text:
|Publication number
|Publication type
|Application number
|Publication date
|3 May 1988
|Filing date
|14 Apr 1987
|Priority date
|14 Apr 1987
|Fee status
|Also published as
|Publication number
|Ross J. Cozens
|Original Assignee
|The B. F. Goodrich Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Referenced by (14), Classifications (16), Legal Events (8)
|External Links: USPTO, USPTO Assignment, Espacenet
Polyvinyl chloride resins when calendered or extruded give products which are very smooth and thus have a glossy finish. For many end uses this glossy finish is desirable, such as packaging films and clear containers. When a rough or dull finish, which is often referred to as a matte finish, is required, it has been suggested that crosslinking the PVC resin would give such a surface. Some end users find the matte finish desirable for their products. Crosslinking the PVC resin makes the resin more rubbery thus resulting in the resin being capable of giving a matte finish. Crosslinked resins can also offer advantages in other properties such as wear resistance.
Many applications where crosslinked resins would be desirable require that the resin be mixed with large amounts of plasticizers. PVC resins normally have porosity which allows the resins to absorb plasticizers. Crosslinking a resin detrimentally effects the ability of a resin to absorb plasticizer quickly. Although the crosslinked resins have porosity, the plasticizer does not incorporate as quickly as it does in a non-crosslinked resin having the same amount of porosity. This creates a problem in that an extra amount of time is required to incorporate the plasticizer. This time is normally referred to as "powder mix time".
It would be desirable to have a crosslinked PVC resin which would quickly absorb plasticizers thereby having a fast powder mix time.
It is an object of this invention to provide crosslinked PVC resin in particulate form which are skinless.
It is a further object of this invention to provide crosslinked PVC resins which have short powder mix times.
It is another object of this invention to provide crosslinked PVC resin in particulate form which are non-spherical, highly porous, friable and which are skinless.
It is a still further object of this invention to provide processes for producing the crosslinked resins.
These and other objects will become apparent from the following description of the invention.
A crosslinked PVC resin in particulate form characterized by more than 90% by weight of said resin particles having the following features:
(a) said particles are skinless as evidenced by an absence of a substantially continuous pericellular membrane;
(b) a complex viscosity of from about 0.9�105 poise to about 1000.0�105 poise, preferably about 1.0�105 to about 100.0�105, more preferably about 4.0�105 to abut 60.0�105 ; and
(c) a tan δ less tan 1.0, preferably from about 0.1 to about 0.95, more preferably from about 0.3 to about 0.7.
It is also preferred that more than 90% of said resin particles have the following features:
(a) a mercury porosity of from about 0.1 cc/g to about 0.8 cc/g, preferably from about 0.3 cc/g to about 0.5 cc/g;
(b) an agglomerated non-spherical shape having a shape factor less than about 0.85, preferably less than about 0.83; more preferably less than about 0.80;
(c) a weight average particle size of from about 70 microns to about 1000 microns, preferably from about 100 microns to about 250 microns;
(d) a friability less than about 2, preferably less than 1, more preferably 0;
(e) a powder mix time of less than about 400 seconds, preferably less than 300 seconds, more preferably less than 250 seconds;
(f) the surface of said particles is greater than about 20% PVC, preferably greater than about 50%, more preferably greater than about 60% as measured by ESCA.
A process is provided for producing the preferred novel particles of this invention comprising polymerizing vinyl chloride monomer in the presence of a crosslinking agent in an agitated aqueous suspension wherein said aqueous medium contains as the primary dispersant small amounts of at least one ionic sensitive dispersant capable of thickening water and at least one secondary dispersant, wherein an ionic material is charged to the polymerization medium at from about 1% to 5% conversion of monomer to polymer and the ionic material desorbs a substantial amount of the ionic sensitive primary dispersant off the monomer droplet, thereby producing a crosslinked skinless, agglomerated, highly porous, friable, PVC resin absent a continuous pericellular membrane.
Alternate processes are also provided for producing the skinless crosslinked PVC particles of this invention.
The resins of this invention, even though highly crosslinked, unexpectedly have short powder mix times and are able to incorporate large amounts of plasticizer quickly.
The FIGURE is a semi-log graph showing the range of skinless, crosslinked resins made in Example II (Runs 1-24) and the commercially available skin type crosslinked resins of Example III (A-D). Complex viscosity is plotted on the Y-axis as 105 poises. The Y-axis is a log scale. The X-axis is tan δ. The numbers indicate the run number of Example II whereas the letters A-D indicate the corresponding resin of Example III.
Polyvinyl chloride resin as used in this invention means polyvinyl chloride homopolymers as well as vinyl chloride polymerized with up to 50%, preferably up to 20%, by weight of one or more other vinylidene monomers having at least one terminal CH2 ═C< grouping. Suitable comonomers that may be polymerized with vinyl chloride are esters of acrylic acid, for example, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate, and the like; vinyl acetate; esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like; styrene and styrene derivatives including α-methyl styrene, vinyl toluene, chlorostyrene; vinyl naphthalene; diolefins including butadiene, isoprene, chloroprene, and the like; and mixtures of any of these types of monomers and other vinylidene monomers copolymerizable therewith; and other vinylidene monomers of the types known to those skilled in the art. The amount of comonomer that can be polymerized with vinyl chloride is a function of the choice of comonomer, as is well understood by those skilled in the art. Preferably, the polyvinyl chloride polymers of this invention are polyvinyl chloride homopolymers. The term polyvinyl chloride homopolymer as used in this specification includes the polymerized vinyl chloride as well as the small amount of crosslinked agents. Technically, the crosslinked resins of this invention will not always be copolymers, because the crosslinking agent copolymerizes with the vinyl chloride. However, the amount of crosslinking agent is so small that in this specification this resin having only vinyl chloride and crosslinking agent as monomers will be referred to as a homopolymer. The invention will be described in terms of a polyvinyl chloride homopolymer as the preferred embodiment of this invention.
The skinless crosslinked resin particles of this invention may be produced by any one of many processes such as an agitated aqueous suspension process, which is the preferred process. They may also be produced by a mass or bulk polymerization process, where polymerization occurs in the substantial absence of water and surfactants. A mass process is described in U.S. Pat. No. 3,522,227, incorporated herein by reference. The mass process produced PVC which is skinless, since there are no surfactants present.
In the mass process, vinyl chloride is polymerized in mass (in the absence of additives except a useful quantity of catalyst) using a two step process in the first of which agitation of high turbulence is used and in the second very mild agitation, usually related only to the maintenance of uniform temperature in the reaction mass. In the first, high speed step the polymerization is carried to 7 to 15 percent completion, preferably about 10 percent. The vessel contents are then transferred to the second vessel for completion of the polymerization to the desired degree of conversion. The first stage is normally referred to as a prepolymerizer. The crosslinking agent would be added in the prepolymerizer vessel. Of course one vessel could be used for the mass polymerization, but two vessels are preferred.
A phase inversion process may also be used to produce the crosslinked skinless resins of this invention. Such a phase inversion process is disclosed in U.S. Pat. No. 3,706,722, incorporated herein by reference. In the phase inversion process, the monomer is the continuous phase during the early part of the polymerization and after about 10% conversion additional water is added such as to make the water the continuous phase and the monomer the discontinuous phase. This process in essence runs a mass type polymerization up to about 10% conversion and then inverts to a suspension type polymerization. The invention will be described in terms of the preferred aqueous suspension process.
The preferred process used to produce the preferred novel resin particles of this invention is an agitated aqueous suspension process. In the process, water is the polymerization medium and a vinyl monomer to water ratio in the range of about 1.0:1.0 to 1.0:10.0 is satisfactory. Preferably, a ratio in the range of about 1.0:1.0 to 1.0:4.0 is employed.
An important feature of the process to prepare the preferred resin particles of this invention is the dispersant system that is employed in the polymerization reaction for the purpose of stabilizing the dispersed monomer droplets. A colloidal unstable system will result in what is known as a solid charge, that is, the monomer droplets will agglomerate into large chunks which are unsuitable for use in normal PVC applications. A dispersant system which will not allow any agglomeration of monomer droplets will result in spherical particles. Such process to produce spherical particles is described in U.S. Pat. No. 4,603,151. To obtain the preferred agglomerated skinless particle of this invention requires a delicate balance of having a few of the monomer droplets agglomerate but not excessive agglomeration such as to result in excessively large particles. An important component of this process is an ion sensitive dispersant which will thicken water. Examples of such thickeners and how they are used are disclosed in U.S. Pat. No. 3,620,988, incorporated herein by reference. The ion sensitive dispersants which will thicken water are usually high molecular weight dispersants or crosslinked dispersants which will thicken water at concentrations of less than 2% in water, preferably less than 0.2%, and more preferably less than 0.1% concentration in water. Suitable ion sensitive thickening dispersants include crosslinked polyacrylic acid polymers, crosslinked ethylene malic anhydride polymers, high molecular weight uncrosslinked polyacrylic acid polymers and ethylene malic anhydride polymers, and the like. The invention will be explained in connection with a substantially unneutralized crosslinked interpolymer.
A suitable ion sensitive thickener is a substantially unneutralized crosslinked interpolymer of one or more carboxylic acid monomers with a polyunsaturated compound having a plurality of terminally unsaturated polymerizable groups, for example, a crosslinked polyacrylic acid polymer. The crosslinking is responsible for making the polyacrylic acid polymer incapable of forming a true solution in water. In this regard, these polyacrylic acid polymers are classified as being substantially insoluble in water. Nevertheless, the structure of the interpolymer must be such that it has enough affinity for water to swell appreciably in an aqueous medium, thus thickening the water phase, but not to the extent that it cannot be agitated rapidly. Interpolymers that have little or no affinity for water and do not swell to any measurable degree, are not suitable for the purposes of the present invention.
With respect to the crosslinked polymeric dispersants used in making the resin of the invention, the carboxylic acid monomers utilizable in preparing the same are those which contain at least one active carbon-to-carbon double bond in the α,β-position with respect to a carboxyl group such as ##STR1## wherein R' is hydrogen or a --COOH group, and each of R" and R"' is a hydrogen or a monovalent substituent group which is linked to one of the doubly bonded carbon atoms. Carboxylic acids within this definition include acids, such as acrylic acid, wherein the double bond is terminal such as ##STR2## or the dicarboxylic acids such as maleic acid and other anhydrides of the general structure ##STR3## wherein R and R' are monovalent substituent groups and especially those selected from the group consisting of hydrogen and halogen groups and alkyl, aryl, alkaryl, aralkyl, and cycloaliphatic radicals.
Included within the class of carboxylic acids, shown by generic formula (1) above, are widely divergent materials, such as the acrylic acids, such as acrylic acid itself, methacrylic acid, ethacrylic acid, α- and β-chloro and bromo-acrylic acids, crotonic acid, maleic acid, itaconic acid, and many others.
Polymerizable carboxylic anhydrides include any of the anhydrides of the above acids, including mixed anhydrides, and those shown by generic formula (3) above, including maleic anhydride, and others. In many cases, it is preferred to copolymerize an anhydride monomer with a copolymer, such as methyl vinyl ether, styrene, ethylene, and the like.
It is preferred to employ polymeric dispersants which are derived from polymers produced by the polymerization of the α,β-monoolefinically unsaturated carboxylic acids. The preferred carboxylic acids are those derived from the acrylic acids and α-substituted acrylic acids having the general formula ##STR4## wherein R is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydroxyl, carboxyl, amide, ester, lactone, and lactam.
The most preferred polymeric dispersants are those prepared from the lightly crosslinked interpolymers of acrylic acid. These dispersants are the most effective.
The crosslinking agents which may be employed with any of the carboxylic monomers, or mixtures thereof, may be any compound, not necessarily monomeric in nature, containing two or more terminal polymerizable CH2 ═C< groups per molecule. Examples of this class of materials include polyunsaturated-hydrocarbons, -polyethers, -polyesters, -nitriles, -acids, -acid anhydrides, -ketones, alcohols and polyunsaturated compounds of this class incorporating one or more of these and other functional groups. Specifically, there may be utilized divinyl benzene, divinyl naphthalene, low-molecular weight and soluble polymerized dienes, such as polybutadiene and other soluble homopolymers of open chain aliphatic conjugated dienes, which soluble polymers do not contain any appreciable number of conjugated double bonds, and other polyunsaturated hydrocarbons; polyunsaturated esters, ester-amides and other ester derivatives, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, allyl acrylate, methylene bisacrylamide, methylene bismethacrylamide, triacrylyl triazine, hexallyl trimethylene trisulfone, and many others; polyunsaturated ethers, such as divinyl ether, diallyl ether, dimethyl allyl ether, diallyl ethylene glycol ether, diallyl, triallyl and other polyallyl ethers of glycerol, butene-1,2-diol, 1-phenyl-1,2,3-propanetriol, the polyallyl, -vinyl and -crotyl polyethers containing from two to seven or more of these or other alkenyl ether groupings per molecule and made from polyhydric alcohols, such as the carbohydrate sugars, and the so-called "sugar alcohols", including erythritol, pentaerythritol, arabitol, iditol, mannitol, sorbitol, inositol, raffinose, glucose, sucrose, and many others, and other polyhydroxy carbohydrate derivatives, the corresponding polyalkenyl silanes, such as the vinyl and allyl silanes, and others. Of this large class of crosslinking agents, the polyalkenyl polyethers of the carbohydrate sugars, sugar alcohols and other polyhydroxy carbohydrate type derivatives containing from two to seven alkenyl ether groups per molecule are particularly useful. Such materials are easily prepared by a Williamson-type synthesis involving the reaction of an alkenyl halide, such as allyl chloride, allyl bromide, methallyl chloride, crotyl chloride, and the like, with a strongly alkaline solution of one or more of the poly-hydroxy carbohydrate derivatives.
In the monomeric mixture, for making the crosslinked polymers employed as primary dispersants in the suspension polymerization process used in this invention, the two essential monomeric materials should be present in certain proportions, although the exact proportions will vary considerably depending on the characteristics desired in the polymer. Small amounts of the polyalkenyl polyether copolymerize quite readily with carboxylic monomers and the crosslinking effect of the polyalkenyl polyether on the carboxylic monomer is so strong that as little as 0.1% by weight thereof, based on the weight of the total mixture, produces a great reduction in the water and solvent-solubility of the resulting crosslinked polymer. When 0.1% to 4.0%, more preferably 0.20% to 2.5%, by weight of the polyether is utilized, water-insoluble polymers are obtained, especially with acrylic acids, which are extremely water sensitive. Useful dispersants are also obtained when 0.1% to 6.0%, and preferably 0.2% to 5%, of the polyether is copolymerized with maleic anhydride. In the dual copolymer, or two-compound interpolymer, this means that the remainder of the monomeric mixture will be the carboxylic monomer.
The monomeric proportions employed in the production of multi-component interpolymers may vary in a somewhat similar manner. However, it is generally desirable to utilize as much of the carboxylic monomer or monomers and as little of the other monomeric constituents as is consistent with the desired water-insolubility and other properties. In these interpolymers, therefore, the carboxylic monomer or monomers should never be less than 25%, and preferably not less than 40%, by weight of the total monomeric mixture. Multicomponent interpolymers may be made from monomeric mixtures comprising from 25% to 95% of a carboxylic monomer, such as acrylic acid, 0.1% to 30% of a polyalkenyl polyether, such as a polyalkyl polyether of sucrose, and 5.0% to 74.9% of an additional monomer or monomers. Preferred multi-component interpolymers are the tripolymers resulting from the polymerization of a monomeric mixtures containing, respectively, from 40% to 95% by weight of acrylic acid, 0.20% to 2.5% by weight of polyallyl polyether, such as that of sucrose, and 4% to 59% of an additional monomer or monomers, such as maleic anhydride, N-methyl acrylamide, methyl vinyl ether, ether vinyl ether, n-butly vinyl ether, and the like, and mixtures of maleic anhydride, a vinyl alkyl ether, such as vinyl methyl ether, and a polyallyl polyether, in which the sum of the moles of vinyl ether and polyallyl polyether is substantially equivalent to the molar quantity of maleic anhydride present. It should be borne in mind that in the above proportions, if a maximum amount of two of the monomers are utilized, that somewhat less than maximum amounts of the other monomers must be utilized.
Suitable for use as additional monomers in the production of multi-component interpolymers are monoolefinic vinylidene monomers containing one terminal CH2 ═C< group, such as styrene, the chloro and ethoxy-styrenes, etc., acrylamide, N-methyl-acrylamide, N,N-dimethyl acrylamide, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, vinyl acetate, vinyl benzoate, vinyl pyridine, vinyl chloride, vinylidene chloride, vinylidene chlorobromide, vinyl carbazole, vinyl pyrrolidone, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, methyl vinyl ketone, ethylene, isobutylene, dimethyl maleate, diethyl maleate, and many others. In addition to the above monoolefinic monomers, many of the divinyl dialkenyl or other polyfunctional esters, amides, ethers, ketones, and the like, may be used in the production of multi-component interpolymers, especially those polyfunctional monomers which nominally function as crosslinking or insolubilizing monomers but which are easily saponified and hydrolyzed to additional hydroxyl, carboxyl and other hydrophilic groups. For example, an interpolymer of acrylic acid and divinyl ether is insoluble in water but upon standing gradually goes into solution probably due to hydrolysis and breaking of divinyl ether crosslinks. The presence of strong alkali or acid speeds dissolution. Spectroscopic analysis confirms the presence in the polymers of non-carboxylic hydroxyls. Similarly, diesters, such as diallyl maleate, ethylene glycol dimethacrylate, acrylic anhydride, betaallyloxy acrylate, and many others, are readily saponified or hydrolyzed by alkali or acid with the introduction of additional hydroxyl and/or carboxyl groups. Of the additional monomers, N-methyl acrylamide, methyl vinyl ether, ethyl vinyl esther and divinyl ether have been found particularly useful in the production of the substantially unneutralized crosslinked interpolymers for use as ion sensitive dispersants in the suspension polymerization of vinyl monomers.
The amount of the water-insoluble substatially unneutralized crosslinked interpolymer useful as an ion sensitive dispersant, in the process of making the novel resins of this invention will vary in the range of about 0.01 parts by weight to about 0.1 parts by weight, based on 100 parts by weight of the monomer or monomers being polymerized. Preferably, the amount used will be in the range of about 0.02 parts by weight to about 0.06 parts by weight per 100 parts by weight of monomer or monomers being polymerized.
In the process to make the novel preferred resins of this invention, other secondary dispersants are preferably employed, along with the ion sensitive dispersant. Dispersants which tend to form a skin on the resin particles such as methyl cellulose and high hydrolysis (above 70%) polyvinyl acetate should be avoided. The secondary dispersants should be monomer soluble and not fully soluble in water. For PVA secondary dispersants, the higher the % hydrolysis, the more water soluble the dispersant. For example, 30% hydrolyzed PVA is monomer soluble and not water soluble, 55% hydrolyzed PVA is very soluble in the vinyl monomer but is also partially soluble in water. 72.5% hydrolyzed PVA is fully water soluble and therefore not acceptable. The fully water soluble dispersants will form a skin on the polymer particle. Oil-soluble non-polyethylene oxide containing secondary dispersants are suitable for use in this invention. Suitable non-polyethylene oxide containing secondary dispersants are those compounds from the sorbitan ester family or the glycerol ester or polyglycerol ester families, as well as the low hydrolysis (less than 70%, preferably less than 60%, and more preferably less than about 55%) polyvinyl acetates, which do not contain polyethylene oxide segments. As examples of such dispersants, there may be named sorbitan triolate, sorbitan tri-stearate, sorbitan monooleate, sorbitan monopalmitate, glycerol monooleate, glycerol monostearate, triglycerol monooleate, 50% hydrolyzed polyvinyl acetate, and the like. A mixture of more than one of these dispersants may be used. The function of the secondary dispersants is to increase the porosity of the polymer particles and to increase the colloidal stability of the polymerization mixture. The non-polyethylene oxide containing dispersant is used at a level of from about 0.005 part by weight to about 1.0 part by weight per 100 parts by weight of monomer, preferably from about 0.1 part by weight to about 0.4 part by weight per 100 parts by weight of monomer. More than one secondary dispersant may be used in this invention to achieve the secondary dispersant level.
The polymerization is initiated with a free radical catalyst. The monomer-soluble or oil-soluble catalysts that may be used in the polymerization process of this invention are the alkanoyl, aroyl, alkaraoyl, and aralkanoyl diperoxides and monohydroperoxides, azo compounds, peroxy ester, percarbonates, and other free radical type catalysts. As examples of such catalysts, there may be named benzoyl peroxide, lauryl peroxide, diacetyl peroxide, cumene hydroperoxides, methyl ethyl ketone peroxide, diisopropylbenzene hydroperoxide, 2,4-dichlorobenzoyl peroxide, naphthoyl peroxide, t-butyl perbenzoate, di-t-butyl perphthalate, isopropyl percarbonate, acetyl cyclohexane sulfonyl peroxide, disecondary butyl peroxydicarbonate, 5-butyl peroxyneodecanoate, di-normal propyl peroxydicarbonate, azo-bis isobutyronitrile, α,α'-azodiisobutyrate, 2,2'-azo-bis-(2,4-dimethyl valeronitrile), and many others. The particular free radical catalyst employed will depend upon the monomeric material(s) being polymerized, the molecular weight and color requirements of the polymer, the temperature of polymerization, etc. Insofar as the amount of catalyst employed is concerned, it has been found that an amount in the range of about 0.005 parts by weight to about 1.00 parts by weight, based on 100 parts by weight of the monomer or monomers being polymerized, is satisfactory. However, it is preferred to employ an amount of catalyst in the range of about 0.01 part by weight to about 0.20 part by weight based on 100 parts by weight of monomer(s).
The preferred suspension polymerization process of this invention may be carried out at any temperature which is normal for the monomeric material to be polymerized. Preferably, a temperature in the range of about 0� C. to about 100� C. is employed, more preferably from about 40� C. to about 80� C. In order to facilitate temperature control during the polymerization process, the reaction medium is kept in contact with cooling surfaces cooled by water, brine, evaporation, etc. This is accomplished by employing a jacketed polymerization reactor wherein the cooling materials are circulated through the jacket throughout the polymerization reaction. This cooling is necessary since most all of the polymerization reactions are exothermic in nature. It is understood, of course, that a heating medium can be circulated through the jacket, if necessary.
The preferred process to produce resins of this invention involves using an ionic material to desorb the primary dispersant off the resin. Suitable ionic materials are bases which will neutralize the polyacrylic acid primary dispersant and form a salt. Preferably, the ionic material is a monovalent inorganic or organic base such as amines, sodium hydroxide, ammonium hydroxide, potassium hydroxide, lithium hydroxide, and the like. The most preferred ionic material is sodium hydroxide. Divalent and trivalent materials can crosslink the polyacrylic acid primary dispersant and would therefore not normally be chosen as the ionic material. The preferred embodiment of this invention will be described in terms of using sodium hydroxide as the ionic material. The primary dispersant protects the monomer droplets at the very early stages of polymerization. Before the primary dispersant can graft polymerize with the vinyl chloride, NaOH is added to the polymerization medium. The ion sensitive primary dispersant will then swell in size and desorb off the droplet. Protection of the droplet is accomplished after this point by the increased size of the primary dispersant. The NaOH must be added early in the polymerization, usually from 0.5% to 5.0% conversion of monomer to polymer. If the NaOH is added at the beginning or before about 0.5% conversion, the primary dispersant will be desorbed off the droplet too early and could result in an unstable suspension. Preferably the NaOH is added at from 1% to 3% conversion, more preferably 1% to 2% conversion. Since the primary dispersant is desorbed from the droplet and polymerization is continued without a primary dispersant on the particle, the resulting resin is essentially skin-free. Of course, some primary dispersant can become attached to the resin particle without departing from this invention but there cannot be a continuous pericellular membrane present as there is in normal suspension PVC resin.
The amount of NaOH typically added is an amount sufficient to raise the pH about 0.5 to 1.0 point. Usually the amount of NaOH needed to desorb the primary dispersant is from about 0.0010 part by weight to about 0.0100 part by weight per 100 parts of monomer. More could be used but it would not serve a useful purpose.
If an ion sensitive dispersant is used which will thicken by lowering pH, then rather than adding NaOH to desorb the dispersant, HCl could be used. The HCl would work in the same fashion as desribed above and should be added at similar low conversion levels as described above.
An alternate process to produce the crosslinked skinless resins of this invention is to use extremely low levels of the ion sensitive primary dispersant. Levels of from about 0.01 to about 0.03 parts by weight per 100 parts by weight of polymerizable monomer should be used in this alternate method. If these low levels are used, then it is not necessary to use the NaOH to desorb the primary dispersant from the monomer droplet. Secondary dispersants at levels described above are used in this alternate method.
An additional alternate process to produce the resins of this invention involves the use of a combination of dispersants. The combination of dispersants are non-polyethylene oxide containing secondary dispersants such as sorbitan esters, for example sorbitan monooleate and non-polyethylene oxide containing dispersants such as low hydrolysis PVA, and primary dispersant polyacrylic acid. Sorbitan esters are effective porosifiers but in amounts greater than 0.1 part they tend to be highly destabilizing. It was also found that higher levels of about 0.2 to 0.4 part of sorbitan ester would prevent the formation of a skin by the primary dispersant. It was also found that low hydrolysis PVA (less than 70%, preferably less than 60%, more preferably less than about 55%) in amounts of from about 0.1 to 0.3 part by weight would counteract the destabilizing effect of sorbitan ester. The level of polyacrylic acid dispersant used in this additional alternate process to give skinless crosslinked resin will vary depending upon the level of PVA. For levels of PVA of about 0.3 part, the polyacrylic acid dispersant needs to be less than 0.04 part, whereas for levels of PVA of about 0.1, the level of polyacrylic acid dispersant can be higher, such as about 0.06. As the level of PVA increases, the level of polyacrylic acid dispersant must decrease to obtain a skinless resin. High hydrolysis PVA's greater than 70% and dispersants such as methyl cellulose should be avoided because they will form a skin on the resin.
In the preferred process to produce skinless resins of this invention, a charging procedure similar to the one disclosed in U.S. patent application Ser. No. 06/846,163 filed Mar. 31, 1986, incorporated herein by reference, should be used. The procedure used is what is known as a one poly floating method. The free radical catalyst is first mixed with a solvent, such as isopropol alcohol, in the preferred process. This technique of using a catalyst solution and its added benefits are fully disclosed in the above incorporated patent application. The polymerization reactor charging procedure is explained in the steps below.
(a) Charge water and ion sensitive primary dispersant(s) capable of thickening water to the polymerization vessel. The primary dispersant(s) can be added as such but is preferably added as a concentrated mixture with water. The water and primary dispersant(s) may be premixed before charging to the polymerization vessel. The charge water is preferably demineralized water.
(b) Agitate the water and primary dispersant(s) until an emulsion is formed.
(c) Reduce or stop the agitation such that non-turbulent flow is achieved.
(d) Charge the monomer(s) and crosslinking agent to be polymerized to the reactor vessel such that said monomer floats on top of the emulsified thickened aqueous layer.
(e) Charge a solution comprising a solvent and the free radical catalyst and optionally the secondary dispersant(s) to the reactor. If the secondary dispersant(s) are not combined with the catalyst solution, then they should have been premixed with the monomer before adding to the reactor.
(f) Allow the catalyst solution to diffuse through the monomer layer.
(g) Increase the agitation such that the entire polymerization medium is emulsified.
(h) Conduct to polymerization until 1% to 2% conversion is reached, then add NaOH to desorb the primary dispersant from the monomer droplet.
(i) Continue the polymerization until the desired degree of polymerization is achieved.
An alternate charging method, known as the two poly method, is to first add the monomer(s) and crosslinking agent to the reactor together with the solution containing the catalyst and secondary dispersant(s). The catalyst solution could, of course, be premixed with the monomer prior to adding to the reactor vessel, in which case agitation would not be necessary after adding to the reactor. This mixture is then agitated thoroughly. The thickened water, which had been previously made up by mixing the ion sensitive thickening primary dispersant(s) with water, is charged into the bottom of the reactor through a bottom entry port. Agitation is then re-started and polymerization conducted as above.
The catalyst could also be charged neat into the water phase containing the primary dispersant. If this method were used, then the catalyst would not first be premixed with the solvent.
To produce the crosslinked skinless resins of this invention, a crosslinking agent is used. The preferred crosslinking agents are those materials which are soluble in the vinyl monomer and the vinyl polymer. The reactivity ratio of the crosslinking agent should be such that it prefers to add to the vinyl monomer rather than to add to itself. The rate constants (k) of the various reactions involved can be expressed as: ##STR5##
The monomer reactivity ration of vinyl monomer (R1) can be expressed as ##EQU1## The monomer reactivity ratio of the crosslinking agent (R2) can be expressed as ##EQU2## Ideally the product of R1 and R2 would be equal to 1 (R1 �R2 =1).
The crosslinking agents should be completely reacted before the normal termination of the polymerization, so as not to have crosslinking monomer present as residual monomer in the vinyl polymer. Vinyl chloride polymerizations are normally run to a % conversion of monomer to polymer of from about 50% to 90%, preferably from about 65% to about 80%. The conversions can of course be higher or lower depending on the desired properties of the resin.
The crosslinking agents which are suitable to produce the novel resin of this invention include, for example, diallyl phthalates such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc.; diallyl esters of ethylenically unsaturated dibasic acid such as diallyl maleate, diallyl fumarate, diallyl itaconate, etc.; diallyl esters of saturated dibasic acid such as diallyl adipate, diallyl azelate, diallyl sebacate, etc.; divinyl ethers such as diallyl ether, triallylcyanulate, triallyl isocyanurate, triallyl trimellitate, ethylene glycol divinyl ether, n-butanediol divinyl ether, octadecan divinyl ether, etc; di(meth)acryl esters of polyhydric alcohols such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol methacrylate, etc.; tri(meth)acryl esters of polyhydric alcohols such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolmethane triacrylate, tetramethylolmethane triacrylate, etc; polyfunctional compounds such as bismethacryloyloxyethylene phthalate, 1,3,5-triacryloylhexahydrotriazine, etc. A mixture of more than one crosslinking agent may be used. Diallyl phthalate is the most preferred crosslinker for making the resins of this invention.
The crosslinking agent may be added to the polymerization medium in any maner known to those skilled in the art; such as premixing with the vinyl monomer before charging, charging directly into the polymerization medium or metering into the reaction during the polymerization. The preferred method is to first premix the crosslinking agent with the vinyl monomer before charging to the reaction vessel. If a mass polymerization is used to produce the corsslinked skinless resins of this invention, then the crosslinking agent should be added in the prepolymerizer.
The amount of crosslinking agent used to make the resins of this invention is from about 0.05 part by weight to about 5.0 parts by weight, preferably about 0.15 part to about 1.0 part by weight, more preferably about 0.25 part to about 0.6 part by weight per 100 parts by weight of vinyl monomer.
The polymer particles produced by the present invention should have an average diameter by weight greater than about 70 microns. The particles could have an average diameter up to 1000 microns but normally, the polymer particles will have an average diameter by weight less than about 300 microns. Preferably, for most end uses, the polmer particles will have a diameter in the range of about 100 microns to about 250 microns, most preferably from about 125 microns to about 200 microns. Resins with an average particle size by weight less than 70 microns tend to be dusty and build up static easily such that they are less desirable.
The preferred resin particles of this invention are agglomerated non-spherical in shape. The preferred agitated aqueous suspension processes described above will give an agglomerated non-spherical resin particle. A mass process and the phase inversion process of U.S. Pat. No. 3,706,722 both give more spherical shaped resins than does the preferred agitated aqueous suspension process. A very good method to measure the spherical shape of resins is to determine the shape factor by optical procedures. The image of the particle is projected onto a flat surface to provide a two dimensional view. The shape factor of a particle is determined by inscribing and circumscribing the resin particles flat image with a circle. The ratio of the diameters of the inscribed circle to the circumscribed circle is the number known as the shape factor.
In the case of a perfect circle, the inscribed and circumscribed circles would have the same diameter and, therefore, the shape factor would be unity (1.0). The more near the shape factor is to 1.0 the more spherical the particle.
The shape factor of the resin particles made by the preferred agitated aqueous suspension process of this invention is less than about 0.85, preferably less than about 0.83, and more preferably less than about 0.80. The shape factor of resin particles made by the mass process and the phase inversion process are from about 0.87 to about 0.91.
The preferred resin particles made by this invention also have high porosity of from about 0.10 cc/g to about 0.8 cc/g as measured using mercury porosimeter. Preferably, the mercury porosity is from about 0.30 cc/g to about 0.50 cc/g. Porosity is measured according to ASTM D-2873 procedure. Sometimes porosity is measured as DOP porosity, which gives results about 0.02 cc/g higher than mercury porosity values reported herein for the same resin. When using a mass process, low conversions of from 35% to 65%, preferably 40% to 50% of monomer to polymer, are used to achieve high porosity.
The resins of this invention must be skinless. The terms skinless as used in this specification means that the resin does not have a continuous pericellular membrane as does a typical PVC resin. There may be discontinuous areas or spots of skin on the resin surface but the resin would still be considered skinless under the meaning used in this invention. The term skinless as used herein includes what is normally referred to as low-skin.
One method to characterize skinless resins is to determine the composition of the surface of the resin particle by use of XPS (ESCA) technique. If a resin was totally skinless, there would not be any primary dispersant on the surface. The surface of the resins of this invention will have less than 40%, preferably less than 25%, and more preferably less than 10%, of the primary dispersant, as measured by ESCA technique. The surface will consist mainly of PVC and secondary surfactants (porosifiers).
The resin particles of this invention have a surface composition as measured by ESCA greater than about 20% PVC, preferably greater than about 50%, more preferably greater than about 60%. This indicates that the particles have a significant portion of holes in their skin, where said holes allow the plasticizer to easily pass into and be absorbed by the particle. ESCA is an acronym that stands for electron spectroscopy for chemical analysis. The ESCA technique involves irradiating the sample with X-rays from an X-ray tube. The X-rays knock electrons out of the atoms that are on the surface of the sample. The energy and number of these electrons are measured. From the information one can determine what elements are present. The depth of analysis of ESCA is about 20 to 30 angstroms which is about 5 or 6 monolayers of atoms on the surface of a sample. One should keep in mind that the ESCA test conducts an analysis of the surface visible to the ESCA. In a skinless or low skin resin, pores are open to the surface, therefore the X-rays are going into the pores and the results reflect an analysis of the bottom of the pore as well as the outermost surface of the resin particle. This explains to a great deal why the ESCA analysis of a skinless resin shows the secondary dispersant present. The secondary dispersant is believed to be present on the primary particles which are visible when looking into the pores.
Another method to determine if a resin is skinless is to look at the resin under magnification or take micro-photographs of resin particles and observe if a continuous skin or pericellular membrane exists. In a micro-photograph, an observer can see into the internal area of the resin particles of this invention. The high porosity, friable particles appear like a sponge with many openings in the surface of the resin particle. These openings allow for fast plasticizer uptake and create a friable particle which is easily broken down into smaller units (primary particles).
The resin particles of this invention also have a fast powder mix time as measured using a torque rheometer according to ASTM D-6373. The resin particles of this invention have a powder mix time of less than about 400 seconds, preferably less than 300 seconds, more preferably less than 250 seconds.
The preferred resins of this invention also have good friability. The friability value of a resin in an indication of the relative ease with which grains break down into agglomerates and finally to primary particles. The lower a resin's friability value, the more desirable the resin. High friability values are known to relate to temporary fish-eyes and surface roughness in flexible extrudates. Fish-eyes are undesirable areas in a product, such as a film, which are areas of non-uniformity. This is especially important in powder extrusion and high plasticizer applications. One method to test PVC resin for friability is to place a given amount of resin in a mortar and grind the resin with a pestle. The better the friability, the easier the resin particles will break apart. The friability is then subjectively graded on a scale of from 0 to 5, with 0 being very friable and equivalent to the best known PVC for friability. A level of 5 is equivalent to a high quality film grade resin. Values between 0 and 5 are rated as to how they compare with reference standards which are blends of a 0 value resin and a 5 value resin. The resin of this invention have a friability value of about 2 or less, preferably they have a friability value of 1 or less, and more preferably they have a friability value of 0.
For reference, make up standards using blends of Geon� 92 (a skinless spherical PVC resin produced by B. F. Goodrich according to the process of U.S. Pat. No. 3,706,722) and well known for its excellent friability and Geon� 30 (a high quality film grade PVC resin with a skin produced and sold by B. F. Goodrich) as follows:
Reference Standard "0" is a mix of Geon 92: 100 parts and Geon 30: 0 parts.
Reference Standard "1" is a mix of Geon 92: 80 parts and Geon 30: 20 parts.
Reference Standard "2" is a mix of Geon 92: 60 parts and Geon 30: 40 parts.
Reference Standard "3" is a mix of Geon 92: 40 parts and Geon 30: 60 parts.
Reference Standard "4" is a mix of Geon 92: 20 parts and Geon 30: 80 parts.
Reference Standard "5" is a mix of Geon 92: 0 parts and Geon 30: 100 parts.
Compare the friability of the resin tested to the friability of the reference standards. Choose the standard which most closely corresponds to the test resin and report that standard as the friability of the test resin.
The behavior of a PVC resin during compounding (and that of the resulting compound during processing) is controlled by such properties as resin particle size, porosity and temperature-shear rate depending rheology. The rheology or flow behaviour of PVC is significantly influenced by resin molecular weight, crystallinity, composition and branch structures that might be present. The best method of characterizing these molecular properties, especially when branch structures are present, is to analyze the viscoelastic properties of the resin. The crosslinked resins of this invention may be characterized by their viscoelastic properties.
The method used for determining viscoelastic properties of the resins of this invention involves subjecting a disk-shape sample to very small deformation (less than 1% strain) in a cyclic fashion using a Rheometrics Mechanical Spectrometer equipped with oscillating parallel plates. During deformation of the sample, a certain amount of energy is lost due to molecular segmental motions. The remaining energy is stored by elastic mechanisms. The two types of behavior are simultaneously measured during testing and are relfected in the magnitudes of the loss modulus (G") and storage or elastic moldulus (G'). Also measured is the complex viscosity (n*), which is analogous to the steady state shear viscosity as might be measured by a capillary rheometer.
Complex viscosity is an indication of molecular weight. Intrinsic viscosity (IV) is normally the method of expressing molecular weight of a PVC resin. However, with crosslinked resins the resin is not completely soluble, thus the IV cannot be accurately determined. Therefore molecular weight of the resins of this invention are expressed as complex viscosity, with the units being poise. The complex viscosity is measured at 210� C. The resins of this invention have a complex viscosity of from about 0.9�105 poise to about 1000.0�105 poise, preferably about about 1.0�105 to about 100.0�105, more preferably about 4.0�105 to about 60.0�105. In terms of behavior, a complex viscosity of 0.9�105 poise corresponds to an IV of from about 0.8, and a complex viscosity of 60.0�105 poise corresponds to an IV of about 1.5.
Another important viscoelastic property of the resins of this invention is the tan δ, which is the ratio of the loss modulus (G") to the energy storage modulus (G'). The tan δ can be expressed by the formula: ##EQU3## Tan δ is an indication of the amount of long chain branching (crosslinking) present in the resin. A PVC homopolymer with no crosslinking would have a tan δ of about 1.0. As crosslinking occurs, the tan δ gets smaller. The tan δ of the crosslinked resins of this invention are less than 1.0, preferably from about 0.1 to about 0.95, more preferably from about 0.3 to about 0.7. The tan δ is measured at 210� C.
To further illustrate the present invention, the following specific examples are given, it being understood that this is merely intended in an illustrative and not a limitative sense. In the examples, all parts and percents are by weight unless otherwise indicated.
This Example is presented to demonstrate a process to produce the crosslinked skinless resin of this invention. An 1100 gallon reactor equipped with agitation and cooling means was used in this Example. The following polymerization recipe was used:
______________________________________Ingredient Parts by Wt.______________________________________Vinyl Chloride 100Water (demineralized) 150Diallyl phthalate 0.260Polyacrylic Acid Dispersant 0.025NaOH 0.0025Isopropyl Alcohol 0.120Low Hydrolysis (55%) PVA 0.3002-ethyl Hexyl Peroxydicarbonate 0.045Phenolic Shortstop 0.020______________________________________
The ingredients were charged according to the two poly method disclosed in this specification. The reaction was conducted at 53� C. The NaOH was charged as a solution in water after 15 minutes into the reaction (about 1% conversion). At 275 minutes the reaction was terminated with the phenolic shortstop. The resin was removed from the reactor, stripped of residual monomer and dried to a free flowing powder.
The resin particles were agglomerated, irregular shaped, porous crosslinked skinless resin particles with the following properties:
______________________________________Weight average particle size 160 micronsMercury porosity 0.407 cc/gmPowder mix time 216 secondsComplex viscosity 20 � 10.sup.5 poiseTan δ 0.5______________________________________
This example demonstrates a crosslinked skinless resin having a fast powder mix time, and high porosity. The tan δ indicates a significant amount of crosslinking. This resin when calendered or extruded will give a matte finish.
This Example is presented to show a broad variety of crosslinked skinless PVC resins with different amounts of crosslinking. The same polymerization recipe and charging procedure was used as in Example I except the amount of crosslinking agent (diallyl phthalate) and polymerization temperature. The part level of crosslinking agent is parts per 100 parts vinyl chloride monomer. The following results were obtained:
TABLE I__________________________________________________________________________Reaction Crosslink Agent Complex cc/g Powder Wt. Avg. ParticleRun No.Temp. �C. Part Level Visc. � 10.sup.5 poise Tan δ Hg Porosity Mix Time-Sec. Size-Micron__________________________________________________________________________ 1 55 2.0 45.00 0.17 0.71 159 236 2 40 0.60 53.00 0.24 0.35 363 136 3 53 0.60 20.00 0.38 0.75 -- 191 4 60 0.75 16.00 0.39 0.44 181 218 5 53 0.45 20.70 0.42 0.42 -- 150 6 53 0.45 20.20 0.45 0.38 -- 235 7 60 0.50 11.00 0.49 0.45 227 150 8 65 0.75 10.90 0.43 0.38 215 163 9 53 0.32 13.00 0.54 0.41 -- 14510 55 0.40 15.30 0.55 0.31 -- 22611 60 0.25 5.40 0.88 0.41 227 14412 70.5 0.76 5.90 0.54 0.31 259 14913 65 0.50 8.05 0.60 0.36 295 18214 50 0.15 16.00 0.73 0.41 -- 23515 53 0.15 10.60 0.82 0.39 -- 15016 64 0.40 6.30 0.75 0.32 240 18517 64 0.30 4.45 0.75 0.31 228 16918 70 0.50 1.90 0.68 0.78 -- 45319 70 0.25 0.92 0.73 0.46 136 21820 65 0.25 2.38 0.79 -- -- --21 58 0.20 6.20 0.80 0.37 225 16622 58 0.15 5.70 0.82 0.36 256 16723 56 0.15 7.40 0.85 0.36 -- 9724 70 0.75 4.50 0.52 0.67 -- 214__________________________________________________________________________
The complex viscosity and Tan δ are plotted on a semi-log graph and shown as the attached FIGURE. The graph shows the broad range of crosslinked resins produced in this Example. The numbers beside the point on the graph correspond to the Run No. of this Example II.
This Example is presented to compare commercially available crosslinked PVC resins which have a skin to the skinless crosslinked resins of this invention.
TABLE II__________________________________________________________________________Commercial Skin Complex Hg Porosity Powder Mix Wt. AverageType PVC Resin Visc. � 10.sup.5 Poise Tan δ cc/g Time - Sec. Particle Size Micron__________________________________________________________________________A 44.50 0.70 0.349 448 119B 31.50 0.62 0.366 556 123C 14.80 0.59 0.204 477 123D 5.75 0.62 0.239 829 109__________________________________________________________________________
As can be seen from the above data, the powder mix time is much longer for the crosslinked resins which have a skin than the powder mix times of the skinless crosslinked resins of this invention.
The above four competitive skin type crosslinked resins are shown on the FIGURE. The FIGURE is a semi-log graph of complex viscosity vs. Tan δ. The letters A-D beside the point indicate the corresponding resin of this Example III.
The resins of this invention have many uses where a matte finish is desired in a PVC product such as house siding and window cladding. The crosslinked resins of this invention may be used as 100% of the PVC required in a PVC formulation or they may be blended with non-crosslinked PVC resins in any proportions to achieve a desired result.
|Cited Patent
|Filing date
|Publication date
|11 Jun 1969
|28 Jul 1970
|Pechiney Saint Gobain
|Polymerization of vinyl chloride
|2 Jul 1970
|19 Dec 1972
|Dow Chemical Co
|Polymers from essentially water-insoluble unsaturated liquid monomers and process for preparing same
|15 Jul 1971
|12 Mar 1974
|Mitsubishi Rayon Co
|Vinyl chloride polymer blended with a cross-linked vinyl chloride polymer
|19 Mar 1979
|21 Oct 1980
|The B. F. Goodrich Company
|Method of preparing spherical porous bead-type polymers
|2 Jul 1980
|20 Jul 1982
|Sumitomo Bakelite Company Limited
|Vinyl chloride type resin composition
|18 Nov 1982
|6 Mar 1984
|The B. F. Goodrich Company
|Process for preparing spherical and porous vinyl resin particles
|27 Oct 1982
|3 Jul 1984
|The Bf Goodrich Company
|Process for producing spherical and porous vinyl resin particles
|1 Jun 1982
|3 Jul 1984
|Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
|Cross-linked vinyl chloride polymer
|24 Jan 1985
|28 Jan 1986
|Toyoda Gosei Co. Ltd.
|Steering wheel made of soft resin
|4 Mar 1985
|29 Jul 1986
|The Bfgoodrich Company
|Spherical polyvinyl chloride particles
|Citing Patent
|Filing date
|Publication date
|17 Nov 1988
|27 Nov 1990
|Memron, Inc.
|Porous fluoropolymer alloy and process of manufacture
|6 Oct 1989
|14 Apr 1992
|The B. F. Goodrich Company
|Plasticized articles having vinyl resin-based products in contact with polymeric or polymer coated substrates
|26 Oct 1989
|14 Jul 1992
|The B.F. Goodrich Company
|Rigid thermoplastic compositions capable of forming articles with matte surface
|29 Jun 1993
|6 Jun 1995
|The Geon Company
|Rigid article having a stucco appearance made from a blend of PVC and crosslinked PVC
|2 Feb 1999
|8 Jul 2003
|Sekisui Chemical Co., Ltd.
|Chlorinated vinyl chloride-based resin and molded articles
|9 Oct 2012
|1 Sep 2015
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|11 Oct 2012
|10 Nov 2015
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|10 Oct 2012
|1 Mar 2016
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|13 Mar 2013
|6 Sep 2016
|X-Card Holdings, Llc
|Information carrying card comprising crosslinked polymer composition, and method of making the same
|13 Mar 2013
|14 Mar 2017
|X-Card Holdings, Llc
|Information carrying card comprising crosslinked polymer composition, and method of making the same
|22 Jul 2015
|27 Jun 2017
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|29 Nov 2007
|4 Jun 2009
|Cheng-Jung Lin
|Method for producing a functional vinyl halide polymer
|2 Feb 1999
|5 Dec 2001
|Sekisui Chemical Co., Ltd.
|Chlorinated vinyl chloride-based resin and molded articles
|2 Feb 1999
|21 Aug 2002
|Sekisui Chemical Co Ltd
|Chlorinated vinyl chloride-based resin and molded articles
|U.S. Classification
|521/56, 521/57, 521/59, 526/81, 526/202, 526/344.2, 521/145
|International Classification
|Cooperative Classification
|European Classification
|14 Apr 1987
Owner name: B F GOODRICH COMPANY, THE, 277 PARK AVENUE, NEW YO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:COZENS, ROSS J.;REEL/FRAME:004720/0470
Effective date: 19870413
|20 Sep 1991
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|20 Jul 1993
Owner name: GEON COMPANY, THE
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|14 Sep 1995
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This is 7.62x25 Tokarev Czech Military 86gr. FMJ Ammo on Stripper Clips. This ammo was manufactured by Sellier & Bellot in the Czech Republic. This ammo is brass cased and berdan primed. This is some excellent surplus military ammo that has not been around in many years. This ammo is packed on 8rd. stripper clips in 40rd. boxes.
Thank you for being part of the AmmoToGo community! We are constantly evaluating our suppliers and our products, and your feedback is very helpful in doing so. By including your email address below, we are able to follow up with you, help solve any issues, and learn from you what our community likes and doesn't like.

subset: commoncrawl


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PS4 2.0 Problems: Sony Comments On Issues
Been experiencing any problems with your PS4 since update 2.0? If so, then you're not the only one.
There have been a number of complaints about PS4s freezing and problems users PS4s booting.
The Evolve alpha was also delayed after Turtle Rock said that the PS4's 2.0 update caused problems.
Sony has now commented on the issues though, saying that it is aware of the problems and is working on a fix.
We're aware of issues happening post PS4 2.00 firmware, including some freezes and boot errors. Working to resolve ASAP, will update soon.
— PlayStation (@PlayStation) November 2, 2014
Let's hope the problems that have appeared since the PS4's 2.0 update are fixed soon.
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text:
Donald Holder is a theatrical lighting designer in New York. He has been nominated for seven Tony Awards and in 1988 won the Tony Award for Best Lighting Design and the Drama Desk Award for Outstanding Lighting Design for The Lion King. He won a second Tony in 2008 for the revival of South Pacific. Additional Broadway credits include Les Liaisons Dangereuses, Radio Golf, Movin' Out, The Times They Are a-Changin', A Streetcar Named Desire, and Prelude to a Kiss.
Holder currently is the head of lighting design in the School of Theater at the California Institute of the Arts.


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New Chris Richardson Songs, Mixtapes & Videos
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Report: Cowboys to meet with Oklahoma All-American receiver Ryan Broyles
Former Oklahoma wide receiver Ryan Broyles is visiting the Cowboys, according to a report by Scout.com's Aaron Wilson.
Broyles was one of the most prolific collegiate receivers in the country during his time in Norman, accounting for 4,586 yards and 45 touchdowns in four seasons.
He caught 131 passes for 1,622 during his junior campaign, finishing second for the Biletnikoff Award and earning an All-American nod. Broyles was on pace to match those numbers in his senior season before he tore his ACL against Texas A&M in November.
Just six months removed from surgery, Broyles has been running, cutting and running routes for several weeks and is now ahead of schedule, according to Wilson.
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text: In-Game Examine Window Scrimshaw Great Maul other resources EQ2U · LootDB · EQ2LL · ZAM · Census xml Scrimshaw Great Maul LEGENDARY NO-TRADE +284 str +284 agi +284 sta 71.7% Multi Attack Chance92.1% Crit Chance16.9% Crit Bonus16.9% Potency14.2% Strikethrough StaffTwo-Handed Crushing Damage 224-1162 (197.9 Rating) Delay 7.0 seconds Level 93 (Tier 10) All Fighters, All Mages, All Priests, Beastlord Obtain: Reward from the quest "Going Home" in Cobalt Scar. What does this information mean? Retrieved from "http://eq2.wikia.com/wiki/Scrimshaw_Great_Maul?oldid=592618" Ad blocker interference detected! Wikia is a free-to-use site that makes money from advertising. We have a modified experience for viewers using ad blockers Wikia is not accessible if you've made further modifications. Remove the custom ad blocker rule(s) and the page will load as expected. Categories: Equipment Staff (Weapon Type) Two-Handed Crushing (Equipment Type) Primary (Inventory Slot) Equipment pages with existing default images Legendary Equipment Multi Attack Chance (Equipment) Crit Chance (Equipment) Crit Bonus (Equipment) Potency (Equipment) Strikethrough (Equipment) Tier 10 Equipment Fighter Equipment Warrior Equipment Berserker Equipment Guardian Equipment Brawler Equipment Bruiser Equipment Monk Equipment Crusader Equipment Paladin Equipment Shadowknight Equipment Mage Equipment Sorcerer Equipment Warlock Equipment Wizard Equipment Enchanter Equipment Coercer Equipment Illusionist Equipment Summoner Equipment Conjuror Equipment Necromancer Equipment Priest Equipment Channeler Equipment Cleric Equipment Inquisitor Equipment Templar Equipment Druid Equipment Fury Equipment Warden Equipment Shaman Equipment Defiler Equipment Mystic Equipment Beastlord Equipment Articles missing itemlink Add category Cancel Save


text:
Trades are a way of life in the OHL.
Eight players currently with the London Knights have been on more than one team.
Centre Dan Fritsche joined the Knights on Jan. 10, coming from the Sarnia Sting.
"It's a whole new world for you all of a sudden," he says, especially when you walk into a rival team's dressing room.
The Sting and Knights aren't exactly on the best of terms.
"You're on a new team, you're with a new family, you're making new friends. It's a lot more than people think," Fritsche says.
Defenceman Dan Girardi has gone through it three times. He started with the Barrie Colts, was traded to the Guelph Storm, then dealt to the Knights Jan. 5.
"Barrie and Guelph wasn't really a rivalry, so it wasn't a big deal," Girardi says. "I also knew (the Storm's) Dan Paille. We grew up together in Welland, so that transition was easy.
"But you know at least one or two players in that dressing room."
But Guelph to London?
The Storm had knocked off the Knights in a heated Western Conference final last spring.
"Guelph to here was a little different for sure after last year's playoffs and the rivalry we had," Girardi recalls of the day he came to London.
"I pulled in the John Labatt Centre parking lot at two o'clock on a Wednesday afternoon and I didn't know where to go. I went in the wrong door and was lost," he said.
"They finally called for (Knights general manager) Mark Hunter and he came and got me.
"The first guy I saw in the dressing room was Dave Bolland. He looked at me and came over and said, 'Hey, I'm Dave Bolland.' We clicked right away and I felt like I was part of the team already."
The Knights are like a family. The players do a lot of things together away from the rink, and just like real siblings they have their moments of disagreement.
But it's all part of learning to exist in a family environment.
There are times when Corey Perry is not patrolling the right wing that he thinks about what he might be doing if he was back home in Peterborough.
"I know I'm missing out on other things back home on a Friday night. Of course you do," he says.
"In your teenager years you want to go out and have fun, but you've got to play hockey that night.
"But right now everybody on this team is like a brother and there's nothing better than coming to the John Labatt Centre on a Friday night and playing hockey and going out for a little bit after the game.
"That's what we do."
Perry adds: "We don't try to abuse the system, but we like to have a good time, too. And we have our squabbles. There's always something going around, but that's the name of the game."
Defenceman Marc Methot thinks every day about what he's going to do once he leaves the OHL. The 19-year-old is a sixth-round draft pick of the Columbus Blue Jackets but knows not all players realize their dream of playing in the NHL.
"I know a few guys back home in Ottawa and they've gone to college and landed good jobs," he says of what happens when the dream ends.
"It's something hard to cope with if you planned on going somewhere in hockey, but you have to be ready for it."
No matter what happens, Methot won't regret his three years with the Knights.
"It's been just positives ever since I moved here. I think of how my people skills have improved. With all the public relations work we do for the team, it makes me really at ease with large groups."


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The Most Unexpected Halloween Candy From Each State
York® Peppermint Patty
BY YORK PEPPERMINT PATTY #55 in Chocolate
4.76 / 5 based on 9,215 Reviews
Product Description
The perfect way to end a meal. Bite into the refreshing sensation of cool peppermint and rich, dark chocolate.see more...
Top Questions See all 114 Q&A
- Does anyone remember the commercials for peppermint patties from ...2 Answers
- Are theses any good and where can you get the from?9 Answers
- Are these good frozen ? I've heard they are amazing frozen in the...17 Answers
York® Peppermint Patty
Reviews (9215)
Media (38)
- "I do not like dark chocolate except for with these...my great grandma would always make sure I had them when I went to go visit her" in 236 reviews
- "This candy bar is the best mint candy out there,it taste great,it has dark chocolate for the health conscious, has less fat,that's always a plus and it'll cure a sweet tooth." in 64 reviews
- "I could eat this candy bar every day it's so refreshing and the dark chocolate is just so good with the peppermint if I could get a box or case I would sit and eat everyone if you never ever had one you have to try it is the candy bar of all candy bars. " in 35 reviews
- "The perfect candy when you need a pick me up at 3:00 in the afternoon, and you won't feel so guilty about having one (low fat!)." in 33 reviews
- "I love york peppermint patties this is my favorite candy by Hershey's.Its so sweet but not too sweet,has a peppermint flavor and dark chocolate flavor.This peppermint chocolate is so inexpensive!" in 31 reviews
If you are low carb, it can be difficult to find an edible sugar free candy. If you are low carb and gluten free/grain free, it can be next to impossible. I can not even buy the ones that are manufactured on the same line as candies containing gluten, because of the very real problems of cross contamination. Some people can tolerate that, but people like me who react to the tiniest amounts can become very ill from ingesting those tiny amounts. For that reason I can't buy Russell Stover or Weight Watchers brands to name two. Not to knock them, because they have excellent candy, but I found out the hard way that I simply can't eat them. I tried these because I was getting tired of the same old things all the time. I was not a particular fan of them in my sugar eating days, but I wanted to try something new. Holy cow, these are really good. They are creamy, smooth, chocolatey, and delicious. My husband and I both loved them. My picky oldest child did too, and he normally doesn't like anything sugar free. They are a wonderful find for low carb and/or gluten free people, and a very nice treat. I find one of them very satisfying, and do not find myself overeating them. I think that might be because they have a stronger taste than most candies, so one is all I want or need. My husband and son can both eat more, so these go fairly quickly. These are excellent, and I love them. One of my favorite treats!
Yes!!! what was the saying associated with Peppermint Patty?! but a childhood favorite of mine that's for sure! I can't remember, but I do recall that on the commercials after biting into a Peppermint Patty the actors' hair would blow back from the coolness of the Peppermint patty! I love the "refreshing" taste of the peppermint patty. I have even had mini Peppermint Patties and the had that same genuine mint taste they always had! I will always buy these. They are great as an after dinner mint too. I would recommend them to anyone.
I have made homemade chocolates every Christmas for the last 20 years. While I do not make as many as I used to I still have a few that will always be on my baking list. I have tried and tried and tried so many different variations of Peppermint Patti Recipes and every one of them .... thumbs down!! I have since given up on that search for the perfect recipe and now stick with the original-- the York Peppermint Patties !! So delicious and so definitely a holiday must!!
This is one of my favorite snacks that i love to get when I'm grocery shopping or when its a movie night. Thisvhas a really strong mint flavor to it which takes over the chocolate flavor but its still very good. I do only recommend this for older people only because of the strong km int flavor to but kids can eat to if they really want to. The one thing i do is i save half because it can get overwhelming with the flavor but other than that it is rwally good.
These are by far my favorite types of candies! I could dance in a long line with frezzing rain drizzling around me as long as I had one refreshing bite of York peppermint patty! Really it is my most favorite ever and if you are skitical in trying it just for The love of life do it! It's a wonderful explosion of all things wonderful and cheerful in The world coming together inside your mouth. Besides who doesn't love chocolate?
At one point, I was OBSESSED with these. It's a very refreshing treat. One patty is enough and you feel satisfied for those of your who are chocolate lovers, and crave it sometimes; like me. I have not had a York Peppermint Patty in a while now, so that's why I gave it 4 stars, because I can't speak for them now, but when I worked at Hallmark, I would pay 25 cents for a little bite sized one and use it as a little treat. Yum!
My favorite candy as a child and what will continue to be my favorite candy until I'm ancient. My aunt buys me two giant York peppermint patties every valentine's day and Christmas as well as random bags of patties every time I visit her house. They're always in Stock when she knows I'm coming to visit. I always have mints with me and I would always have York patties with me if it weren't for the risk of melting.
Love these things! I get the minis all the time. My instructor for AHIT used to put these on our desks on test days, which was really a great refreshing treat when you're brain is being fried with health insurance information. The peppermint flavor goes along great with the chocolate coating. To top it off peppermint oil is good for soothing the stomach as well as is purported to aid in digestion and headaches.
I absolutely love peppermint patties, they are one of my favorite chocolates since forever!! They taste so good and minty I am obsessed. My kids love these as well thanks to me, lol. One of my favorite cakes I make is using york peppermint patties, everyone loves that cake thanks to the major ingredient of peppermint patties. I will always love this chocolate, I could eat a whole bag in one sitting.
Sometimes after lunch or dinner, I'm looking for a sweet finish or a minty treat to cleanse my palate. Especially if I'm at work, I tend to reach for a mint since I interact with many people at my workplace throughout the day. That's why I love York Peppermint Patties! Just one is all I need to satisfy my sweets craving. Just a forewarning though, these babies are sugary with 27g of sugar a pop.
Has anyone every tried to freeze and eat the peppermint pattie? It last longer. yum.
How do you eat your peppermint patty?
York Peppermint Pattie or Junior Mints?
Do you like to eat these room temperature or straight out of the fridge?
Am i the only one who thinks they're even better when kept in the freezer?
See All Photos & Videos


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Yearly horoscope forecast Scorpio (October 24 to November 22)
Horoscope 2014 Scorpio: OPPORTUNITIES FOR SCORPIO IN 2014
Until mid-July at least, you will have the curious planetary combination of a spendthrift who loves to travel – Jupiter – being in his own solar ninth house of travel. So you want to get away and have some fun. I think not only do you need a break, and deserve one, you are destined to have one! I think you're likely to make the best use of your frequent flyer miles, your hotel guest rewards cards, your [insert company name here] loyalty program that gives you membership discounts not to mention those social group-buying offers as well as your list of contacts to ensure a trip goes ahead! Circle 18 April as the Golden Day to depart or book a holiday with your lover. It is such a fertile day that couples who hadn't considered children yet could get pregnant. Single Scorpio on holidays could meet The One. You'll also enormously enjoy holidays taken on 18 June and 6 May.
On 16 July, Jupiter wants to raise your public profile by taking a year-long journey through your solar tenth house of career. This is the best time to get your CV ready, contact recruiters, tell your boss you'd like a promotion thank you, do projects which will propel you into the corporate eye, do high-level presentations, launch your own company or to hire a PR company to ensure your own business gets much needed coverage. Make important presentations on 24 July when your charm will win them over and use all your psychological techniques and black book contacts for a left-field business pitch on 18 August and 25 September. With Jupiter going retrograde between 8 December until 31 December 2014, your business prospects may seem to be in "Park" as you play phone, email, contract and meeting tag with someone senior but all will move ahead from February 2015.
Horoscope Scorpio 2014: CHALLENGES FOR SCORPIO IN 2014
Whatever your actual age, with Saturn in your solar first house of personality, since 6 Octomber 2012, you may have felt like you've skipped a decade or two and gone straight to middle age. Saturn here can prematurely create grey hairs, wrinkles, age spots, love handles, bone density, flexibility, mobility, vision and hearing problems (and some of those Gen Ys are in for some hearing problems already with the volume seemingly cranked up to 11 on their iPods). But he also gives you (eventually) hard-earned wisdom and the sense of security that comes with being true to yourself. You become more authoritarian and somewhat less social. Part of this is that you may feel a more serious side coming out and you fear that others won't like you for it. Don't worry, they admire the extra depth within you. Curiously, this transit also makes it much easier to lose weight – don't lose too much though, that really IS ageing!
If you had internal "niggles" that something had to change before, it will be unavoidable now. You may attract rather critical types who will tell you your shortcomings in no uncertain terms. You may also start to feel older, with the weight of responsibility on your shoulders. If you've never been into comedies much before, I'd overdose on them now. It will be all too easy to feel depressed and morose and unlovable, which is obviously ridiculous! Letting your guard down and letting them seeing the true you AND knowing they still love you anyway will be incredibly touching. You may also see a vision of the "future adult" in your children. Use 13 November to have a deeply intimate conversation with someone about yourself. Their laser-focus insights may help you see what you need to change to feel truly happy
Saturn goes retrograde from 2 March to 20 July, creating a four-month period when you may feel more than a little insecure, serious, pragmatic, cautious and afraid of rejection. You may find it harder than usual to get your goals achieved and you may rethink your life's direction, too. Try to count to 10 when someone criticises you, like for the millionth time. Your leadership ability will return.
2014 Horoscopes for Scorpio
Scorpio 2014 Horoscope
Scorpio Love Horoscope
Scorpio Money Horoscope
|Scorpio Career Horoscope


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Complaint Review: SEOleads.me
SEOleads.me, Brian Deceitful Practices, Bogus Leads, Non Quality Internet
*REBUTTAL Owner of company: This Individual Contacted 1 Lead Then Complained
SEOleads.me is a company that provides digital marketing leads for SEO and PPC companies. They sell in batches with the cheapest cost of a batch at 325.00. They claim that all of the leads they provide are from interested parties and that they have been verified multiple times prior to purchase. They also claim that if you have a bogus lead, to notify them within 48 hours of receipt, and they will provide you another lead. They also claim a 20% closing ratio for the leads they provide.
My experience was bad from the beginning. I paid the 325.00 for a batch of exclusive leads and when I called every single one of them, not one was aware or had ever heard of anything relating to SEO or PPC. I complained to Brian from the company and he was helpful at first. He provided me with another batch and was apologetic. He then also provided me a little insight as to how these leads should be addressed. This was a little concerning as I am a professional sales person and have multiple years experience in handling Digital Marketing Clients.
When I finally was able to get a hold of one of these business owners, I asked her how she was approached and what she recalls. Turns out, that she happened to answer a call from a company claiming to be taking a survey! She said that she answered about 50 questions. The 2 questions that she answered that SEOleads.me claims make her a qualified are, "Would you like to be on the first page of Google?" and the 2nd was, "Do you have or have you ever had a website?" Because she answered yes to both of those questions, they sold this to me as a qualified SEO/PPC lead!
When I called back in to complain about the quality and to request a refund, I was told by Brian that I had every opportunity to ask questions prior to getting a batch sent to me! He is claiming that he did his job! He's saying that it doesn't state anywhere that the leads are going to be from people who are wanting SEO????? How do you even argue with somebody like this? I am writing this for any SEO startups or anyone who is out there looking for qualified SEO/PPC leads. Avoid this company at all costs!!!
Does your business have a bad reputation?Corporate Advocacy Program™Fix it the right way.
Set the record straight:Arbitration Program
This report was posted on Ripoff Report on 02/24/2014 07:21 AM and is a permanent record located here: http://www.ripoffreport.com/reports/seoleadsme/internet/seoleadsme-brian-deceitful-practices-bogus-leads-non-quality-internet-1125991. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year. Ripoff Report has an exclusive license to this report. It may not be copied without the written permission of Ripoff Report. READ: Foreign websites steal our content
If you would like to see more Rip-off Reports on this company/individual, search here:
#1 REBUTTAL Owner of company
This Individual Contacted 1 Lead Then Complained
AUTHOR: SEOLeads.me - ()
SUBMITTED: Tuesday, February 25, 2014POSTED: Tuesday, February 25, 2014
This individual named Jeremy Burgen is a habitual fraud. Not sure why he is hiding behind an anonymous label.
Maybe it has something to do with his track record, which you can read more about right here:
This scammer contacted one (1) lead, then claimed that the leads were no good and demanded a refund. Really? Is that how things work in the real world?
This is after knowing that there is nothing that I would do to recoup the leads that were already delivered to him.
As I stated clearly to Jeremy Burgen, the leads are from business owners who are surveyed and answer yes to two questions:
1. Do you want your business listed on the 1st page of Google? Yes.
2. Are you willing to move forward with a plan so long as it is within your budget? Yes.
So through the power of deduction, it can be determined that these are SEO leads.
Jeremy Burgen is a complete fraud as you can see from his willingness to defraud his past insurance client. Luckily, the proper action was taken and his insurance license was suspended.
ZipBooks Accounting Software
Advertisers above have met our
strict standards for business conduct.


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Gift To New Grandmother Totes
You want to be the very best? Like no one ever was? Now you can, when you walk into your gym wearing this brand new Pokemon Go-themed T-Shirt! The Pokemon shirt to end all Pokemon shirts, you can impress and intimate everyone who's either just starting to play the popular Pokemon Go mobile app, or the unfortunate trainer who's brave (or dumb) enough to challenge for your home turf! Whether you're on Team Valor, Team Mystic, or Team Instinct, you will make them look good with your new shirt!
Tags: game, quotes, i-go-to-the-gym-every-day, pikachu, pokeball
When you're a mutant whose weapon of choice is playing cards, a poker room seems like a logical place to retire to. I've posted two different versions of this design - one is distressed; the other is not. This way, you guys can choose your preference, rather than be subject to mine.
Tags: comic, superhero, movies, superheroes, marvel
It is finally here, the former champion Dan Murrell has the New Murrell Order exclusively on this store. He is arguably the most devestating competitor we have ever seen in the Schmoedown. Thanks to Hunter "HDmex" DeSander now we have it. Enjoy!! Check out Hunter on Twitter. @HDmexiqtioner
Tags: schmoedown, schmoes-know, schmoedown-spectacular
Realtor & new homeowners gift shirt - housewarming gift Be Unique with this Original Design T Shirt by Zone 365 Tees. Our shirt designs are original, created in the U.S.A. Feel good about Yourself wearing Zone 365 Custom designed T-Shirts. The PERFECT shirt to celebrate your new house for the new home owner!
Tags: housewarming, home-owner, house-warming, gift, mothers-day
Some Cat (At) psychologists have suggested thatwhat they're giving to you isn't so much a gift as it is doing your hunting for you. He doesn't think you can catch that rebel scum by yourself. (An update to an old piece, with a more film accurate ship).
Tags: pew-pew, darth-vader, star, wars, empire


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Babies R Us Diaper Coupon
This awesome deal on Babies R Us Diapers is back again! Right now Babies R Us has Special Value Babies R Us brand diapers priced at just $10 plus there are over $50 in coupons inside the box including a coupon for $6 off Babies R Us Brand diapers making them just $4 a box or just around $0.05 a diaper, depending on the size you're buying! Yay!
The coupon is good for 72 ct or larger so you could not use it on the size 5 diapers which are 56 ct. All coupons expire on 3/5/14.
Last time we saw this deal I asked if I could open the box to get the $6 coupon to use on my purchase and I was allowed to. One coupon takes off $6 for each box you buy! I stocked up big time last summer when these diapers were actually free, and I'm still using them on my 4-month old boy. We have never had an issue with them and I think for free or super cheap, they work great! No complaints here for an awesome deal on diapers, which can be such a huge expense for families.
Let us know if you scored them at your Babies R Us!


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Rambus acquires Uni-Pixel backlighting display IP
Post a comment
SEATTLE Rambus has acquired a portion of Uni-Pixel's intellectual property portfolio relating to dynamic backlighting, field sequential color displays, and Time Multiplexed Optical Shutter display technology for $2.25 million.
In addition, Uni-Pixel has entered into an engineering services agreement with Rambus for future collaboration and technology development.
Backlight technology based on TMOS display technology can be applied to current LCD display panels to create a more efficient and cost-effective device.
TMOS can potentially lower the LCD bill-of-materials and manufacturing costs by as much as 40-60 percent, while improving display performance and power characteristics, according to Uni-Pixel.
"The alignment with Rambus leverages strong business and technical synergies around the licensing, development and manufacturing of advanced micro-optics, backlight systems and display technologies," said Reed Killion, president and CEO of Uni-Pixel, in a statement.
"This acquisition recognizes the significant contributions Uni-Pixel's innovative technology can make to our solutions for LCD displays" said Jeff Parker, senior vice president of the Lighting and Display Technology group at Rambus.
Uni-Pixel's business model was to license the TMOS display and backlight technology to existing panel and backlight manufacturers.
It will continue to supply current and future licensees with what it calls Clearly Superior Performance Engineered Film.
Uni-Pixel is presenting a paper at the Society for Information Display here this week detailing a film printing process that does not rely on the use of lithography or etch steps.
Rambus's Marc McConnaughey, Vice President of Strategic Development, is on a SID panel discussing "The Future of Lighting & Backlighting."


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WFIU Public Radio
WTIU Public Television
Choose which station to support!
Pianist and composer Émile Naoumoff holds the unique distinction of being the last protégée of Nadia Boulanger.
At WFIU, we're thawing out with some fine classical music in March.
What is RSS? RSS makes it possible to subscribe to a website's updates instead of visiting it by delivering new posts to your RSS reader automatically. Choose to receive some or all of the updates from Indiana Public Media Arts & Music:
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by Joanne Lovito-Nelson
The Student Planning Association is hosting a School of Urban and Public Affairs end-of-year party at Bowl & Barrel located at 8084 Park Ln., Suite 145, Dallas, TX 75231.
The event will take place May 18, 2013 at 8:00 pm. For more information contact David Stark at email@example.com.
Come join the fun!


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When I started blogging I wanted to share ideas and inspire others when decorating your home.
I wanted to show that you don't have to have a big budget or allot of money to make your home beautiful.
And I wanted to share that sometimes you don't have to spend any money at all and still decorate or change your home.
I am just like you,I love sitting down in a cozy spot with my warm beverage and look at beautiful magazines for inspiration.
When I was a little girl I loved decorating my bedroom.
I would often move my furniture around and place my pretty things in different spots for a new look.
And I remember going to garage sales with my Grandparents.
I think that is what inspired me the most.
Hunting for treasures for such a little money.
I love finding pieces that were once loved,pieces that have history.
If I find a piece that has drippy paint from a not so good paint job,I love that piece even more.
Nothing in my home is perfect,nothing.
And that is just the way I like it.
Yes in photos that I share my home looks all put together,but it's not like that everyday.
How could I live in a home like that?
But just like a pretty magazine I am hoping to inspire you.
Use what you have,what you love.
It does not have to be perfect.
And paint can change any room,and it's cheap!
These bottles were found a few years ago while out thrift shopping.
They are just bottles,nothing fancy at all.
You can find really pretty soda bottles at the store,after you use them keep them.
They make great vases.
A teapot,another great vase.
Nothing fancy or expensive,but it looks so pretty on a tablescape or on an accent table.
Don't ever be intimidated when you see a home with pretty photos.
They are just like you,no one has a perfect home.
Just enjoy what you have and make it the best home you can.
If you surround yourself with things you love you cannot go wrong.
Enjoying these roses as they start to wilt.
During the winter months flowers are a must in my home.
I am ready for spring,are you?
Cedar Hill Farmhouse The Scoop


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Turning digital has become a well-understood imperative. Although digital has commonly found its way into corporate strategies, the path to transforming adequately remains unspecified.
As part of an international cross-industry study, Arthur D. Little has considered the digital maturity of more than 100 European companies from seven industries in detail and systematically assessed them. The Arthur D. Little Digital Transformation Index (DTI) shows that few firms can be considered "digital oriented" or "digital centric". Only about 20 percent of companies know how to make digitization active, and the rest are simply trying to respond to digital developments - without a conclusive overall concept. Read more and take a deep dive into our study results:
+ Digitization will change the competitive environment of all industries significantly
+ Most industries are already affected by digital disruption or realize that they will be soon
+ Few companies yet follow a consistent digitization approach for their whole business mode
+ Companies underestimate opportunities in Operations and in Business Model Redesign
+ There is a huge demand and backlog for the majority to deal with "Digital" properly
+ No industry can claim to be a digital front-runner; however, each industry has its outperformers
+ Most companies are either not aware of or ignore potential threats from digital disruptors
+ Companies are too slow in transformation, though they face rapidly evolving digital competition
+ Third-party integration is often underrated, as companies still try to solve problems on their own
+ The usage of "smart data", and thus also personalized offerings, lag behind
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text: I just drooled over 117becca's GFG for her aunt and I notice that the flowers have only 2 rings. I always had only seen 3 rings. But since I've seen hers, I notice other quilts with the 2 rings on the flowers. Which is more historically correct? Or is it just a matter of choice of the quilter?


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Edit Article
wikiHow to Manage Your Online Self With UnHub.Com
You have a definite presence on the Internet and are hard pressed to remember all of the URLs. Now you don't have to. Read this article to learn how you can manage all of your social networking from one place...UnHub.Com.
1Go to UnHub.Com. Create your account. It's very easy. Type in the account name, password, email, and a website that you use a lot, or that you want to put there.
2Take a look at the UnHub Dashboard. You have a few options that can prove very useful to someone trying to improve their social network value.
3Start making changes. A tool like this isn't helpful unless you learn it and use it. Begin with your personal profile. Click on to see what the end result will be.
4Check out the analytics of your pages that you have added to your profile.
5Examine the link shortener. UnHub has a variety of ways to shorten URLs, see which one works best for you.
6UnHub It!. UnHub a site with the URL shortener and the toolbar button you can add, and UnHub will track the analytics for you! You can see when your sites that you shortened are getting visited.
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Friday, March 26, 2010 | 12:50 p.m.
Year-Round Elementary Schools Converting to Nine-Month Calendar 2010-11
- Beatty
- Brookman
- Cahlan
- Carl
- Cortez
- Crestwood
- Diaz
- Diskin
- Edwards
- Frias
- Gragson
- Hayden
- Hickey
- Hummel
- Lamping
- Moore
- Petersen
- Smith (Hal)
- Steele
- Tartan
- Watson
Citing concerns about the potential impact to students, families and staff, the Clark County School Board voted today to hold off on converting all 76 year-round elementary campuses to nine-month calendars as a cost-savings measure.
Under the existing district policy for triggering calendar conversions, 21 schools are set to move to nine-month schedules beginning in August. Those plans will proceed, saving the district an estimated $5.5 million.
Had the School Board approved sidestepping its own policies and allowed all 76 schools to make the switch, the savings would have been about $15 to $20 million. The district needs to trim $123 million from its operating budget for the upcoming fiscal year.
But the potential harm to student learning and the negative impact on some campus communities was too high a price for School Board members. Support employees at year-round schools face a cut in pay if they are moved to a nine-month schedule, as do some licensed personnel in specialist positions.
The vote to maintain the current policy was 4-3, with members Chris Garvey, Larry Mason, Sheila Moulton and Linda Young in support.
Opposing the motion were School Board President Terri Janison, Vice President Carolyn Edwards and member Deanna Wright, who wanted to give schools more flexibility than the current policy allows.
Edwards said the district should be looking at the downturn in enrollment (expected to drop this fall for a second consecutive year) as an opportunity. She recommended expanding the guidelines to give campuses more of a chance to make the calendar switch if it's logistically reasonable, even if the current regulation's "triggers" aren't met.
"I don't see why it has to be all or nothing," Edwards said. "We can be a little bit in between here. There are schools that can come off (the year-round calendar) and want to come off. For those that it's really a struggle, they can stay on."
During Thursday's meeting, which was continued to this morning for the vote, members heard from several constituencies that opposed the change, including staff and parents.
Many of the year-round schools serve high numbers of minority students from low-income households. Principals and teachers told School Board members they feared student achievement would suffer if at-risk students had a long summer break from learning, rather than the year-round schedule's shorter track breaks. Some national studies have suggested that English language learners (who account for about 19 percent of Clark County's student enrollment) do better following a year-round calendar.