text:
|Publication number||US3549569 A|
|Publication date||Dec 22, 1970|
|Filing date||Jun 29, 1967|
|Priority date||Oct 10, 1966|
|Publication number||US 3549569 A, US 3549569A, US-A-3549569, US3549569 A, US3549569A|
|Inventors||Basil S Farah, Herbert M Schroeder|
|Original Assignee||Textron Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (20), Classifications (26), Legal Events (1)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Int. Cl. C08g 22/06 US. Cl. 26018 30 Claims ABSTRACT OF THE DISCLOSURE Urethane prepolymer coating compositions are made from 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane and aliphatic polyols or water at a total NCO to OH ratio of at least 1.2:1. When the coating composition is moisture-curing the polyol preferably has as its major component aliphatic polyol having a molecular weight of at least about 500. When the coating composition is polyolcuring the polyol used in making the prepolymer preferably has as its major component aliphatic polyol having a molecular weight of up to about 200, and the polyol used to cure the composition preferably has as its major portion aliphatic polyol having a molecular weight of at least about 500. These prepolymer coating compositions may contain about 3 to 35 weight percent of free isocyanate groups and the compositions are of application viscosity, at least when in a solvent, even when derived from a polyol component containing a significant proportion of polyol having three or more hydroxyl groups and therefore exhibits cross-linking tendencies. Cured coating made from the prepolymer compositions exhibit outstanding resistance to the discoloring action of ultraviolet light rays and possess other desirable properties such as good adherence to substrates and excellent abrasion resistance and strength.
This application is a continuation-in-part of application Ser. No. 585,262, filed Oct. 10, 1966, abandoned and application Ser. No. 630,528, filed Apr. 13, 1967, now abandoned.
This invention relates to polyurethane compositions. More particularly, the invention concerns polyurethane prepolymers made from 1-isocyanato-3-isocyanatomethyl- 3,5,5-trimethyl cyclohexane and aliphatic polyols or water. These prepolymers can be cured by reaction with an active-hydrogen containing material which reacts with free isocyanate groups, e.g. water, aliphatic polyol, etc. or mixtures thereof, and when formed as coatings, exhibit outstanding resistance to the degradative and yellowing action of ultraviolet light rays. The cured coatings, moreover, are stable, adhere firmly to various substrates and possess excellent abrasion and strength properties. The use of l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane is highly advantageous in coating compositions whose prepolymers are made from aliphatic polyol at least a portion of which has at least three hydroxy groups.
It has been known for several years that polyurethane coating films which have been cured by reaction of free residual isocyanate groups in the polymer, become increasingly yellow on continued exposure to sunlight. Since light from an ultraviolet lamp gives a similar effect, it is apparent that the ultraviolet part of the spectrum of sunlight causes most of the yellowing. Coatings made from aromatic diisocyanates yellow to the greatest extent, but polyurethane coating films made from several aliphatic diisocyanates also yellow significantly, although less, when ice exposed to ultraviolet light. Furthermore even though the aliphatic diisocyanates are relatively advantageous in this regard there may be difficulties in producing satisfactory coatings from urethanes from these diisocyanates, especially where the urethane prepolymer is made from aliphatic polyol having at least three hydroxl groups and thus is cross-linked with a tendency to form intractable gels before being cured.
In spite of these problems such coating vehicles are highly desirable. The moisture-curing vehicles are especially of interest since their viscosity does not change if contact with water is limited and, accordingly, with proper care the viscosity can remain more or less constant during storage prior to application of the coatings to substrates. Curing in the can can be stopped even when only a portion of the contents are used, simply by rescaling the can or otherwise holding the composition out of contact with moisture. Moreover, moisture-cured coatings are generally hard, chemically-resistant and of low water permeability.
By the present invention, we have discovered that the prepolymer-type polyurethane coating compositions derived essentially from l-isocyanato-3-isocyanatomethly- 3,5,5-trimethyl cyclohexane, that is,
and one or more aliphatic polyols, water or their mixtures have, when cured as coatings, excellent resistance to yellowing under the influence of ultraviolet light and at the same time possess other desirable properties needed in cured polyurethane coatings and finishes. Even the prepolymers derived from this diisocyanate and polyol components composed in part or entirely of polyols having three or more hydroxl groups, can be made to remain in an essentially liquid state and are highly suitable prepolymer coating compositions. Although the essential isocyanate used in making our prepolymers is 1-is0cyanato-3-isocya natornethyl-3,5,5-trimethyl cyclohexane minor amounts of other polyisocyanates may be present providing the coatings are not unduly deleteriously affected, for instance, the use of aromatic diisocyanates could lower the resistance of the coatings to the effects of ultraviolet light and the presence of diisocyanato dicyclohexyl methane makes the prepolymers more susceptible to gellation. German Pat. 1,202,785 and Belgian Pat. 666,023, disclose l-isocyanato- 3-isocyanatomethyl-3,5,5-trimethyl cyclohexane which can be made by phosgenation of 1-amino-3-arninomethyl-3,5,5- trimethyl cyclohexane, preparation of the latter being described in Belgian Pat. 621,259.
Due to the high resistance of the l-isocyanato-S-isocyanatomethyl-3,5,S-trimethyl cyclohexane-derived coatings t0 the deteriorating and yellowing action of ultraviolet ligh we can prepare clear coatings which remain of considerably lighter color than those which can be produced from many isocyanates, especially the aromatic diisocyanates such as toluene diisocyanates. Moreover, when our compositions are colored, for instance through the addition of pigments, the polyurethanes remain stable over prolonged periods, whereas coating vehicles and coatings derived from other diisocyanates may darken continually on exposure to light, for example, when the vehicles are stored in transparent containers. Thus, the polyurethanes of the present invention have potentially wider areas of use than most polyurethanes heretofore available and our compositions can, for instance, be employed in clear or pigmented, non-yellowing wood finishes such as floor finishes and marine finishes; non-yellowing and non-chalking, enamel finishes, e.g. for automobile bodies; and for many other uses. This great potential for the compositions of our invention is further made possible since our coating films having high strength, abrasion resistance and hardness, do not crack or mar easily and have good substrate and intercoat adhesion properties so that the coatings resist peeling and blistering upon weathering.
The urethane polymers of the invention are essentially made by reaction of l-isocyanato-3-isocyanatomethyl- 3,5,5-trimethyl cyclohexane with urethane-forming aliphatic polyols or water, and the urethanes prior to curing, which takes place after application of the urethane prepolymer as a coating, are in the essentially liquid state either as the polymer per se or dissolved in a solvent. The uncured polymer or prepolymer is generally stable in the sense that the prepolymer will not cure to a solid unless further contacted with water, aliphatic polyol or other active-hydrogen containing material. These prepolymers can have a free isocyanate group content of about 3 to 25 or even 35 or more weight percent based on polymer content or solids.
The prepolymer-forming reaction mixture contains a ratio of total isocyanate groups to total hydroxyl radicals (including the OH of water) of at least 1.2:1, often up to about 3.5 :1 or more. In the case of moisture-curing prepolymers this ratio is often 1.2 to 2.5 :1, preferably 1.3 to 2.1:1, and the ratio of isocyanate groups to hydroxyl groups can affect the properties of the moisturecuring coating compositions. Increases in the ratio give coatings of greater film hardness and mar resistance while flexibility and impact resistance may be adversely affected. Also, larger amounts of free isocyanate groups increase the toxicity and cost of the compositions. The free isocyanate groups in such moisture-curing prepolymers are often from about T to 12 weight percent, with about 5 to 1'0 percent being preferred, based on polymer content or solids.
In the case of aliphatic polyol-curing prepolymers the prepolymer-forming reaction mixture generally contains a ratio of total isocyanate groups to total hydroxyl radicals of 1.4 to 3.511 or more, preferably 1.6 to 2.1:1. The ratio of isocyanate groups to hydroxyl groups can affect the properties of the coating composition, but undesirable results can be offset somewhat by using an aliphatic polyol for curing of appropriate molecular weight, e.g. polyol whose major portion by weight has a molecular weight of at least about 500. With a given prepolymer, increases in the ratio of NCO to OH give coatings of greater film hardness and mar resistance while flexibility and impact resistance may be adversely affected, but these effects can be modified by using a long chain polyol for curing. The free isocyanate groups in such polyol-curing prepolymers are generally about to 25 or even 35 or more weight percent, with about to weight percent being preferred, based on polymer content or solids.
Aside from water a component used in making the prepolymer compositions of the present invention is, as noted, one or more aliphatic polyols, for instance, the diols, triols, other polyols, including the ether polyols, or their mixtures. The polyols have at least two hydroxyl groups attached to aliphatic carbon atoms, and may be selected from a wide variety of polyhydroxyl materials which may be aliphatic, including cycloaliphatic, hydro carbon compounds, including substituted-hydrocarbon compounds. A minor amount of aromatic polyols or phenols may, if desired, be included in the polyurethane prepolymers but they may lead to unsatisfactory results. The polyol may often have a molecular weight up to about 5000 or more, but preferably has a molecular Weight of up to about 3000. As the molecular weight of the polyol increases at a given NCO/ OH mole ratio in the reaction mixture for forming moisture-curing prepolymers, cured coatings of decreased hardness are obtained. On the other hand the same amount of isocyanate if employed with low molecular weight polyols can lead to moisture-cured coatings which are hard and brittle. Thus in moisture-cured coatings, brittleness and hardness are in general increased as the amount of diisocyanateis increased or the molecular weight of the polyol is reduced.
Representative polyol classes and individual compounds useful in making the various prepolymers are given below. In making the moisture-curing prepolymers of this invention it is preferred that the major portion of the total polyol component have a molecular weight of at least about 500. In the case of moisture-curing prepolymers it is preferred that they be made from polyols having 2 to 3 hydroxyl groups which may or may not be terminal, ie, at an end of the longest chain of the molecule. Also, when the polyol component used in making moisturecuring prepolymers contains lower molecular weight aliphatic polyol, which will often be theminor amount by weight of the total polyol, such lower molecular weight material preferably has a molecular weight of up to about 200. Sometimes in such cases the low and high molecular weight polyols are used in approximately equal molar ratios. In making the polyol-curing prepolymers it is preferred that on a weight basis the major portion up to all of the polyol has a relatively low molecular weight of up to about 200. In this case the aliphatic polyol added for curing can be one or more of the various types mentioned herein, but we prefer that the curing polyol be composed to a major extent on a weight basis, of aliphatic polyol having a molecular weight of at least about 500. The curing polyol may also be composed entirely of such high molecular weight material.
The aliphatic polyol employed in making the polyurethane-type prepolymers or cured products of the present invention may be one or more polyhydric alkanols which can be the only polyol used or other polyols may also be employed. The aliphatic alcohols have at least 2 carbon atoms, and among the wide variety of such materials which can be used are those represented by the formula:
in which R is an aliphatic hydrocarbon radical, preferably saturated, and R is an :alkylene radical of 2 to 4, preferably 2 to 3 carbon atoms, R preferably has 2 to 12 advantageously 2 to 6 carbon atoms. The letter 11 represents a number from 0 to about 50, preferably 2 to 30 or even about 5 to 30, for more flexible coatings, while the letter m is 0 to 2 or more. When n is other than 0, R may often be the same as R". Also, n may be a number which gives a polyol of desired molecular weight for mak- 4 ing the prepolymer or for curing. The aliphatic alcohol reactant can be substituted with non-deleterious su-bstitucuts and the lower molecular weight polyether glycols, e.g., of 2 to 4 ethylene oxide units, are preferred reactant materials.
Suitable aliphatic alcohols include the polyether glycols of up to about 5000 or more molecular weight, such as the polyethylene glycols, for instance, of up to about 3000 molecular weight, propylene glycol, polypropylene glycols, for instance, of up to about 3000 molecular weight, ethylene glycol, glycerol, polybutylene glycols, trimethylol propane, butane diols, trimethylol ethane, 1, 6 hexamethylene glycol, 1,2,6 hexanetriol, sucrose, sorbitol, etc.
Others among the non-drying polyols useful in the invention include the hydroxy esters such as castor oil, polyol-modified castro oils, other polyol-modified nondrying oils and hydroxy-terminated polyesters. The hydroxy-terminated polyester materials are generally made by reaction of one or more aliphatic polyhydroxy alcohols, such as the aliphatic polyols mentioned above, with one or more aliphatic, including cycloaliphatic, or aro matic polycarboxylic acids or esters, and such polyesters may have hydroxyl values in the range of about 25 to 150. Frequently in these polyesters, the polyhydroxy alcohols are predominantly diols and the acids are dicarboxylic acids, including their anhydrides, and preferably contain from 4 to 50 carbon atoms, e.g., phthalic acid, adipic acid, sebacic acid, dimers of olefinically-unsaturated monocarbozylic acids, such as linoleic acid dimer, etc. Modified castor oil partial esters can be made by ester interchange of the oil with polyols such as low molecular weight polyols, including glycols, glycerine, pentaerythritol, etc.
The reaction of diisocyanates with aliphatic polyols does not of necessity give satisfactory coating compositions. Thus, the isocyanate-polyol prepolymers must be stable and in an essentially liquid state, at least when in a solvent, to be useful as coating compositions. There is a greater tendency to produce intractable prepolymer gels when the polyol contains a cross-linking component which has at least three hydroxyl groups per molecule, yet such cross-linked prepolymers if of proper viscosity are highly desirable coating compositions.
The difliculty encountered with cross-linked prepolymers is illustrated by the fact that when a mixture of trimethylolpropane, polypropylene glycol of about 1000 molecular weight and butylene glycol (2:1:1 mole ratio) was reacted with diisocyanato dicyclohexyl methane at an NCO to OH ratio of 1.65:1, an intractable gel was obtained. When, however, this isocyanate was replaced with an equivalent amount of 1- isocyanato 3 -isocyanatomethyl 3,5,5 trimethyl cyclohexane, a coating composition of application viscosity was produced and moisture-cured coatings of the composition had excellent properties. Thus, the prepolymer compositions of the present invention especially include those in which at least a portion of the polyol reactant is an aliphatic polyol having at least three hydroxyl groups per molecule such as those mentioned before including the polyols of the defined formula where m is 1 to 2, trimethylol propane, trimethylol ethane, 1,2,6-hexanetriol, sucrose, sorbitol, etc. Such cross-linking aliphatic polyols often have about 3 to 12, preferably about 3 to 6, carbon atoms. By using the cross-linking polyols with 1-isocyanato-3-isocyanatomethyl 3,5,5 trimethyl cyclohexane, lesser amounts of the diisocyanate can be employed and still obtain an ungelled prepolymer vehicle than when the diisocyanate is, for instance, diisocyanato dicyclohexyl methane. Also the 1 isocyanato 3 isocyanatomethyl-3,5,5-trimethyl cycolhexane permits the use of larger amounts of the cross-linking alcohol without obtaining gels. When the polyol component used in making the prepolymer contains cross-linking polyol essentially the entire polyol may have at least about three hydroxyl groups per molecule and often at least about 10, preferably at least about 30, mole percent of the hydroxyl groups are supplied by the cross-linking polyol.
The polyurethane-type prepolymer reaction products of the present invention can be made by simultaneous reaction of excess 1-isocyanato-3-isocyanatomethyl-3,5,5- trimethyl cyclohexane and polyol or water. Alternatively, the diisocyanate can be reacted with part or all of one or more of the polyols or water prior to the reaction with the remaining portion of these materials. Stepwise mixing of the diisocyanate with the polyols or water may be used to enhance temperature control. The reaction temperatures for making the various urethane prepolymers of the present invention are often in the range of about to 150 C., with about to 130 C. being preferred; and the reaction is preferably continued until there is essentially little, if any, unreacted hydroxyl functionality remaining. As noted above wide variations in the nature and amounts of the polyol, water or their mixtures used in the preparation of the prepolymer coating compositions of this invention can be made. Catalysts may be used in forming the prepolymers to accelerate the rate of reaction, e.g. the catalysts may be similar to those which can be employed to accelerate curing.
The rate of curing of the coating compositions of this invention may be enhanced as desired by incorporation of appropriate amounts of a catalyst which promotes the reaction of isocyanato groups with water or polyols. Typically organotin compounds, for example dibutyl tin dilaurate and stannous octoate may be used. Other useful catalysts include tertiary aliphatic and alicyclic amines, such as triethyl amine, triethanol amine, tri-n-butylamine, triethylene diamine, alkyl morpholines and the like. Complex mixtures containing such catalysts in modified form may also be employed. In any event the free isocyanate groups in the prepolymer when exposed to moisture of the atmosphere or aliphatic polyol form cross-links which produce tough and relatively permanent coatings.
The prepolymers of the present invention may be prepared in the presence of an essentially inert solvent. The solvent serves to insure that the reactants are in the liquid state and the solvent permits better temperature control during the reaction by serving as a heat sink and, if desired, as a refluxing medium. Various solvents including mixtures of such materials may be employed and among the useful organic solvents are the aliphatic and aromatic hydrocarbons, esters, ethers, keto-esters, ketones, glycolether-esters, chlorinated hydrocarbons, and the like and mixtures thereof. Frequently, the solvents are volatile materials which will be removed from the composition while it cures as a coating or film, and in such case, there may be no need to remove any portion of the solvent from the reaction product prior to application as a coating. The amount of solvent employed may vary widely and large volumes may be uneconomic or give materials with undesirably or inconveniently low viscosity. The amount of solvent may be selected in order to provide a reaction product of film application viscosity, but products of greater viscosity can be cut-back before use. Often about 0.25 to 6 weights of solvent, preferably about 0.5 to 3 weights of solvent, per weight of the total isocyanate and polyol or water in the prepolymer are used. Among the suitable normally liquid solvents are toluene, xylene, ethylbenzene, Z-ethoxyethyl acetate, 1,1,1-trichloroethane, methylisobutyl ketone, dimethylformamide, dimethylsulfoxide, dioxane, etc. and their mixtures; and it is preferred that the solvent not contain more than about 10 carbon atoms per molecule.
The coating compositions of this invention are normally applied to solid substrates as films of less than 10 mils thickness and can contain other additives to impart special properties such as plasticizers, etc. Also, the substrate for the coating may be specially treated materials, including flammable members impregnated with fire-resistant chemicals or coated with a sealant.
The following examples will serve to illustrate the present invention. In the examples the parts indicated are by weight and the percents NCO are reported on the basis of the total weight of the vehicle. The prepolymer-forming reactions were conducted under a nitrogen atmosphere.
EXAMPLE I A mixture of 89 parts 1-isocyanato-3-isocyanatomethyl- 3,5,5-trimethyl cyclohexane, 113 parts of a polyether polyol prepared from the addition of propylene oxide to 1,2,6-hexanetriol to a molecular weight of about 700, 0.2 part dibutyl tin dilaurate (or 0.1% of solids) and 135 parts of a 50/50 mixture of xylene and ethoxy ethanol acetate are heated at about C. for about 3 hours. The reaction product is an isocyanate-terminated prepolymer which when coated on a metal plate and allowed to cure by exposure to atmospheric moisture, produces a tough and flexible film of good gloss. The prepolymer has an NCO content of 5.24% (8.8% on solids), a Gardner- Holdt viscosity of A% and Gardner color of 1-. A portion of the prepolymer cast on a Morest Chart at a 3 mil thickness dried in 15 hours after curing. The film is exposed to ultraviolet radiation for 2 hours using a Burdick Type QA-450A.C. 60 cy. ultraviolet lamp at a height of 18 inches from the light source to the film surface. The exposed film is not yellowed to any extent by exposure to the radiation source.
EXAMPLE II A moisture-curing coating composition is prepared as described in Example I except that the amount of dibutyl tin dilaurate catalyst is increased to 2.0 parts (or 1.0% of solids). A film cast from this curing composition has a curing time of 5.5 hours compared to the cure time of 15 hours of the composition of Example 1.
EXAMPLE III A sample of the prepolymer from Example I is treated with 2 weight percent (based on total solids) of N-coco morpholine catalyst and heated for about 3 hours at 130 C. The composition obtained has an NCO content of 3.80 weight percent. A film cast from the composition and exposed to atmospheric moisture becomes tack free in 4 hours and is completely cured throughout in about 13 hours.
EXAMPLE IV A mixture of 43.6 parts of polypropylene glycol of molecular weight 1025, 3.7 parts 1,4-butylene glycol, 11.3 parts trimethylol propane, 78.5 parts 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane and 139 parts of a 50/50 mixture of Cellosolve acetate and xylene is heated at about 90-95 C. for about 3.5 hours. To the prepolymer obtained 2.02 parts (or 2 weight percent of total solids) of N-coco morpholine catalyst is added to produce a moisture-curing composition having an NCO content of 4.15 percent (8.3% on solids). Films produced from the composition do not yellow on exposure to ultraviolet radiation as described in Example I.
EXAMPLE V An oil-modified, moisture-curing polyurethane coating composition is prepared by heating a mixture of 87.6 parts 1-isoeyanato-3-isocyanatomethyl-3,5,5-trimethy1 cyclohexane, 81.5 parts dielectric grade caster oil, 207 parts toluene and 1.38 parts dibutyl tin dilaurate for 6 hours at about 45 C. The prepolymer composition has an NCO content of 3.12 percent (about 8% on solids), viscosity of A and APHA color of 55. A 3 mil film of the composition cast on a Morest Chart dried in about 13 hours to produce a coating which showed no detectable yellowing on exposure to ultraviolet radiation, as described in Example I.
EXAMPLE VI A polyester is prepared by heating a mixture of 588 parts of commercial linoleic dimer acid (Emerys Empol 1018, 150 parts phthalic anhydride, 99 parts maleic anhydride, 1257 parts diethylene glycol and 200 parts xylene at 150-210 C. while water is continuously removed. The temperature of the reaction mixture is gradually in creased to about 230250 C. and heating is continued until the product acid value decreases to about 9.2. There is obtained a polyester having a viscosity of 3600 poises, hydroxyl number 46. 6 and Gardner color of 9+. Seventy parts of this polyester, 13.8 parts trimethylol propane, 5 parts 1,3-butylene glycol, 257 parts of a 50/50 mixture of Cellosolve acetate and xylene, 0.19 parts dibutyl tin dilaurate and 100 parts 1-isocyanato-3-isocyanatomethyl-3, 5,5-trimethyl cyclohexane are heated at about 90 C. for about 4 hours. There is obtained a coating composition having an NCO content of 4.04% (about 9.5% on solids), a viscosity of G+ 1/ 4 and Gardner color of 4+. Moisturecured coatings derived from the composition showed outstanding resistance to ultraviolet light.
EXAMPLE VII An isocyanate-terminated prepolymer is prepared by heating together 100 parts 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, 16.4 parts trimethylol propane and 77 parts of a 50/50 mixture of xylene and 8 Cellosolve acetate at about 65 C. for about 3 hours and at about C. for about 6 hours. The product has an NCO content of 8.53 weight percent (about 18% on solids), a viscosity of U and Gardner color of 1. The prepolymer is mixed at 1:1 NCO/OH ratio with esterified castor oil having an equivalent weight of about 200 obtained by esterifying castor oil with pentaerythritol, to produce a composition which when coated on a substrate and baked at C. for about 15 minutes dried to a tough film of excellent gloss. The dried film is not affected on exposure to ultraviolet radiation for two hours using a Burdick Type QA450A.C. 60 Cy. ultraviolet lamp at a height of 18 inches from the light source to the film surface.
EXAMPLE VIII About 100 parts by weight of a polyoxypropylene glycolcol of approximately 1000 molecular weight was mixed with about 18.5 parts 1,4 butanediol and about 26 parts trimethylol propane in a 2 liter, four neck, round bottom flask provided with a nitrogen inlet tube, a mechanical stirrer, a temperature indicator and a Dean Stark trap under a reflux condenser. parts of xylene and 160 parts of ethylene glycol monoethylether acetate were added and the mixture was boiled for a one hour period with stirring under nitrogen cover while azeotropically removing moisture. The mixture was then allowed to cool. parts of 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane was added to the mixture. A small heat of reaction was evolved. Following this the mixture was heated to 80 C. and was held at this temperature for 5 hours. The resultant vehicle had a viscosity of one stoke, a free isocyanate content (NCO) of 4.27 percent (8.54 on solids), a Gardner color of less than one, and a non-volatile content of 50 percent. After the addition of 1% of dibutyl tin dilaurate at 3 mil wet film of vehicle was cast. The film was set in one hour and dried hard in 5 hours. The tough color-free, moisture-cured film was substantially color stable to high intensity ultraviolet light.
EXAMPLE IX A mixture of 800 parts by weight of polyoxypropylene glycol 1025, 272 parts polyoxypropylene glycol 2025 and 50 parts of xylene are heated to reflux temperature in a reaction vessel with inert gas blanket and held at this temperature for one hour. After cooling to 40 C., 1.5 parts of dibutyl tin dilaurate and 476 parts of 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane are added. The temperature is increased to 90 C. and held at 90 C. for about 30 minutes. The resultant vehicle had a viscosity of 34 stokes at 93% non-volatile, water white and contained 6.2% NCO. Upon the addition of 1% dibutyl tin dilaurate or 2% of 2,4,6-tri (dimethyl aminomethyl) phenol slow, moisture-curing films were obtained at room temperature. The curing rate could be accelerated with heat, e.g. 30' at 150 C. The films retained suflicient tack to be useful for color stable, pressure-sensitive adhesives.
EXAMPLE X To a clean, dry, three-neck, two-liter, round-bottom flask was charged 30 3 grams of a polyoxybutylene glycol of approximately 538 molecular weight, 42.5 grams of trimethylol propane, 3.4 grams of 2,6-ditertiary butyl, 4- methyl phenol and 232 grams of xylene. With a nitrogen atmosphere in the flask and stirring, the mixture was held in a state of reflux for 1 hour. Approximately twenty grams of distillate were collected in a Dean Stark water trap and discarded. When the mixture had returned to room temperature, 3.4 grams of dibutyl tin dilaurate were added, followed by 343 grams of 1-isocyanato-3- isocyanatomethyl-3,5,5-trimethyl cyclohexane. When exothermic heat of reaction ceased being emitted at about 88 C., heat was applied and the mixture held at 90 C. for three hours. An additional 763 grams of xylene was added along with 2.3 grams of 3 percent magnesium as neodecanoate. The temperature was increased to and held at 130 C. until the reaction mixture reached a viscosity of 0.5 stoke. The finished vehicle had a nonvolatile of 43.4 percent, a free isocyanate content (NCO) of 2.9 percent, a viscosity of 0.7 stoke and a Gardner color of 1 minus. A three mil wet film of the vehicle showed a set time a of hour and tack free time of /s hour. A film of this vehicle was essentially non-yellowing, while a similar toluene diisocyanate type vehicle yellowed considerably when exposed to ultraviolet light for the same period of time.
EXAMPLE XI A two-can polyurethane coating composition is derived by combining a prepolymer composition prepared as described in Example V with an esterified castor oil of equivalent weight of about 200 obtained by esterifying castor oil with pentaerythritol. The prepolymer and the esterified castor oil are mixed at an NCO/ OH ratio about 1/1. Films cast from the resulting composition have a dry time of about 4.5 hours. Coatings are obtained which are not visibly affected by ultraviolet radiation.
EXAMPLE XII A polyurethane prepolymer was prepared from 224 grams (2 equivalents) of 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, 26 grams (1 equivalent) of pentaerythritol, 220 grams of dimethyl foramide, 0.25 gram of dibutyl tin dilaurate and 50 grams of toluene. The reaction was carried out in a glass flask provided with a thermometer, inlet for nitrogen, mechanical stirrer, reflux condenser, water trap and glass mantle for furnishing heat by electrical means. The pentaerythritol, dimethyl formamide and toluene were heated under azeotropic conditions (130 C.) to remove water, the procedure being performed under nitrogen cover with continuous stirring. Following this the mixture was allowed to cool. The diisocyanate and dibutyl tin dilaurate were added. The mixture was then heated to 80 C. and maintained at this temperature for 1 hour and 35 minutes until the percent of free isocyanate (NCO) in the resulting prepolymer reached a value of 6.51.
Five grams (.025 equivalent) of castor oil interesterified with pentaerythritol to a hydroxyl value of 280 were mixed with 16 grams (.025 equivalent) of the above prepolymer and cast on a Morest Chart in a 3 mil wet film. This film was set to the touch and tack free in 4 /2 hours and mar free in 9 hours. When this dry film was exposed for 2 hours to ultraviolet light from a 400 watt mercury arc lamp at a distance of 18 inches, very slight yellowing occurred. This film remained very flexible after exposure to ultraviolet light.
EXAMPLE XIII An ester-based vehicle was prepared in the following manner from Emery Dimer Acid known as Empol 1018 having an acid value of 190, a saponification value of 195 and unsaponifiable material one percent. This dimer acid is made from linoleic acid and contains about 83 percent C dibasic acid, 17 percent trimer acid with a small amount of monobasic acid. The reaction mixture consisted of 588 grams (2.01 equivalents) dimer acid, 150 grams (2.01 equivalents) phthalic anhydride, 99 grams (2.01 equivalents) maleic anhydride, 420 grams (7.95 equivalents) diethylene glycol and 200 grams of xylene, all of which were placed in a 2 liter flask under nitrogen. The mixture was heated for 1% hours over a temperature range of 155-210 C. to remove water by azeotropic distillation. The total amount of water collected in a Dean Stark trap was 92 grams as compared with a theoretical amount of 108 grams (6 equivalents). The mixture was heated for a further period of 7% hours over a temperature range of 210-230 C. The final ester product had a viscosity of 3600 poises, a Gardner color 10 of 9 plus, an acid value of 8.4 and a hydroxyl value of 46.6
A polyurethane vehicle was prepared from the ester by placing 70 grams (.058 equivalent) of ester, 13.8 grams (0.307 equivalent) trimethylol propane, 5 grams (0.111 equivalent) of 1,3-butane diol, 128.5 grams ethylene glycol ethyl ether acetate and 128.5 grams exylene in a suitable reaction flask provided with a thermometer, mechanical stirrer, heating mantle, inlet for gaseous nitrogen, reflux condenser and Dean Stark water trap. This mixture was heated for 1 hour at C. to remove water by azeotropic distillation from the reaction components. The temperature was then allowed to drop to 55 C. when 100 grams (0.905 equivalent) l-isocyanato- 3-isocyanatomethy1-3,5,5-trimethyl cyclohexane and 0.19 gram dibutyl tin dilaurate were added and stirred in. The temperature was kept at 90 C. for 1% hours after which the vehicle was allowed to cool to room temperature. A sample of the polyurethane prepolymer vehicle had a Gardner viscosity of G a Gardner color of 4 plus, a free isocyanate value of 4.04 percent NCO and a nonvolatile content of 40 percent.
Fifteen and seventy five one hundredths grams of the polyurethane prepolymer (equivalent weight 1050 and 40 percent nonvolatile) were mixed with 18 grams of the ester made from the dimer acid (equivalent weight 1200, hydroxyl value 46.6) and 18 grams of xylene. A 3 mil film of this mixture was cast on a Morest Chart and placed in a constant 77 F. temperature room having a relative humidity of 50 percent. The film. was found to be set to touch in 3 hours. The film was still slightly tacky after 5 6 hours but was mar free. When this film was exposed to the ultraviolet light from a 400 watt mercury arc lamp for 4 hours, at a distance of 18 inches, it dried to a non-tacky condition and did not discolor.
EXAMPLE XIV The following reacants were used to prepare a polyurethane having a free isocyanate group content that could be cured with a diol or polyol; 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, 400 grams (3.57 equivalents); trimethylol propane, 72.7 grams (1.61 equivalents); 1,3-butane-diol, 18.4 grams (0.41 equivalent); dibutyl tin dilaurate 0.5 gram; ethylene glycol ethyl ether acetate grams; and xylene 165 grams. The diisocyanate, dibutyl tin dilaurate and the solvents were placed in a one liter flask and heated to about 45 C. The trimethylol propane was added slowly over a 2 hour period and the temperature kept at about 45 C. for 5 hours more. The 1,3-butanediol was added during one hour at this same temperature and the temperature maintained for 3 hours more. The reaction was conducted under a blanket of gaseous nitrogen with continuous stirring, the heating being supplied by means of a glass mantle from an electric power source. The flask was provided with a thermometer and reflux condenser. The polyurethane prepolymer vehicle made in this manner had a nonvolatile content of 60.9 percent, a free isocyanate percentage of 8.3 as NCO, a Gardner viscosity of X+% and a Gardner color of one minus.
Forty grams of the pentaerythritol interesterified castor oil of Example XII having a hydroxyl value of about 280 were mixed with 101 grams of the polyurethane prepolymer. The nonvolatile content of the mixture was reduced to 50 percent with ethylene glycol ethyl ether acetate. A 3 mil wet film of this vehicle was cast on glass and dried at room temperature in approximately 24 hours and showed a Sward hardness of 73 after one week. When the film was exposed for 2 hours at a distance of 18 inches from a 400 watt mercury arc lamp giving ultraviolet light, no change in the excellent colorless appearance of the film occurred. A similar film made from a vehicle containing tolylene diisocyanate in the polymer structure showed some yellowing when exposed under conditions identical to those used with the vehicle made from 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane.
EXAMPLE XV Two hundred twenty one grams (2 equivalents) of 1- isocyanato-3-isocyanatomethyl 3,5,5-trimethyl cyclohexane, 88.7 grams of ethlyene glycol ethyl ether acetate, 88.7 grams of xylene and 0.67 gram of dibutyl tin dilaurate were charged to a flask provided with a heating mantle, a mechanical stirrer, a thermometer, a reflux condenser and an inlet for gaseous nitrogen. Heating and stirring were started and when the temperature was 35 C., 45 grams (one equivalent) of trimethylol propane were added over about one hour. Heating with stirring was continued for four hours with the temperature kept at 65 to 68 C. After this the temperature was raised to 90 to 110 C. for 2 hours and the batch cooled to room temperature under gaseous nitrogen. The Gardner viscosity of the vehicle was Z1-|-% at 61.7 percent nonvolatile content, Gardner color one minus and percent NCO 8.80. The dry time of this prepolymer vehicle at 3 mils wet film thickness on a Morest Chart was 1% hours.
Four hundred eighty grams of the prepolymer and 200 grams of the pentaerythritol interesterified castor oil of Example XII were mixed thoroughly and a 3 mil wet film was cast on a glass plate. This film dried in 3 /2 hours to a flexible film. When the dried film of this two component vehicle was exposed to ultraviolet light from a 400 watt mercury arc lamp at a distance of 18 inches from the sample for 2 hours, no change in color or appearance of the film occurred.
EXAMPLE XVI Ten grams (.0204 equivalent) of the prepolymer whose preparation is described in Example XV with an equivalent weight of 491 and 10.55 grams (.0204 equivalent) of polypropylene glycol of equivalent weight 518 were mixed thoroughly along with 5 grams of xylene. After 16 hours standing the Gardner viscosity of this vehicle was A plus and its Gardner color was one minus. A 3 mil wet film of this vehicle cast on a Morest Chart was set to touch in 18 hours and dry in 24 hours. When this film was exposed for 2 hours to the ultraviolet light from a 400 watt mercury arc lamp at a distance of 18 inches from the film, only slight yellowing of the film occurred as shown by visual observation.
EXAMPLE XVII One hundred grams (0.725 equivalent) of l-isocyanato 3-isocyanatomethyl 3,5,5 trimethylcyclohexane, 38.5 grams of xylene and 38.5 grams ethyl glycol ethyl ether acetate were placed in a flask which has a mechanical stirrer, a reflux condenser, a thermometer, an inlet for gaseous nitrogen and a fiber glass heating mantle. With the temperature of the batch at 35 C.,' 16.4 grams (0.362 equivalent) of trimethylol propane was added during the course of two hours while stirring continually. The reaction temperature was then raised to 65 C. and kept at this level for 3% hours. A further heating period at 90 C. for 7% hours was used after which the nonvolatile content of the prepolymer vehicle was 53.3 percent by Weight, the percent NCO 8.53, the Gardner viscosity U and the Gardner color one minus.
This prepolymer (100 grams) was reacted in 1:1 ratio of NCO/ OH with 40.6 grams of a castor oil interesterified with pentaerythritol to a hydroxyl value of 280. A 3 mil wet film required over 24 hours for this two component vehicle to dry at room temperature. However, it dried hard in minutes at 130 C. When the film on a Morest Chart was exposed to ultraviolet light from a 400 watt mercury arc lamp at a distance of 18 inches for 2 hours, no yellowing or other visible alteration of the film occurred.
1?; EXAMPLE XVIII To a suitable reaction flask 111 grams (1.0 equivalent) of l-isocyanato 3 isocyanatomethyl 3,5,5 trimethyl cyclohexane, 3 grams (0.33 equivalent) of water, 40 grams of ethylene glycol ethyl ether acetate, 1 gram of triphenyl phosphate and 1 gram of dibutyl tin dilaurate were added. These reactants were stirred together under gaseous nitrogen at 27-l00 C. for 2 /2 hours after some heat of reaction was released. The resulting prepolymer vehicle had a percent NCO of 18.75, an American Public Health Association color of 30, a nonvolatile content of 61.9 percent by weight and a viscosity of 1.20 stokes.
Fifty grams of this prepolymer were mixed with 44.6 grams of castor oil interesterified to a hydroxyl value of 280 with pentaerythritol and 0.45 gram (.06 percent basis of solids) of dibutyl tin dilaurate. When a 3 mil wet film of this vehicle was cast on a Morest Chart it dried in 26 /2 hours. After one week the Sward hardness of the dried film was 57. This film yellowed slightly when exposed to the ultraviolet light produced by a 400 watt mercury arc lamp for 4 hours at a distance of 18 inches. A film cast in the same way from a similar vehicle made from an aromatic diisocyanate and exposed in the same manner to ultraviolet light yellowed to a greater degree than the one made from 1-isocyanato-3-isocyanatomethyl- 3,5,5-trimethyl cyclohexane.
1. A composition which comprises a liquid polyurethane prepolymer composition made from l-isocyanato 3 isocyanatomethyl-3,5,5-trimethyl cyclohexane and aliphatic polyol, said polyurethane being made at an NCO/OH ratio of at least 12:1 and said aliphatic polyol having at least about 30 mole percent of the hydroxyl groups supplied by aliphatic polyol having at least three hydroxyl groups per molecule.
2. The composition of claim 1 in which the aliphatic polyol contains aliphatic polyol having two hydroxyl groups.
3. The composition of claim 2 which contains about 3 to 25 percent of free isocyanate groups based on the polyurethane content of the composition.
4. A composition which comprises a liquid polyurethane prepolymer composition made from 1-isocyanato3- isocyanatomethyl-3,5,5-trimethyl cyclohexane and aliphatic polyol, the major portion by weight of said aliphatic polyol having a molecular weight of at least about 500, said polyurethane being made at an NCO/OH ratio of 1.2 to 25:1 and said aliphatic polyol having at least about 30 mole percent of the hydroxyl groups supplied by aliphatic polyol having at least three hydroxyl groups per molecule.
5. The composition of claim 4 which contains about 5 to 10 percent of free isocyanate groups based on the polyurethane content of the composition.
6. The composition of claim 4 in which the aliphatic polyol having a molecular weight of at least about 500 has the formula:
in which R is aliphatic hydrocarbon of 2 to 12 carbon atoms, R" is alkylene of 2 to 4 carbon atoms, n is a number sufficient to provide a polyol of at least about 500 molecular weight, and m is 0 to 2.
7. The composition of claim 6 in which the aliphatic polyol contains a minor portion by weight of aliphatic polyol of up to about 200 molecular weight.
8. The composition of claim 7 in which the low molecular weight polyol is trimethylol propane.
9. A composition of claim 6 in which in is 0.
10. The composition of claim 4 in which the at least three hydroxyl-containing aliphatic polyol has the formula:
in which R is aliphatic hydrocarbon of 2 to 12 carbon atoms, R" is alkylene of 2 to 4 carbon atoms, n is a number sufiicient to provide a polyol of at least about 500 molecular weight, and m is 1 to 2.
11. A moisture-cured coating of the composition of claim 1.
12. A claim 2.
13. A claim 4.
14. A claim 6.
15. A claim 9.
16. A claim 10.
17. A composition which comprises a liquid polyurethane prepolymer composition made from l-isocyanato- 3-isocyanatomethyl-3,5,5-trimethyl cyclohexane and aliphatic polyol, the major portion by weight of said polyol being aliphatic polyol having a molecular weight of up to about 200, said polyurethane being made at an NCO to OH ratio of 1.4 to 3.5 :1 and said aliphatic polyol having at least about 30 mole percent of the hydroxyl groups supplied by aliphatic polyol having three hydroxyl groups per molecule.
18. The composition of claim 17 which contains about 15 to 20 percent of free isocyanate groups biased on the polyurethane content of the composition.
19. The composition of claim 17 in which the aliphatic polyol has the formula:
in which R is aliphatic hydrocarbon of 2 to 12 carbon atoms, R" is alkylene of 2 to 4 carbon atoms, n is a number which provides a polyol having a molecular weight of up to about 200, and m is 1 to 2.
20 The composition of claim 17 in which the aliphatic polyol is trimethylol propane.
21. An aliphatic polyol-cured coating of the composition of claim 17.
22. An aliphatic polyol-cured coating of the composition of claim 19.
moisture-cured coating of the composition of moisture-cured coating of the composition of moisture-cured coating of the composition of moisture-cured coating of the compostion of moisture-cured coating of the composition of 23. An aliphatic polyol-cured coating of the composition of claim 17 wherein the composition is cured by admixture with aliphatic polyol whose major portion by weight has a molecular weight of at least about 500.
24. An aliphatic polyol-cured coating of the composition of claim 17 wherein the composition is cured by admixture with aliphatic polyol whose major portion by weight has a molecular weight of at least about 500.
25. The composition of claim 10 in which the at least three hydroxyl-containing aliphatic polyol is trimethylolpropane and the aliphatic polyol having two hydroxyl groups is polypropylene glycol having a molecular weight of up to about 3000.
26. A moisture-cured coating of the composition of claim 25.
27. A composition which comprises a liquid prepolymer made from 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane and water, said prepolymer being made at an NCO/ OH ratio of at least 1.2: 1.
28. An aliphatic polyol-cured coating of the composition of claim 27.
29. An aliphatic polyol-cured coating of the composition of claim 27 wherein the composition is cured by admixture with aliphatic polyol whose major portion by weight has a molecular weight of at least about 500.
30. The composition of claim 29 in which the curing aliphatic polyol is an ester of castor oil and pentaerythritol.
References Cited UNITED STATES PATENTS 2,929,800 3/1960 Hill 26077.5 3,352,830 11/1967 Schmitt et al. 260-775 3,351,573 11/1967 Skreckoski 26018 OTHER REFERENCES Saunders et al.: Polyurethanes, Part II, pp. 477-485 and 601-607 relied upon, 1964.
DONALD E. CZAJ A, Primary Examiner M. J. WELSH, Assistant Examiner US. Cl. X.R.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2929800 *||Jun 30, 1953||Mar 22, 1960||Du Pont||Polytetramethylene ether polyurethane polymers|
|US3351573 *||Jun 13, 1961||Nov 7, 1967||Allied Chem||Catalyzed storage-stable quick drying coating composition containing polyurethane-polyisocyanate film former|
|US3352830 *||Jul 16, 1965||Nov 14, 1967||Scholven Chemie Ag||Polyurethanes from 1-isocyanato-3-isocyanatomethyl-3, 5, 5-tri-alkylcyclohexane|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3691134 *||Apr 27, 1970||Sep 12, 1972||Nat Distillers Chem Corp||Polyurethanes prepared from cyclo-alkyl diisocyanates|
|US3892895 *||May 21, 1973||Jul 1, 1975||Ajinomoto Kk||Method for adhering polyamino acid coating to plasticized polyvinyl chloride|
|US3904796 *||Apr 20, 1973||Sep 9, 1975||Bayer Ag||Process for the production of polyurethane coatings|
|US3919173 *||Nov 23, 1973||Nov 11, 1975||Contech Inc||Moisture curable polyurethane systems|
|US3948829 *||Apr 5, 1973||Apr 6, 1976||Hitco||Strippable, thin, protective coating|
|US3989662 *||Mar 27, 1974||Nov 2, 1976||Veba-Chemie Ag||Single component polyurethane varnish of long shelf life|
|US3991003 *||Jun 24, 1975||Nov 9, 1976||Prolux Paint Manufacturers Limited (Pty)||Coating compositions|
|US4005041 *||Jun 24, 1975||Jan 25, 1977||Prolux Paint Manufacturers (Pty) Limited||Air-drying or heat-curable polyurethane coating compositions|
|US4034138 *||Oct 9, 1975||Jul 5, 1977||Hitco||Aromatic polyamide fibers coated with a polyurethane|
|US4038239 *||Aug 19, 1975||Jul 26, 1977||Contech Inc.||Moisture curable polyurethane systems|
|US4095404 *||Apr 25, 1977||Jun 20, 1978||Hitco||Method of manufacturing a high-strength, polyurethane-impregnated polyamide cable|
|US4145515 *||Dec 1, 1976||Mar 20, 1979||Congoleum Corporation||Method of forming storage-stable polyurethane prepolymers|
|US4390678 *||Jan 7, 1982||Jun 28, 1983||H. B. Fuller Company||One-package heat curable aromatic polyurethane composition useful for joining substrates and as an in-mold coating comprising an isocyanate terminated prepolymer and a polyhydroxy compound|
|US4412033 *||Sep 13, 1982||Oct 25, 1983||H. B. Fuller Company||One-part, curable polyurethane|
|US4523003 *||Jan 4, 1984||Jun 11, 1985||American Cyanamid Company||Storage stable, one package, heat curable polyurea/urethane coating compositions and method of preparation|
|US4598136 *||Mar 26, 1985||Jul 1, 1986||Akzo Nv||Embedding material and process for the production thereof|
|US4747953 *||Feb 21, 1986||May 31, 1988||Allied Corporation||Composite membranes based on interpenetrating polymer networks|
|US5085775 *||Dec 5, 1990||Feb 4, 1992||Allied-Signal Inc.||Thin film composite ultrafiltration membrane|
|US5145584 *||Oct 31, 1991||Sep 8, 1992||Allied-Signal Inc.||Processes for using a thin film composite ultrafiltration membrane|
|US6077381 *||Jun 7, 1995||Jun 20, 2000||Raytheon Company||Method of making a high strength, high modulus continous polymeric material for durable, impact resistant applications|
|U.S. Classification||528/74.5, 528/77, 528/272, 528/306, 528/308, 528/80|
|International Classification||C08G18/75, C08G18/10, C08G18/36, C08G18/66, C08G18/80, C08G18/30|
|Cooperative Classification||C08G18/302, C08G18/6611, C08G18/8032, C08G18/36, C08G18/8045, C08G18/755, C08G18/10|
|European Classification||C08G18/10, C08G18/80B3D6, C08G18/66C2D, C08G18/75B6C3, C08G18/80B5, C08G18/30D, C08G18/36|
|Jan 22, 1986||AS||Assignment|
Owner name: NL SPENCER KELLOG, INC., 1230 AVENUE OF THE AMERIC
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TEXTRON, INC., A CORP. OF DE.;REEL/FRAME:004496/0495
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Bright and eager Accounts Assistant/Accountant is needed to assist the Financial Manager with everyday finances. Top Excel Skills are required!!!
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Assistance to the Financial Manager re the full financial portfolio. This position can be very suitable to a Junior Accountant or Bookkeeper.
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The tastes of summer in a unique and savory salad.
1/2 C Balsamic glaze
8 Shrimp per salad, peeled & deveined
4 C Baby Arugula
3 C Seedless grilled watermelon, cubed
1/2 C Pickled Red Onions
1/2 C Feta cheese, crumbled
1/4 C Pecans
3 Tbsp Extra virgin olive oil
Kosher salt to taste
1.) Toss the shrimp in half the oil and grill till the shrimp turns pink and is completely cooked.
2.) Grill Watermelon until they have the desired grilled lines. Then, cut watermelon up into bite size pieces.
3.) Drizzle arugula with a little bit of olive oil and season with Kosher salt.
4.) Plate seasoned greens and top with cubed grilled watermelon, pickled red onions, feta cheese, pecans and grilled shrimp. Drizzle generously with the balsamic reduction.
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Stringing Blocks and Accessories
When Allied forces landed at Normandy, Sherman+Reilly blocks were there to help offload supplies from the LSTs. When something provides a critical function, it is important to know it can be relied upon. With over 80 years of experience in manufacturing sheaves and blocks, S+R blocks can be relied upon. From snatch blocks to bundle blocks – we have been building line stringing blocks longer than any active lineman has been alive. The Sherman+Reilly “Forever Warranty” is a testament to our confidence in our product.


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RIPK1-dependent Cell Death
What's on at the University of Plymouth: RIPK1-dependent Cell Death. Institute of Translational and Stratified Medicine research seminar. University of Plymouth, 8 October 2019.
Hematopoiesis and immune cell cancer
Plymouth University research: Hematopoiesis and immune cell cancer. Research into the signalling mechanisms involved in hematopoiesis and the pathogenesis of leukaemia and lymphoma

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Elsa Pendleton received her bachelor's degree from Oberlin College and her master's degree in library science from Louisiana State University. Her interest in the Owens Valley resulted from the many visits she and her husband made to the area while they lived in the Mojave Desert.
Public libraries are supposed to be calm and peaceful places, but a murder can happen almost anywhere. When a corpse is discovered in Victoria Public Library's Conference Room, the library staff become suspects as well as potential victims. Set in the pre-Internet days of the mid-1980s, Death by Chocolate is a mystery and a nostalgic look behind the scenes of the library.

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User review on Aston Martin V12 Vantage S written by Altaf hussain memon on 15 April 2015
Altaf hussain memon's review on Aston Martin V12 Vantage S Coupe
Year of Manufacture : 2015 | Driven no. of Kms. : NA
- Pros: Safety features are at par
- Cons: Low fuel economy
Aston Martin V12 Vantage is the most powerful sports car. I took a test drive of it and I am extremely impressed with it's performance. This sports car is not only good looking but extremely well performer also. It's a perfect combination of power and comfort. The car has several comforts and convenience features such as automatic climate control, malty function power steering wheel, cruise control, power windows. The safety features are at par with other contenders, it's a complete security package. The V12 Vantage has advanced suspension and braking system which adds to its advantage. The power full engine provides remarkable performance. The fuel economy and Ground clearance are very low of the Aston Martin V12 Vantage.
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Fall Protection Anchors are an important component of the fall arrest system in the construction industry. Anchorage connector straps attach to a tie-off point like a column, rebar, scaffolding or I-beam if a direct connection does not exist. When attaching an anchorage connector, please make sure that the connection is high enough to avoid contact with the ground or a lower level. For the ultimate safety protection, anchorage connectors should have a minimum breaking strength of 5000 lbs. All anchorage connectors on this page meet ANSI Z359.1, ANSI A10.4, and OSHA standards.


Mixing & Mastering Engineers, Producers & Songwriters who worked with Composed and produced Lone Monk Orchestra
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I have over 25 years experience in the music industry and have worked on tracks by David Bowie, The Damned, Amy Macdonald and One Eskimo. Aside from production and studio recording I offer a remote mixing and mastering service. I have mixed anything from live classical recordings from the likes of Vera Lyn to pop/dance tracks for chart acts.
Music Producer & Remote MixingJorge Chikiar - Concepto Sonorus Studio, Buenos Airesfavorite_borderfavorite
Chikiar has a solid academic background in musical composition, has held various compositions of music for ballet film, produced and arranged several bands in Argentina and collaborated with other musical productions. Winner Garder and Clarin Award, has one of the most interesting collections of synthesizers and analog equipment in Buenos Aires
I have been singing professionally for 6 years now, I write lyrics as well! I’m open to working on backgrounds, demos or features and can record myself at home using Ableton. Also open to different genres of music!
Paris based Tony Allen Percussionist with +40 years of Session, Drumming, Producing, Engineering and Mixing experience. More than 1300 Refs My track focus on delivering the best Performance of the perfect part for your Song with emphasis on Energy, Groove, Sound, and Vibe. I Serve your Vision and the Song by Enhancing without ever Distracting.
I write songs that I would sing myself. I’ve been a professional singer for 8 years and have always feared that I’d be forced to perform a song that I hated. I’m here to ensure that you will never sing a song that you hate. Any direction you’d like to go in I can accommodate, just give me a genre and a preference & we will get along.
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Besides meals, the government is providing essentials such as buckets, toothpaste, toothbrush, lungi (loincloth), gamchha (towels), plates, glasses and other required utensils to every migrant reaching the quarantine centres.
“Those migrants who arrived in the state on May 2-3 have already spent their 14 day-period of mandatory stay at different quarantine centres. They are now being asked to submit a self-declaration that they would be home-quarantined for a week after leaving the centres,” said a Bihar government official. According to him, the migrants remain under close observation of government workers such as accredited social health activists and ICDS employees during their home quarantine.
The government has deployed about 4,500 buses for the transportation of migrants to different quarantine centres across the state. The first task for the administration at the railway station is proper registration of every migrant. Then, they are sent to the block-level quarantine centres concerned.
Again, at the block level quarantine centres, their registration is done before they undergo medical screening. At the block level too, there are health quarantine centres which work in coordination with the block quarantine centres concerned.
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text:
Crash Bandicoot: The Wrath of Cortex was developed by Traveller's Tales and released in 2001 for the PS2 and 2002 for the Xbox and Gamecube. It's the last Crash game to follow the classic formula of warp rooms, crystals, gems, relics etc and the first game in the main series (ignoring Eurocom's party game Crash Bash) not to be developed by Naughty Dog. Like Crash 1-3 the focus is less on simply clearing every level, but going for 105% completion, a feat that requires nothing short of game mastery. The plot is pretty much copy-pasted from Crash 3, an ancient evil is released to aid Dr Neo Cortex in a dastardly scheme and only a vast assortment of precious stones can stop them. This marks the debut (and indeed, only appearance) of many types of gimmick level, including the atlasphere and helipack as well as bringing in Coco as a fully playable character in some levels, rather than leaving her with various vehicles.
This is going to be a 105% run. This will not be easy since some of the later collectibles are absolute bitches to get. However I did it when I was 14, so I at least know I can do it. The plan is to have at least one video a week, each one covering a world and the occasional backtracking/collecting video.
As a kid I played the Xbox version, but this is going to be the PS2 version. There are no real gameplay changes beside the PS2's analog sticks being far inferior to the Xbox's.
But NJ, What About Crash 1-3?
Glad you asked, Envisioned did a great megathread covering those games which is archived here!
Relics: 30/30 (1 Sapphire (argh!), 16 Gold, 13 Platinum)
The uncut version of me time trialling Gold Rush, not for the faint hearted
The main marsupial, Crash is the result of one of Cortex's experiments gone wrong (yes really) and as a result seeks to thwart the bad doctor at every turn. He's our main character and in accordance with videogame law, the least interesting thing in the game despite being a pretty cool guy.
(actually a more recent look, but it fits her in this game)
Crash's sister and chief technical girl. Rides a jetski, has a pet tiger, kicks ass on a scooter, snowboards, hacked into Cortex's Time Twister in Crash 3, built the entire damn warp room in this game. Is beyond cool and awesome but dear god don't google her. Is also voiced by the same woman who voiced Jimmy Neutron, which I think is cool.
Crash and Coco's mask guardian. Upholder of all that is right and good, he appears in levels to provide protection against enemies.
Dr. Neo Cortex
Crash's creator and nemesis, a bumbling genius skilled in the creation of mutant animal superweapons. Despite his name being in the manual for every Crash game, Wrath of Cortex is the first time he's mentioned by his first name in the actual game.
Aku-Aku's evil brother, the mask who pulls Cortex's strings and facilitates evil thanks to his ancient sealed mask rolodex.
Cortex's latest mutant animal creation. A roided, jacked up bandicoot with bad taste in trousers who could probably beat Crash's ass day after day in a fair fight. However he uses the Elementals to gain the advantage, so naturally finds himself on the receiving end of Crash's various vehicles.
A crew of 4 masks representing the ancient elements of fire, wind, earth and water. Sealed away because of their past destruction they're released by Uka-Uka to provide the power Cortex needs to bring Crunch to life. The fire mask Py-Ro is voiced by Mark Hamill, which is odd. Even odder is that Lo-Lo the wind mask is voiced by Jess Hamell, who previously voiced Crash's main platform rival Spyro.

domain: entertainment


text:
Title: Hurt for the Right Reasons
Warnings: AU sixth year, hogwarts era, underage, bottom!draco, first time, shower!sex, angry!sex
Summary: Everything was so cocked up. He just wanted this one thing. He wanted to hurt for the right reasons for once.
God this was so great. I loved the realistic takes on their characters, it sort of feels like something that could happen organically, it isn't all fluffy love-conquers-all. But the ending is hopeful and really perfect.
Title: Save It For Me (Sequel to Don't Think Twice and It's All Right)
Word Count: 6,000
Warnings: bathtub sex, blowjob, rimming, bottom!draco
Summary: Harry returns to Hogwarts after Christmas. Malfoy's been waiting for him.
This entire series is really fantastic and this is a lovely addition! We get to see a bit more of the feelings that may be developing between Draco and Harry and, of course, some hot filthy sex! And the Hermione cameo in this one is wonderful.
Title: The Invisible Man
Word Count: 9,984
Warnings: auror!harry, invisible!sex, sex toys, voyeurism, exhibitionism, technically bottom!draco but there are some bottom!harry implications
Summary: Sometimes unforeseen side effects aren't the worst thing that can happen to a person.
Funny and sexy as is the usual with faithwood's fics! Ron is especially lovely in this (I love his interactions with Draco) and Draco is wonderful and hilarious. Plus some seriously hot sex!
Title: All Our Secrets Laid Bare
Pairing: Harry/Draco, Ron/Hermione, Harry/OMC
Word Count: ~145,000
Warnings: auror!fic, auror!harry, auror!draco, switching, first time, tattoo!kink
Summary: Over the six years Draco Malfoy has been an Auror, four of his partners have turned up dead. Harry Potter is assigned as his newest partner to investigate just what is going on.
This fic was so unbelievably fantastic! It was perfectly paced and the build-up was believable. The characterizations of Harry and Draco were amazing, and the side characters were fantastic (one of my favorite Ron's ever!). There was mystery, and plot, and hot sex and it was just a really fantastic read.
Title: It Takes Three (Sequel to In Three)
Pairings: Draco/Teddy, Draco/Teddy/Harry
Word Count: ~2,500
Warnings: dirty talk, threesome, m/m/m, bottom!teddy
Summary: Draco's never one to miss an opportunity, especially when they come twice in one night.
A sexy sequel to In Three, which I definitely suggest reading first because it is fantastic and sets this fic up wonderfully. Draco is just so sexy and seductive here, poor Harry never stands a chance at resisting such a dirty mouth! And I loved the way Teddy is written, just so desperate for it, but definitely not a pushover.
Title: Charlie Weasley's Fuck Autobiography
Pairings: permutations of Charlie/Harry/Draco/Teddy, (Harry/Draco, Charlie/Teddy), past Teddy/Victoire, [Spoiler (click to open)]Bill/Charlie, reference to Bill/Fleur
Warnings: first person, threesome, m/m/m, foursome, m/m/m/m, Daddy!kink (between Charlie and Teddy), godfather/godson, bottom!Draco, bottom!harry, bottom!teddy, some mild D/s, brief and mild whipping, cousincest, rough sex, [Spoiler (click to open)]incest, infidelity, bottom!charlie
Summary: Charlie doesn't think that this is his Fuck Autobiography. But it so is.
This was crazy, ridiculously hot. Kinky and dirtyfilthyhot. And while there is a fuckton of awesome sex, there is a good balance of emotions and feelings without being too heavy or angsty.


text:
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domain: health


After two years at the helm, Alex Ballinger is stepping down from his role as editor of BikeBiz, and will be replaced by staff writer Daniel Blackham.
Blackham joined the BikeBiz team in March 2023 as staff writer, moving into bike media from his role in local journalism.
Since joining the team, Blackham has impressed with his passion for all things two-wheeled and his natural understanding of the issues that face the industry.
Ballinger, who joined BikeBiz in November 2021 from his previous role as digital news editor at Cycling Weekly, will be leaving cycling media after five years of writing about bikes, and two years as BikeBiz editor. His new role will see him take up a deputy editor position for a medical publication.
On leaving his current role, Ballinger said: “It’s hugely bittersweet to be leaving BikeBiz after two years leading this esteemed magazine. I am hugely proud of what we have achieved over the past few years, helping steer the bike industry through one of the most turbulent eras in recent memory.
“From redesigning the magazine layout, to revamping our product pages, representing the title at events, and striving to provide a voice to independent retailers across the country, it has been a great privilege to serve this industry. I will miss it very much.”
Ballinger’s last day with BikeBiz will be Friday, September 22, at which point Blackham will take reins as editor.
On Blackham’s appointment, Ballinger said: “Dan has been a phenomenal asset to BikeBiz since he joined earlier this year, and I have been continually impressed with his professionalism and his understanding of what we are trying to achieve with BikeBiz.
“I am confident the magazine is being left in the safest hands and that BikeBiz will continue to be a leading voice for the cycle industry, from retailers through to distributors, brands and media.”
Blackham said: “It feels slightly strange to be part of this announcement, but I’m thrilled to be taking on the role of editor.
“Special thanks to Alex for giving me the opportunity to join BikeBiz and for all of his support throughout. The positive feedback we receive shows that his efforts have been recognised beyond BikeBiz towers and the magazine is in a better place after his editorship.
“For readers and advertisers it’s very much ‘business as usual’ to ensure we remain a trusted and respected resource for the industry.”
With the majority of 2023 now in the rear view mirror, we are asking you,…
Le Col, the performance cycling apparel brand, has extended its use of Polartec materials with…
Prestacycle has announced the opening of its new UK office as a part of its…
Canyon Bicycles is steering towards a successful close of the 2023 business year. At the…


Celebrity Chef Eduardo Garcia Stars in Saucony's Inspiring Film About Running, Food and the Outdoors
Sneaker Brand's Beautifully Filmed Spot Will Strike a Chord With Runners
Jul 20, 2015
Saucony profiles Eduardo Garcia, aka "The Bionic Chef," in this inspiring and uplifting film that shows how he finds inspiration in cooking, foraging and of course running, having vowed to find new meaning in life after he lost his left arm in a hiking accident in 2011.
Chef Garcia, founder of the food brand Montana Mex, stars in this short shot in beautiful landscapes around Montana. where he grew up. In it, he explains how he decided to "milk more out of life daily" following his accident.
He's great on the subject of food, but it's his words on how running helps him reconnect with the outdoors that will really strike a chord with the brand's target audience. The film, part of a series by Saucony called "Seeker Stories", was directed by Co.Lab at Persuade & Influence, for agency Mechanica. Whitehouse Post and Carbon VFX also worked on the spot.


text:
Nordic Plast, a leading Latvia-based polyethylene and polypropylene recycler that is part of Baltic environmental and waste management group, Eco Baltia, has completed a modernisation project that involved a €2.8 million investment into a new, automated sorting line. The company says the new line will raise its recycling capacities by upwards of 30% as well as provide a significant boost to production quality and efficiency. The company was previously largely dependent on manual sorting for its packaging sorting operations, which limited its growth in production capacity, it said.
The new equipment will make it possible to process materials of various purity, enabling the sorting of even the more difficult packaging streams, for which recycling rates have remained consistently low.
In the European Union, plastic packaging recycling goals are set to rise from the current 22% to 50% of the total volume of marketed plastic packaging by 2025.
“Eco Baltia’s mission is to find value in things that others already consider unnecessary. That’s why we treat waste as a resource to create new materials and promote circular economy. Therefore, we are constantly developing options to recycle a wider range of packaging and other materials. Investments in the modernisation of Nordic Plast is a significant step to achieve this goal and creates a foundation for the development of new recycled products,” said Māris Simanovičs, Chairman of the Management Board at Eco Baltia.
The investments in the new Nordic Plast line have been partially covered by using the funds received from the European Union fund project “Polymer Recycling Park of the SIA “Nordic Plast”” (No.22.214.171.124/17/A/005).

domain: news


The Champions League proper got underway this evening as the first wave of group stage matches took place across Europe.
In Group A, Arsenal profited from a wasteful Paris Saint-Germain side – Edinson Cavani was particularly guilty – and were able to claim a 1-1 draw at the Parc des Princes.
In the other game in that group, FC Basel got off to a poor start as they could only claim a 1-1 draw at home to Bulgarian outfit Ludogorets.
The results leave the group exactly the same as it was earlier tonight, Arsenal on top alphabetically and PSG at the bottom by the same principle.
In Group B, Napoli had to come from behind to claim a 2-1 victory away at Dynamo Kiev. Denis Garmash put the home side in front just before the half-hour mark, but two goals from new €35m signing Arkadiusz Milik gave Maurizio Sarri’s side a vital three points.
In the other game in that group, Benfica played out a 1-1 draw in an even contest against Besiktas at the Estadio da Luz. Benfica thought they had won the match with a Franco Cerv effort after twelve minutes, but there was to be late drama when Anderson Talisca, who joined Besiktas from Benfica this summer, equalised for his new side in the dying minutes of the game.
The results leave Napoli on top of the group at this early stage.
In Group C, Manchester City’s clash with Borussia Monchengladbach was called off due to torrential rain – that game will now take place on Wednesday at 7.45.
That said, Barcelona’s throttling of Celtic provided enough goals for both games. A reunited MSN tore the away side to shreds as Barca won 7-0 – Messi scored three, Suárez scored two and Neymar assisted four. A missed penalty from Celtic’s Moussa Dembélé compounded the away side’s misery.
The result, unsurprisingly, leaves Barcelona on the top of the table and Brendan Rodgers with plenty to think about.
Finally, to Group D, where Bayern Munich went on a bit of a rampage of their own with a 5-0 victory. FC Rostov were the victims as Carlo Ancelotti’s first Champions League game with the Bundesliga champions went exactly to plan. Robert Lewandowski opened the scoring before Thomas Muller added a second just before half time.
Two rare efforts from Joshua Kimmich ended any hope of a Rostov fightback before Juan Bernat put the icing on the Bavarian cake.
Atlético Madrid travelled to PSV Eindhoven in the other game in the group, but it proved to be far trickier. They got the win thanks to a brilliant Saúl Ñíguez strike in the 43rd minute, and had Jan Oblak to thank for saving a penalty from Andres Guardado just before the half time break with the game later finishing 1-0.
It was a win Diego Simeone’s side badly needed, as they welcome Bayern to the Calderón in the next round of Champions League fixtures.


text:
ETFs or individual stocks and navigating the future
Hi, As an interested but unsophisticated investor, I like ETFs' (index funds). Given the Covid situation, in the coming years, do you think investors looking for yield and growth will have to look more to individual stocks or do you think that ETFs (like InvestSmarts' portfolios) will continue to deliver comparable returns. I have listened to the Robin Bowerman (Vanguard) and James Kirby interview but am interested in your thoughts and wonder how InvestSmart plans to navigate the economic future ...thanks Dianne - Submitted by Dianne
Although I cannot give you advice about which avenue to take regarding individual stocks or ETFs, I can point out that having a diversified portfolio structured around multiple asset classes and products has been proven to perform well over the long-term and it can also assist in buffering your portfolio from events like the one we are currently experiencing. To achieve that diversification, it can mean having both stocks and ETF in your holdings.
Regarding how InvestSMART is navigating the current and future economic environment - we are making sure our portfolios are as tightly aligned with their benchmarks, and consensus asset allocations. We have seen that even during this current scenario they continue to outperform peers with the lowest fees we can. We believe this strategy will continue to outperform over the coming decades and is the best way to navigate future economic cycles.

domain: economics


text:
Complain all you want about the Oscars (I certainly do), but give the academy major props for bypassing a clunker like “Cars 2” and handing a Best Animated Feature Film nomination to something as wonderful as “Chico & Rita.”
Fernando Trueba, who won the Foreign Language Feature Oscar for the live-action “Belle Epoque” (1992) joined with Spanish graphic artist Javier Mariscal to co-direct this swooningly beautiful, adults-only drama.
It’s a star-crossed romance between jazz pianist Chico (voiced by Eman Xor Ona) and the sultry Rita (Limara Meneses), surely the most voluptuous animated female character since Jessica Rabbit.
I don’t recall Jessica ever having a full-frontal nude scene, much less having onscreen sex like Rita does with Chico in 1948 Havana.
And you certainly won’t find a drug subplot in 1959 New York straight out of “Sweet Smell of Success” in anything from Pixar.
Bookended with scenes in present-day Cuba, this is a swooningly romantic, decades-spanning saga that also takes the frequently separated lovers to Las Vegas, Hollywood, London, Paris and several other cities — all ravishingly depicted in period detail.
If that’s a feast for the eyes, and the soundtrack delights the ears with great music by Bebo Valdes, Dizzy Gillespie, Thelonious Monk, Charlie Parker and Tito Puente.
There are cartoon cameos by Woody Herman, Fred Astaire, Humphrey Bogart, Nat King Cole and many more.
But “Chico and Rita’’ beguiles first and foremost as a bebop romance that evokes a bygone era as well as, or maybe even better than, “The Artist.”

domain: artistic


text:
The Star is profiling Southern Arizona high school athletes whose seasons were cut short by the coronavirus pandemic. Each high school was asked to nominate an exceptional spring sport athlete who exemplifies greatness on and off the field, court or track.
Ryan Zuniga first slipped his hand into the cool, stiff leather of a new baseball glove when he was 4 years old. He can barely remember a time when he hasn’t played the sport.
And while he dreams of making it to the big leagues, Zuniga is taking it one level at a time. The 18-year-old Rio Rico High School junior says he wants to play baseball in college.
“I grew up watching my cousin, who went on to go to college, so he was one of the role models for me to continue pitching,” Zuniga said.
Keith Zuniga was a 2010 graduate of Nogales High School who went on to pitch at Pima College and Bethune-Cookman University.
The Miami Marlins took Keith Zuniga in the 35th round of the 2014 amateur draft, but he turned down the offer to keep the promise he’d made his mother to graduate from college. The decision paid off for Keith Zuniga, who is now an assistant coach at his alma mater in Florida.
Rio Rico baseball coach Hector Zuniga, Ryan’s uncle, is certain that the pitcher will follow in his cousin’s footsteps.
“I’ve seen (Ryan) grow up and become a skilled player. He’s courageous and bows to no team,” Hector Zuniga said. “He always wants the ball even if it’s just with one or two days of rest. Ryan has a deceiving arm, which is definitely a special gift.”
Ryan Zuniga’s 2020 season was off to a solid start before it was cut short. So good, in fact, that he said the season opener is his favorite memory from high school.
“We just had this boost of confidence going into what we thought was the long run of the season,” Zuniga said.
When he’s not playing baseball, Zuniga is helping his parents out on the family ranch, feeding horses or tending to the roosters.
“I ride horses when it’s not really hot,” Zuniga said. “I enjoy it — just not every single day.”
Zuinga is working hard to keep his game sharp in anticipation of a summer club season. But with nowhere to play, it’s a little different.
“I’ve been throwing weight balls into a pad and now I’m starting to run hills,” he said. “I’m working a lot to start to get better with no baseball field. I’m trying to get better every single day so I can get somewhere by the end of this next school year.”
The goal: playing college baseball.
“I’m continuing to work hard on my craft, and pretty much just staying in shape so I can start off my senior year with a bang,” he said. “If any college gives me the opportunity (to play), I’ll gladly take it.”
And as coronavirus-related precautions in Arizona begin to be lifted, Zuniga is more and more hopeful that he’ll get a chance to play with his club team, the Angels Scout Team. He started playing with the Angels last year.
“I really enjoy playing with the guys up there. They boost me up,” he said. “When summer ball ends, I come back down to my high school team and try to get everyone better and boost everyone’s self-esteem and confidence by giving them pointers I learned.”
But after nearly three months without baseball, Zuniga isn’t about to be picky.
“Really, I just want to get back out on the field and start playing with the guys,” he said.
Leo and Ivan Villa
Refugio "Kito" Del Cid
Cheyenne Hudson and Laneya Wright
Contact reporter Caitlin Schmidt at firstname.lastname@example.org or 573-4191. On Twitter: @caitlincschmidt
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domain: sports


text:
A set of hearings about missing and murdered Indigenous people is about to wrap up
SCOTT SIMON, HOST:
The national registry says Native Americans make up less than 1% of the U.S. population but account for nearly 4% of all missing persons reports. Federal commission investigating the issue is now concluding hearings it's been holding around the country. Jeanette DeDios from member station KUNM in Albuquerque reports on some of the solutions Indigenous people have suggested.
JEANETTE DEDIOS, BYLINE: Tiffany Reid is one of nearly 200 Native people known to be missing in New Mexico and the Navajo Nation. Her big sister, Deiandra, remembers her always adopting stray cats and writing poetry.
DEIANDRA REID: She did a poetry slam contest in, I want to say, Missouri - the last place that she went just right before she went missing.
DEDIOS: One day in 2004, when she was 16, she left to go to school in Shiprock.
REID: That was it. We never seen or heard from her since then.
DEDIOS: Reid is one of dozens of people who testified at the Not Invisible commission hearing in Albuquerque, raising long-standing complaints about police response.
REID: It's really hard for me to get in contact with anybody, and when I do, they're constantly changing officers. So I've talked to maybe three different officers so far within the last two years. It's really frustrating to me.
DEDIOS: Policing in Indian country is often a confusing jumble of state, local, tribal and federal agencies. Again and again at the hearings, people complain those agencies rarely coordinate well in missing persons cases. Amber Crotty, a delegate on the Navajo Nation Council, says families organize their own searches, investigations and protest marches.
AMBER CROTTY: The families are tired of walking. They're tired of protesting. They're tired of just everything. They just want justice.
DEDIOS: Patricia Lightfoot, whose sister disappeared decades ago, testified police often seem ill-prepared to deal with Native communities.
PATRICIA LIGHTFOOT: What kind of education is being done and conducted, particularly with non-Native officers and our own tribal officers as well? What do you know about the history of our people? What do you know about historical and cultural oppression?
DEDIOS: These hearings are the result of a yearslong quest by America's first Indigenous cabinet member, Interior Secretary Deb Haaland. Before she was appointed, she represented New Mexico in Congress and got the Not Invisible Act passed.
(SOUNDBITE OF ARCHIVED RECORDING)
DEB HAALAND: A real solution will never be found without the voices of Indigenous survivors, which is what is so special about this bill.
DEDIOS: The act requires the U.S. Department of Justice to partner with Interior to coordinate federal law enforcement response to missing Native persons. At the Albuquerque event, U.S. Attorney Alexander Uballez announced some new help.
ALEXANDER UBALLEZ: A new nationwide program to support the effort to locate missing and murdered Indigenous people, to seek proactive strategies to prevent future murders.
DEDIOS: Justice is assigning 39 assistant U.S. attorneys to offices in nine states to provide specialized support for missing and murdered Native cases. Justice has also promised to address crimes it says underlie missing persons reports like domestic and sexual violence and trafficking humans and drugs. Celina Montoya Garcia, from the Coalition to Stop Violence Against Native Women, traces some problems to decades of the federal government displacing Native people from their homelands and forcing kids into abusive boarding schools.
CELINA MONTOYA-GARCIA: Like, the trickling effects of all of that has also come down to our people, who have learned violence.
DEDIOS: Other violence comes from outside, like camps where largely male workers live while working coal mines or oil wells on Native lands.
MONTOYA-GARCIA: These camps are causing an increased rate in sex trafficking, sexual assault, domestic violence, the - like, there's more, like, drugs, substance use happening.
DEDIOS: The commission will meet in Billings, Mont., this month and then for a virtual session later in the summer. In the fall, it is due to make recommendations aiming to stop disappearances like Tiffany Reid's.
REID: I don't think I'll ever give up until I do find her or find out what happened to her. I just want to bring her home one way or another, you know, good or bad.
DEDIOS: For NPR News, I'm Jeanette DeDios in Albuquerque. Transcript provided by NPR, Copyright NPR.
NPR transcripts are created on a rush deadline by an NPR contractor. This text may not be in its final form and may be updated or revised in the future. Accuracy and availability may vary. The authoritative record of NPR’s programming is the audio record.

domain: sociology


text:
Even a gem can dull over time, so Franklin & Marshall’s Phillips Museum of Art was polished this summer with vibrant paint, updated lighting and refinished floors. The newly arranged space displays the fall exhibits, from never-before-seen collection items to pop-up books and from photography to etchings.
“Nissley Gallery is undergoing a complete transformation as part of a two-phase process, thanks to the generosity of Thomas Nissley '55 and his wife, Emily Baldwin Nissley,” said Amy Moorefield, director of the Franklin & Marshall College museum.
For this reinstallation of the Nissley, museum staff removed old cases, pedestals and outdated lighting and replaced them with custom pedestals, mounts and LED lighting. They covered the walls in a dark granite paint, against which 100 pieces from the permanent collection will show.
The museum’s collection has more 8,000 objects, from pre-Columbian, African and Japanese objects, regionally created furniture, fiber arts and crafts, as well as paintings, sculptures, works on paper, and glass created from the 1800s to present day, Moorefield said.
In the museum's stairwells, a bright white paint, "Chantilly Lace," was used to increased visibility.
“We also painted this color in the Dana Gallery as a good neutral to Colette Fu's colorful and large-scale pop-up books,” Moorefield said.
Fu’s one-of-a-kind pop-up artist books, displayed for the exhibit, “We Are Tiger Dragon People,” are based on her ancestral explorations in China’s Yunnan Province, where 25 of the country’s 55 minority tribes reside. Fu said her books reflect “ideas on how our selves relate to society today.”
Downstairs, in the museum’s Rothman Gallery, are photographs of Civil War soldiers developed on the flesh of leaves for “War Memoranda: Photography, Walt Whitman and Memorials.” The wall color that highlights the worksofBinh Danh and Robert Schultz is "Sharkskin.”
With their exhibit, artist Danh and poet Schultz examine the question, “How do Americans remember war?” The two men also will speak at the Oct. 18 Common Hour about their work.
In the Gibson Gallery, a shade darker than Sharkskin complements an exhibitof the works of 19th-20th century German artist KätheKollwitz. Her series of powerful etchings, “Bauernkrieg/Peasant War,” represent the brutal treatment of peasants in 16th-century Germany, their revolution and eventual demise.
Kollwitz created the etchings between 1903 and 1908. They served as a vehicle to criticize and protest the anticipated violent events that started to unfold across Europe at the time. The works are on loan from Dickinson College’s Trout Gallery.
“The new exhibitions highlight our mission to present art and material culture being made globally and that ties broadly into other interdisciplinary areas such as history, science, and math among others. We look forward to welcoming all to the museum this fall season,” Moorefield said.
For more information on the Phillips Museum’s exhibits and events, visit here.
The exhibits in the Nissley and Dana galleries run from Aug. 28 to Dec. 7; the exhibits in the Rothman and Gibson galleries run from Sept. 4 to Dec. 7. The museum is open Sunday, Tuesday, Wednesday, Friday and Saturday, noon to 4 p.m., and Thursdays, 2 p.m. to 6 p.m.