguese-style chicken restaurants gears up for its opening day on Nov. 13, according to a company representative.
Nando's has about 1,200 restaurants in 23 countries on five continents. It was founded in 1987 in South Africa, with its first location debuting in the United States in D.C. nearly nine years ago. Other restaurants are located at One Loudoun and the Mosaic District.
The business will open a little over a month after a Starbucks opened next door. The Starbucks is the fifth in Reston and progress continues at Mezeh Mediterranean Grill, which will also sit next to Nando's.
The company is hiring for all positions. Company representatives dispersed information outside the location early this week.
Reminder: RA Board Special Meeting Tonight — The special meeting of the Reston Association Board of Directors originally scheduled for March 14 will be held tonight at 6:30 p.m. at RA Headquarters (12001 Sunrise Valley Drive). The purpose of the meeting is to discuss the findings in StoneTurn Group's review of Reston Association's purchase of the Tetra/Lake House property and the subsequent overruns in the cost of its renovation. [Reston Association]
New Town Center Restaurant Seeks Employees — Hen Penny is the newest restaurant by Pheast Food Group, a subsidiary of Thompson Hospitality. Management says it is planning to open March 30 at 1820 Discovery St., the former home of Pheast's BRB. The business is looking to hire cashiers, delivery drivers, cooks and more. [Pheast Food Group]
St. Johns Wood Redevelopment Again on Agenda — The Reston Planning & Zoning Committee will have an informational meeting March 27 at 7:30 p.m. on Bozzuto's planned redevelopment of St. Johns Wood. [Reston Planning & Zoning Committee]
SLHS Grad's Team Falls in NCAA Tournament — Princess Aghayere, South Lakes High School Class of 2015, played 12 minutes for the University of Pennsylvania Quakers in their NCAA Women's Basketball Tournament first-round game Saturday against Texas A&M. Penn led by 21 points early in the fourth quarter; however, Texas A&M staged the biggest comeback in women's tournament history and came out victorious, 63-61. Aghayere scored 2 points and recorded 2 rebounds. [Penn Athletics]
Students Named to All-State Band, Orchestra — The All-Virginia High School Band and Orchestra will both perform April 8 in Manassas. Among the performers will be 77 students from Fairfax County, including several local students. On the All-State Band are Catie George and Mason Moy (South Lakes High School); and Nathan Coughlin, Noah McKee and Emma Rood (Herndon High School). Members of the All-State Orchestra include Herndon High's James Adams and Ethan Morad. [Fairfax County Public Schools]
Photo via @FunInFairfax on Instagram
The Greater Reston Chamber of Commerce and other regional chambers are sponsoring the fifth annual Northern Virginia Restaurant Week, Monday through March 27.
Northern Virginia Restaurant Week is designed to offer the opportunity for people to enjoy dining at a number of participating restaurants at reduced prices. Restaurants participating in the event offer selections from their menu at special prices.
Restaurants in Fairfax, Loudoun, Arlington and Prince William counties are all participating. In Reston, participating eateries include:
- American Tap Room (1811 Library St.)
- Carrabba's Italian Grill (12192 Sunset Hills Road)
- Il Fornaio (11990 Market St.)
- M&S Grill (11901 Democracy Drive)
- McCormick & Schmick's Seafood & Steaks (11920 Democracy Drive)
- Mon Ami Gabi (11950 Democracy Drive)
- Morton's The Steakhouse (11956 Market St.)
- Not Your Average Joe's (1845 Fountain Drive)
- Red's Table (11150 South Lakes Drive)
- Tavern64 (1800 Presidents St.)
- The Melting Pot (11730 Plaza America Drive)
- Vinifera Wine Bar & Bistro (11750 Sunrise Valley Drive)
- World of Beer (1888 Explorer St.)
To see special menus being offered as part of Restaurant Week, as well as a full list of participating businesses, visit the event's website.
Still Waiting for Willard's — We reported in January that Willard's BBQ would soon open at 11790 Baron Cameron Ave., in the Home Depot Shopping Center. On its Facebook page, the restaurant later said it was aiming for a March 14 opening. In a response to a follower's question Tuesday, though, it now says it hopes to open by the "end of this month." [Willard's BBQ]
Red's Table Chef Talks About Life of Cooking — Adam Stein, the executive chef at Red's Table (11500 South Lakes Drive), talked with a culinary website about what fuels his passion for food. [The Daily Meal]
Young Professionals Event Slated for Brewery — The Greater Reston Chamber of Commerce will host an event Thursday from 5:30-7:30 p.m. to celebrate the ribbon cutting of Crooked Run Brewing (22455 Davis Drive, Sterling). The event will be the kickoff of the Young Professionals Cocktail Connection Networking for the year. [Greater Reston Chamber of Commerce]
Reston-Based Company Sold — ObjectVideo, which develops video analytics software for automated security surveillance systems, is headquartered at 11600 Sunrise Valley Drive. The 19-year-old company, whose work has been widely used by the U.S. defense and intelligence communities, has been acquired by Tysons-based Alarm.com. [Washington Business Journal]
'Rock of Ages' Gets Good Review — Reston Community Players' performance of "Rock of Ages" opened last weekend at CenterStage (2310 Colts Neck Road) and will play through April 1. A review says Chris Dore's "sexy, fun" choreography does an excellent job "showcas[ing] very talented dancing in the ensemble." Carole Steele's costumes are said to be "transformative and appropriately gaudy" for the '80s theme. [DC Metro Theater Arts]
South Lakes in Basketball Tourneys — The South Lakes varsity basketball teams are playing in regional tournaments this week. The girls team defeated Annandale 67-36 in a tournament in Oakton yesterday, while the boys team fell to Trinity Episcopal 74-56 in a tournament in Henrico.
Reston's Missed Connections — Craigslist's Missed Connection section is an interesting (albeit sometimes creepy) study in human interactions. The past three Reston missed connections have all been in chain restaurants: Panera Bread, Five Guys and Boston Market.
Flickr pool photo by Vantagehill
Top 5 Restaurants, Per OpenTable — According to OpenTable customer reviews, the top 5 restaurants in Reston are PassionFish, Big Bowl, Vinifera Wine Bar & Bistro, Il Fornaio and Neyla Mediterranean Bistro. [Patch]
Tetra Misses Revenue Forecast — Local advocacy group Reston 20/20 faults the Reston Association for "horrible" revenue forecasting for the RA's Tetra/Lake House. Programming revenue for Tetra is expected to be $82,535 for 2016 compared to the $175,000 budgeted in May. Total costs, however, were below budget. [Reston 20/20]
Arlington to Reston Commute — Redditors are weighing in on the feasibility of an Arlington-to-Reston reverse commute. The emerging consensus: mornings aren't too bad but evenings are rough. [Reddit]
Photo courtesy @MrErrett
Not Your Average Joe's, a new restaurant coming to the space formerly occupied by Romano's Macaroni Grill, will open on Jan. 4, a spokesman said.
NYAJ was originally slated to open at 1845 Fountain Dr. on Dec. 21.
The Reston restaurant will be the fifth Massachusetts-based Not Your Average Joe's to open in the Washington metropolitan area. There are outposts in Leesburg and Woodbridge, Va., as well as in Gaithersburg and Bethesda, Md.
NYAJ will be open for lunch and dinner, and has an extensive menu featuring seafood, steaks, creative appetizers, salads, stone hearth pizzas, and burgers. The menu also features seasonal selections.
Some of the specialty dishes: ahi tuna wontons served with pickled ginger and wasabi aioli; red-wine braised short ribs; and sage pecan salmon with a sage pecan pesto, chipotle mashed sweet potatoes and roasted brussels sprouts.
NYAJ will also feature an extensive wine list and more than 20 beers on tap, including several local craft brews such as Devil's Backbone Vienna Lager, Lost Rhino Faceplant IPA, and Flying Dog's seasonal brew.
The 7,300 square-foot restaurant will seat 218, with a full bar and two seasonal outdoor patios offering an additional 100 seats. A private dining space accommodates 22 seated guests. The Reston location — which will take reservations — will feature an open-kitchen.
Not Your Average Joe's will partner with local non-profit Cornerstones during its grand opening. All proceeds raised during the two-day preview celebrations will be donated to the organization, which is dedicated to providing support and advocacy for people in need of food, shelter, affordable housing and other human services.
NYAJ will continue to support Cornerstone through January with its ongoing "Not Your Average Cause" program, which provides 15 percent of proceeds to a selected cause every Tuesday.
Don't feel like cooking Christmas Eve or Christmas Day? Several area restaurants are ready for you.
Christmas Eve
PassionFish at Reston Town Center is open. Check out the special menu on PassionFish's website.
Red's Table at South Lakes Village Center is open until midnight with its regular menu until 10 p.m.
Christmas Day
- Tavern 64 at the Hyatt Regency Reston
- Vinifera Wine Bar & Bistro at the Westin Reston Heights
- M&S Grill at Reston Town Center
- McCormick & Schmick's at Reston Town Center
Visit Open Table to make reservations and see business hours and special menus for the Reston restaurants above.
Generally, most Asian restaurants are open. Call your favorite one ahead of time to see if they are open.
Starbucks and Dunkin Donuts are also expected to be open limited hours on Christmas Day. Check with your neighborhood store.
Passion Fish file photo


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Average customer review 3.5 out of 5 stars64 reviews
It may not be a robot in disguise but there's certainly more than meets the eye with this simple wand attachment. Designed to instantly transform your magic wand into a powerful orgasmic G-spot vibe, prepare for spellbinding, targeted stimulation.
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Product Description
It may not be a robot in disguise but there's certainly more than meets the eye with this simple wand attachment. Designed to instantly transform your magic wand into a powerful orgasmic G-spot vibe, prepare for spellbinding, targeted stimulation.
Flexible and super-easy to use, slide the rubber attachment over the head of your magic wand to realise the new climactic possibilities at your fingertips. With its curved shaft and rounded head, it effortlessly locates and stimulates your G-spot or P-spot for a mind-blowing release, while its grippy head ensures it stays in place even when vibrations go off the Richter scale.
A jolly good load of water-based sex lube is all that's need for pleasure of the slippery variety.
Please note: This product is waterproof, but your wand might not be. Please check manufacturer instructions before putting your wand anywhere near water.
Key Features:
- G-spot stimulating magic wand attachment for incredible internal massages
- Curved 6 inch shaft with 3.25 inch circumference and rounded head expertly stimulates G-spot with ease
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Product Videos
Lovehoney Curved G-Spot Pleaser Magic Wand Attachment
Give your Classic Magic Wand a makeover and send those famously powerful vibrations straight to your G-spot with this luxurious G-spot Pleaser attachment. Slip the sleeve over the head of your wand and get ready for breathtaking orgasmic bliss!
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Customer Reviews
Lovehoney G-Spot Pleaser Wand Attachment 64 3.5 out of 5 stars
See all 64 customer reviewsOrder by:Write your own review
- 5 star
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Lovehoney G-Spot Pleaser Wand Attachment
Reviewed: September 27, 2017 by Annie2705, a Straight Married Female
I thoroughly recommend this product.
Sits nicely on top of your magic wand. Hits the G-spot perfectly with fantastic results. OMG, what a result! OH had fun! I think the neighbours in the next village heard the results too!
This really was worth it and couldn't recommend it enough.
- Pros
- Easy to attach to wand.
- Cons
- Was a little floppy!
- Bottom line
- Fantastic results.
- 2 people found this review helpful. Was this review helpful to you? Yes
On the spot
Reviewed: September 2, 2017 by Curiouscouple87, a Straight Married Female
Where do I start with this little beauty!
I bought this for my OH not long after our very good purchase of the Lovehoney wand. Now there is nothing wrong with the wand on its own and my partner still loves using it that way but having this has kicked up its usage another notch.
Standard quick delivery from Lovehoney and we couldn't wait to try this thing out. The reviews were very good and they were right. We lubed it up and I probed and teased the OH until she was begging for it. I can assure you that when we did finally use it in its full she absolutely loved it! She squealed and squirmed and begged for more, climaxing multiple times.
This probably has been our best purchase and we use it most times even now. It never gets old and never fails. It's super easy to keep clean and a must in the bedroom!
- Pros
- Everything, clean and easy to use with super reactions from the OH.
- Cons
- Bottom line
- Must-have.
- 2 people found this review helpful. Was this review helpful to you? Yes
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The anal and cookie master
Reviewed: August 22, 2017 by Kevkris, a Straight Going Steady Female
Wow wow wow. The wife screamed moaned and shouted with excitement. Then a couple of nights later she was playing with me and decided it was time to try it on me with this attachment on her magic wand while playing and a blowjob.
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She was a bit harsh and was sliding it in and out, but that with the extreme vibration was the magic.
- Pros
- Everything.
- Cons
- Nothing, all good.
- Bottom line
- Mind-blowing.
- Was this review helpful to you? Yes
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See all 64 Lovehoney G-Spot Pleaser Wand Attachment reviews…
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listlessness (countable and uncountable, plural listlessnesses)
- The state of being listless; apathetic indifference; lethargy.
- 1749, John Cleland, Fanny Hill: Memoirs of a Woman of Pleasure, Letter the First,[1]
- But every thing must have an end. A motion made by this angelic youth, in the listlessness of going off sleep, replac'd his shirt and the bed-cloaths in a posture that shut up that treasure from longer view.
- 1851, Herman Melville, Moby-Dick, Chapter 35,[2]
- […] lulled into such an opium-like listlessness of vacant, unconscious reverie is this absent-minded youth by the blending cadence of waves with thoughts, that at last he loses his identity; takes the mystic ocean at his feet for the visible image of that deep, blue, bottomless soul, pervading mankind and nature; and every strange, half-seen, gliding, beautiful thing that eludes him; every dimly-discovered, uprising fin of some undiscernible form, seems to him the embodiment of those elusive thoughts that only people the soul by continually flitting through it.
- 1749, John Cleland, Fanny Hill: Memoirs of a Woman of Pleasure, Letter the First,[1]


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Feature: Of Honours and Creative Inclusivity: Christopher Cozier receives Prince Claus Award in Atmosphere of CollaborationFriday, March 28th, 2014 Categories: Awards, Events, Features, Updates
Each year, The Prince Claus Awards are presented to eleven individuals or organisations whose work and actions have left an indelible mark on the culture and development of their societies. Among the 2013 laureates is Christopher Cozier, an artist, writer and critic from Trinidad and Tobago. According to the 2013 Prince Claus Award Committee Report, Cozier is honoured "for his influential role and open, inclusive approach in developing art and culture across the Caribbean."
On March 18, 2014, Cozier was presented with the award at Alice Yard, Trinidad – a backyard space in the capital city of Port of Spain conceptualised as a site of creative experimentation, dialogues, exhibitions, screenings and performances. Cozier is a co-founder of the space, which uses an ecology model to expand Alice Yard beyond its physical location to a broad and ever-widening network of relationships and collaborations between various people, including painters, writers, photographers, filmmakers and musicians. The occasion of the conferment of the award brought scores of people into relation with each other at the yard, as Ambassador of the Kingdom of the Netherlands to Trinidad & Tobago, Lucita Moeniralam, and Prince Claus Fund Awards Programme Coordinator, Fariba Derakhshani, conducted the formal part of the proceedings.
Yet, the award was not the only memorable part of the evening. Cozier was determined to honour a spirit of collective, creative input. There were feelings of pride and elation as guests witnessed Cozier receiving the award, but the event fostered an even greater affective experience. There was too, an air of artistic democracy surrounding the setting of the ceremony within a poetics of inclusivity and relationality, as Cozier literally shared – through the interaction of artists and audiences – the latest versions of three contemporary art projects.
Visitors to the yard were first struck by the sights and sounds of the Sound System street installation. The roadway between Murray and Carlos streets were cordoned off, and several vehicles bedecked with custom-engineered speakers and sound systems were strategically lined up. One car, with its scissor or switchblade doors lifted, seemed to both welcome guests with open arms and present itself in such a way as to facilitate little or no obstruction of the flow of sound. The scissor doors were a visual signifier of the sound cutting through the air and across the space of the city.
Sound System is a collaborative project which began in 2001 with its first version displayed in Rotterdam. Other versions have been shown in Oslo Norway, St Maarten and Kentucky USA. It is an accumulation of audio contributions over the years: recordings of Cozier's own voice as he narrates fragments of the texts that can be found in his drawings, mixes by sound producers Robin Foster and Martin Raymond and DJs Daniel Haun and Kevon Walker, and sound sequences by Yvette Grey, Trinidadian musician Sheldon Holder, Bahamian/Trinidadian poet Christian Campbell, Trinidadian jazz musician Chantal Esdelle, visual artists Sheena Rose of Barbados and Ebony G. Patterson of Jamaica, and trombonist/composer Jomo Slusher of Barbados. This latest iteration – the largest so far in Cozier's continued experimentation – was also supported by the involvement of Suspex Auto Club of Gasparillo, Trinidad.
The installation was a complex, multilayered soundscape that commented on the giving of voice and the capacity of sound to define and (re)configure areas. It interrogated notions of mobility (sound travels) and proximities (relationships between here and there; near and far). It attended to the idea of acoustic identities, that is, the way a bass track can take possession of the body or, put another way, the overlap of sound and rhythms with a sense of being. With its intensity and a volume that took on huge decibel proportions, the installation also addressed psychological states of dissonance and discomfort, as well as concerns about the politics or the power that is bound up in cultural productions and the control of spaces and knowledge – considering, for example, what is allowed to fall within and outside our earshot; what is muffled and what is rendered audible for us and the silences within the "noise" of existence.
Another collaborative feature was version two (read about version one here) of a series of projected images of Cozier's drawings from his recent project entitled The Arrest: Hands Up, Hand Out. The images were appropriated and reinterpreted through motion/animated sequences by artists Nadia Huggins of St Vincent and Rodell Warner of Trinidad. With technological support from North Eleven, projections of various elements – birds, a hand, a spot of blood, a gas pump, a foot, a coin – inundated the senses and invited engagement and translation. The changing shadows cast by guests passing in front of the screen added to the sensory flood of signs and served as indicators of the ephemeral, shifting nature of any meanings we might have attempted to construct and hold on to with certainty and finality. The images meant this; no, they meant that – all in a continuous play of personal associations and possibilities that could arrest us forever.
Cozier also shared his Made in China project, a three-dimensional version of an image that has appeared in his works on paper. It is a box (made possible with the assistance of Trinidadian designer Marlon Darbeau) with the engraved label: MADE IN CHINA. Cozier uses the structure and the words to reflect on narratives of development, progress, value and consumption. It is a pedestal of sorts upon which a person might stand to feel important, "big" and influential, or it is perhaps an instrument of our demise. At Alice Yard, guests were invited to stand on the object as photographer Shaun Rambaran captured pictures of shoe-clad and bare feet. Guests became creative performers who interacted with the box in diverse ways that gave a tangible dimension to acts of manufacturing and branding (constructing and labelling self) and demonstrated relationships to notions of importation, commodities and trade.
These three art projects pointed the way for us to see the development of Caribbean societies as resting on cornerstones of partnership, inclusivity and participation, with efforts at advancement being decentralised rather than confined to a monopoly. Christopher Cozier's contemporary art resonates with a cotemporality and contemporaneousness that are understood as our coming into being with each other – our contemporaries – at the same time.


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Cure For a Toothache
- Nov 1, 2005
- Topics:
Abby is a Tennessee Walking Horse mare who was recently purchased by a Virginia family as a 5-year-old and shipped there from Tennessee to train and show. A dental examination six months after purchase found that her right and left lower first cheek teeth, 306 and 406 on the Triadan numbering system (a system used consistently to number teeth across different animal species), were cut off at the gum line sometime the previous year.
This practice has become recognized in some equine sports as molar cutters and power tools have become more common. Use of these tools without appropriate training has led to more aggressive removal of normal tooth surface. Some trainers have encouraged the practice, thinking the bit is interfering with the lower teeth. The common practice of slightly rounding the front edge of the lower cheek teeth with hand floats has progressed to leveling off the entire tooth at the gum line.
Abby had complications from the pro-cedure, most likely due to the age at which it was done and the technique used. In a young adult horse, the five to six normal pulp horns of the premolar ex-tend from just below the crown down the length of the tooth root. When the teeth were cut, it left all of the pulp horns exposed. Pulp is the living tissue within the pulp chambers and root canal. It is comprised of blood and lymph vessels, nerves, collagen, and connective tissue.
The new owners had Abby examined by respected veterinarian and equine dentistry specialist, Bayard A. Rucker, DVM, of Lebanon, Va. Rucker's examination noted swellings on the lower jaw similar to eruption bumps (the normal condition of bone development around a newly erupting permanent tooth). In a 5-year-old mare, these were not eruption bumps, but swelling due to osteomyelitis or bone infection from abscessed tooth roots. Radiographs showed the classic signs of tooth root infection. The lamina dura (bony area around the tooth socket to which the periodontal ligament anchors the tooth to the jaw bone) was eroded and invisible on radiographs. The normal radiographic space around the tooth typically occupied by the periodontal ligament was widened, indicating loss of the ligament attachment and destruction of the bone. Rucker also noted on visual assessment that the pulp horns of the two affected teeth were open and draining, indicating infection down the length of the root.
Rucker said, "The cutting off of the premolars appears to be an extreme type of 'putting in a bit seat,' and there is no valid reason for doing this procedure. Whoever did this was grossly uninformed on the reasons for doing this, and on the complications that could follow."
The prognosis for these dead teeth is poor—they will not continue to erupt over the course of the horse's life, as would healthy teeth. Two treatment options were considered. In this case, the teeth were extracted intra-orally (from within the mouth). If enough of the tooth surface can be grasped with forceps, after a releasing incision of the gum tissue, intra-oral extraction can be performed. If the tooth cannot be removed from inside the mouth, a trephine procedure can be performed where the tooth is removed from the lower jaw surface after drilling away the supporting bone. Postoperative care consists of daily lavage (rinsing) of the extraction sites and an extensive antibiotic regimen to treat the bone infection.
A more technically challenging procedure is to cap the pulp horns on the tooth surface and perform a root canal from the lower jaw surface. The difficulty level is high due to the intricacy of the canal lining and the necessity for complete removal of the pulp material and tight packing of the root canal. Lengthy antibiotic treatment is necessary to prepare for endodontic procedures on infected teeth.
Long-term aftercare requires a dental exam every six months and floating (filing) the opposing upper premolars. Normally, wear against the lower teeth keeps them level with the other teeth of the upper jaw. Without the opposing grinding action of the lower premolars, these teeth will grow longer than their neighbors, creating tooth and jaw interference. Because of financial considerations, the owners elected to remove the affected teeth. The procedure was performed under general anesthesia. Rucker was able to remove the right lower cheek tooth by the intraoral method. The left lower cheek tooth required the trephine procedure. The teeth were removed without complication.
Abby's prognosis is good. Her comfort and performance will improve and the bumps on her jaw should resolve, leaving a pleasing cosmetic appearance. Rucker's advice to readers: Engage the services of trained and experienced veterinary dentists to perform endodontic and periodontal procedures. The health of the horse and the financial investment will both be optimized.
About the Author
Kimberly Peterson, DVM
Kimberly Peterson, DVM, is an AAEP member and assistant professor in the Department of Veterinary Technology at Morehead State University in Morehead, Ky. Her husband, Eric, is an equine practitioner, and their family lives in Lexington.
Related Content
AAEP On Call Program at the Kentucky Derby
Equine Dental Care (AAEP Convention 2012)
Veterinary Ethics (AAEP Convention 2012)
Equine Dental Issues
Keeping Your Veterinarian Safe
Help Sick Horses Heal with Nutrition
Study Examines Post-Anesthetic Myelopathy in Horses
'Pinch Grafting' for Equine Lower Limb Wounds (AAEP 2011)
Understanding Equine Sleep Deprivation
Granulation Tissue Management in the Horse (AAEP 2011)


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"My mom always made this when she needed to bring an appetizer to a party. It's a super easy recipe. The thing that makes it tastier than other cheeseballs are the pickles."
Mom's Dill Pickle Cheese Ball
0 recipe photos
READY IN:10mins
Ingredients Nutrition
- 8 ounces cream cheese (room temperature)
- 1 cup grated cheddar cheese
- 1⁄2 cup diced dill pickle
- 2 tablespoons mayonnaise
- 1 teaspoon Worcestershire sauce
- 1⁄2 cup chopped walnuts
- Mix first 5 ingredients together in a medium sized bowl (you will probably have to use your hands for this to mix it thoroughly).
- Shape into ball.
- Roll in chopped walnuts until ball is covered.
- Refrigerate for at least an hour to harden it up a bit before serving. Serve with crackers.
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Bendon Women's Yvette Nouveau Underwire Bra - Splatter Print/White
The Yvette Underwire Bra by Bendon is the perfect go-to bra you need on an everyday basis. It features printed lightweight microfibre fabric and printed front straps, giving it a bit more oomph than your plain-coloured lingerie pieces.
Available in women's bra sizing - see size chart for correct fit!
- Bendon apparel
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- Style: Yvette Nouveau Underwire Bra
- Colour: Splatter Print/White
- Italian-style scalloped lace
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- Machine washable
- Country of origin: China
- Please note: change of mind returns will not be accepted for this item due to hygiene reasons
For more than 65 years, Bendon has been providing women with comfortable and fashionable lingerie. Quality, excellent fit and affordability are the hallmarks of every piece of Bendon lingerie. Everyday basic intimates from lacy bras and cotton briefs, to sports bras, contour bras, PJs and maternity wear, Bendon is the comfortable lingerie for every occasion!