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Siloxane-polyether copolymers with unsaturated functionalities, and process for making them
This invention discloses hydrophilic additives in polysiloxane gels, elastomers and coatings, and novel processes for producing them. The process comprises:(a) redistributing into polysiloxane-polyether copolymers an unsaturated silane or siloxane,(b) adding to the mixture of reagents a catalytically effective amount of a basic catalyst; and(c) heating the reaction mixture to effect reaction.Novel siloxane structures of unsaturated aliphatic modified polyerther siloxane copolymers are also taught.
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The present invention relates to siloxane-polyether compositions with unsaturated functionalities, such as alkenyl and alkynyl groups, which are capable of being hydrosilylated. These compositions are usefuil as hydrophilic additives for addition -cure polysiloxane gels, elastomers and coatings.BACKGROUND OF THE INVENTION
Siloxane-polyether copolymers may be linear, branched, hydrolyzable or nonhydrolyzable structures. U.S. Pat. Nos. 4,657,959 and 4,752,633 disclose their use as semipermanent hydrophilic additives in dental impressions.
Polydiorganosiloxane having terminal or pendant unsaturated hydrocarbon groups are known. Typical examples are the linear polydimethylsiloxanes having a vinyl group attached to the silicon atom at each terminus of the chains, and the linear polydimethylsiloxanes with vinyl groups randomly distributed on silicon atoms in the chains. Polysiloxane-polyether copolymers bearing terminal methacrylate groups impart durable hydrophilicity to the contact lens compositions of U.S. Pat. Nos. 4,259,467 and 4,260,725. Aoki, et al., Macromolecules, Rapid Communications, 18 (1997) 31-36, synthesized hydrolyzable siloxane-polyether copolymers of general formula, [(R'.sub.2 SiO)--(C.sub.2 H.sub.4 O).sub.7 ].sub.20-35, wherein R'=vinyl. While all of these functionalized polysiloxane-polyether copolymers can be reacted into polymer matrices or onto surfaces to improve hydrophilicity, water absorption, lubricity and/or adhesion, the reactions do not result in the formation of Si--C bonds between the matrix or substrate and the functionalized polysiloxane-polyether. Si--C bonds are desirable because they are strong and nonhydrolyzable.
U.S. Pat. No. 5,580,921 discloses storage-stable polysiloxane compositions which impart permanent hydrophilicity to addition cure dental impression compounds. Permanent hydrophilicity is provided by polysiloxane-polyether copolymers which have 10-400 silicon atoms per molecule, which contain unsaturated functionalities and which are free of noble metal catalysts. The copolymers become bound to the polysiloxane matrix by Si--C bonds during the curing step. Synthesis of the copolymers comprises the preparation of a distillable silane-polyether compound followed by its hydrolysis, condensation and equilibration with alkenyl siloxanes. The copolymer chain lengths are greater than 10 and are miscible with the .alpha., .omega.-divinylpolysiloxanes used in addition cure formulations. This feature facilitates storage stability of the two part formulations and avoids the need to use the copolymer as a separate component. However, the copolymers of long siloxane chain length do not afford the most rapid spreading of water and wetting of the cured polysiloxane surface.BRIEF SUMMARY OF THE INVENTION
Accordingly, the instant invention discloses noble metal-containing, unsaturated siloxane-polyether copolymer compositions synthesized by the base-catalyzed equilibration of unsaturated silanes and siloxanes with saturated siloxane-polyether copolymers or ring opening of cyclic siloxane polyether copolymers with unsaturated siloxanes. Base-catalyzed equilibration of an alkenyl silane or siloxane with siloxane-polyether copolymer products affords unsaturated siloxane-polyether copolymers which impart permanent hydrophilicity to addition cure polysiloxane compositions, as well as to polyethylene, polypropylene and polyester matrices. Besides the hydrophilic modifiers, the equilibration reaction mixtures also contain polyethers and noble metal catalyst residues.DETAILED DESCRIPTION OF THE INVENTION
It is an object of the instant invention to provide unsaturated, nonhydrolyzable siloxane-polyether copolymers that are capable of forming further Si--C bonds via hydrosilylation. Another object of the instant invention is the provision of unsaturated siloxane-polyether copolymers useful as hydrophilic modifiers in polysiloxane, polyethylene, polypropylene, polyester and other thermoplastic substrates. A still further object is control of the content of unsaturated groups in the hydrophilic modifier so that both desirable hydrophilicity and optimum catalysis (cure time and working time) are realized in addition cure polysiloxane compositions. Another aspect of the invention is products of the following reaction, particularly those products in which there are up to nine silicon atoms present. In nonhydrolyzable siloxane-polyether copolymers, the polyether and siloxane segments are linked by Si--C bonds, which are resistant to cleavage under aqueous acidic and alkaline conditions.
A method for the synthesis of the said unsaturated polysiloxane-polyether copolymers of controlled unsaturation content includes the following steps:
(a) combining polysiloxane-polyether copolymers and an alkenyl or alkynyl silane or siloxane, or an, capable of undergoing addition or redistribution reactions with the copolymers in an amount sufficient to achieve the desirable degree of alkenyl or alkynyl substitution to form a first mixture,
(b) adding to the first mixture of reagents a catalytically effective amount of a basic catalyst to form a reaction mixture; and
(c) heating the reaction mixture.
Preferably there is also a purification step to remove by-products and catalyst.
The polysiloxane-polyether copolymer may be obtained, for example by hydrosilylation as described in U.S. Pat. Nos. 3,299,112, 4,847,398, 4,857,583, 5,191,103 or 5,159,096, all of which are incorporated herein by reference, or from commercial sources. The copolymer can contain bound and free platinum, unreacted polyether and reaction byproducts such as acetals and propanal. The copolymer may be cyclic, linear, or branched (in either T or Q formation). The exact structure of the copolymers for use herein will depend on the desired end structures, examples of which are set forth below.
The copolymer may be represented by the formula
[R.sub.3 SiO.sub.1/2 ].sub.m [ZR.sub.2 SiO.sub.1/2 ].sub.n [O.sub.1/2 Si(R.sub.2)O.sub.1/2 ].sub.o [O.sub.1/2 SiRZO.sub.1/2 ].sub.p [SiO.sub.3/2 R].sub.q [SiO.sub.4/2 ].sub.r
R is a C.sub.1 -C.sub.20, preferably C.sub.1 -C.sub.12, saturated, monovalent organic group. Illustrative of the saturated monovalent groups represented by R are the alkyl groups (for example, methyl, ethyl, isopropyl, octyl and dodecyl groups), the aryl groups (for example, the phenyl and naphthyl groups), the alkaryl groups (for example, tolyl and nonylphenyl groups), the aralkyl groups (for example, benzyl and phenethyl groups) and the cycloalkyl groups (for example, cyclopentyl and cyclohexyl groups). R may also be a functionalized organic group such as the chloropropyl, heptafluoroisopropyl, and cyanoethyl groups. Most preferably R is methyl.
Z is a polyether-containing group that is linked to the polysiloxane block by a silicon-carbon bond. Z has general formulae of the type, --C.sub.x H.sub.2x O(C.sub.a H.sub.2a O).sub.b R" and --C.sub.x H.sub.2x OG[(C.sub.a H.sub.2a O).sub.b R"].sub.r wherein x is an integer in the range 1-20, and is preferably 2-8. The subscript, a, is an integer having a value greater than or equal to 2. Preferred values of a are 2, 3, and 4. Illustrative of the oxyalkylene groups in the polyether portion of the copolymer are the oxyethylene, the oxy-1,2-propylene, oxy-1,2-butylene, oxy-2,2-dimethyl-1,3-propylene groups and the like. The polyether portion of the copolymer may contain oxyalkylene units of more than one type. For optimum hydrophilicity, it is desirable that at least 40 weight percent, and preferably at least 70 weight percent, of the oxyalkylene groups be oxyethylene groups. The subscript, b, is a positive number that is preferably greater than 3 up to 12.
G is a polyhydroxy group capable of being alkoxylated. The subscript, r, represents the number of alkoxylated hydroxyl groups. Examples of G are alkylene glycols, alkyne glycols, glycerol, pentaerythritol, hydroquinone, trimethylolpropane, sorbitol, glucose and sucrose.
R" is hydrogen or a polyether capping group such as an alkyl group of 1-8 carbon atoms, or an acyl group of 1-8 carbon atoms, or a vinyl ether or an organosilyl group. Alkyl groups exemplifying R" are methyl, tertiary butyl and 2-ethylhexyl. Examples of acyl capping groups are acetoxy, acetoacetoxy, acryloxy, methacryloxy and benzoyl. Organosilyl capping groups comprise the saturated trialkylsilyl groups such as trimethylsilyl, triethyl, ethylisopropyl, thexyldimethyl, t-butyldimethyl, t-butyldiphenyl, the unsaturated capping groups such as the vinyldimethyl, divinyloctyl, ethynyldimethyl and propynyldimethyl. Examples of vinyl ether end groups comprise dihydropyranyl and vinyloxyethoxy (H.sub.2 C.dbd.CH--O--CH.sub.2 CH.sub.2 O--). Owing to the variable efficiency of polyether capping reactions, uncapped polyether molecules are likely to be present during the hydrosilylation synthesis of the polysiloxane-polyether copolymer starting material. Accordingly, nominally capped copolymer products may also contain uncapped polysiloxane-polyether copolymers.
m=0 to 5, preferably 0 to 2; n=0 to 3; preferably 0; o=0 to 100, preferably 0 to 50; p=0 to 30; preferably 0 to 10; q=0 to 4; r=0 to 2. If p=0, then n>0 and if n=0, then p=0. m+n+o+p+q+r=3 to 100, preferably 3 to 50.
The copolymer is reacted with linear and/or cyclic siloxanes and silanes bearing non-aromatic unsaturated groups bonded to silicon through an Si--C bond so that either a redistribution of saturated and unsaturated groups occurs, or siloxane segments bearing unsaturated groups become incorporated into the polysiloxane blocks of the polysiloxane-polyether copolymers. If ethylenic, the unsaturation is .alpha.,.beta., while if the unsaturation is acetylenic, it may be internal to the unsaturated substituent. The unsaturated group may be terminal or internal to the siloxane. The silanes may be represented by the formula R.sub.a R.sup.1.sub.b Si(OR).sub.4-a-b with a=1 to 3, b=1 to 3 and a+b.ltoreq.=3. The siloxanes may be of the structure of the siloxane above, excpet that Z is replaced with R.sup.1. R.sup.1 is a C.sub.1 -C.sub.20, preferably C.sub.1 -C.sub.12, unsaturated monovalent organic group that can be hydrosilylated to yield silicon-carbon bonds. Illustrative of the unsaturated groups represented by R.sup.1 are the alkenyl groups (for example, vinyl, allyl, methallyl, vinylcyclohexanyl), and, the alkynyl groups (for example, acetylenic and propargyl). Specific examples of the siloxane/silane are [H.sub.2 C.dbd.CHSi(CH.sub.3).sub.2 ].sub.2 O or [H.sub.2 C.dbd.CHSi(CH.sub.3)O].sub.3-25, or (H.sub.2 C.dbd.CH).sub.x Si[OSi(CH.sub.3).sub.3 ].sub.4-x, (H.sub.2 C.dbd.CH).sub.x Si(OC.sub.2 H.sub.4 OCH.sub.3).sub.4-x, x=1, 2, or 3).
Equations (1-3) exemplify the chemical transformations expected. ##STR1##
Redistribution is accomplished in the presence of basic catalysts such as KOH, CsOH, Ca(OH).sub.2, (CH.sub.3).sub.4 N.sup.+- OSi(CH.sub.3).sub.3, (CH.sub.3).sub.4 N.sup.+- [OSi(CH.sub.3).sub.2 ].sub.s O.sup.-+ N(CH.sub.3).sub.4 (s=4-100) and K.sup.+- OSi(CH.sub.3).sub.3 at temperatures up to about 200.degree. C., preferably up to about 150.degree. C. Catalysts containing the tetramethyl ammonium cation, or another tetra alkyl ammonium cation, are preferred because they are readily destroyed by heat at the end of the reaction. The reaction mixture may be stripped in vacuo to remove unreacted alkenyl siloxane and volatile by-products of the thermal decomposition such as trimethylamine and redistribution by-products such as (CH.sub.3).sub.3 SiOH, (CH.sub.3).sub.3 SiOSi(CH.sub.3).sub.3 and H.sub.2 C.dbd.CHSi(CH.sub.3).sub.2 OSi(CH.sub.3).sub.3. Neutralization with (CH.sub.3).sub.3 SiCl or with strong acid (for example, HCl) is preferred when catalysts containing the alkali or alkaline earth metals are used. Thereafter, the reaction mixture is subjected to filtration and in vacuo stripping of volatiles. The base should be present at a catalytically effective amount, which generally is 0.05 wt % to 5 wt %, preferably 0.1 wt % to 1 wt %.
The stoichiometric ratio of unsaturated siloxane to polysiloxane-polyether copolymer during the equilibration or ring opening covers the broad range, 0.05-20, but is preferably 0.5-4 and most preferably 0.75-3. When a cyclic polysiloxane-polyether copolymer is used (as shown in Equation 3 above), the stoichiometric ratio is desirably 1-2. It is not necessary that every molecule of unsaturated siloxane-polyether copolymer be at least doubly substituted with hydrosilylatable alkenyl or alkynyl groups. It is only necessary that sufficient molecules be at least singly substituted so that they become bound to the matrix or substrate requiring permanent hydrophilicity. Thus, the addition reaction depicted in equation (3) can be done with mixtures of [(CH.sub.3).sub.3 Si].sub.2 O and [H.sub.2 C.dbd.CHSi(CH.sub.3).sub.2 ].sub.2 O to control the vinyl content of the product. In some instances, a high content of unsaturation can lead to inhibition of cure when the unsaturated polysiloxane-polyether copolymer is used in addition cure polysiloxane formulations. That the reaction product contains hydrosilylatable unsaturated groups bound to silicon can be established and quantified by spectroscopic measurements, particularly .sup.13 C and .sup.29 Si nuclear magnetic resonance. These unsaturated groups are distinguishable from others such as allyl and propenyl, which are associated with unreacted polyether.
A preferred process is one wherein the starting siloxane-polyether copolymer is cyclic (m, n, q, and r are all 0] which is ring opened with a disiloxane of the structure R.sup.1 R.sub.2 SiOSiR.sub.2 R.sup.1 or R.sub.3 SiOSiR.sub.2 R.sup.1 (preferably, the former) with R and R.sup.1 as above.
Unsaturated siloxane-polyether copolymers are the principal products of the two step synthesis. The remainder of the reaction mixture comprises saturated siloxane-polyether copolymers, unreacted polyethers such as allyl, propenyl, methallyl, vinyl and propargyl polyethers, and free and/or chemically bound platinum. If the composition is prepared with uncapped polyethers, some of the copolymers and polyethers might be linked by acetal groups. The presence of acetals is not detrimental to the performance of the reaction product as a hydrophilic additive, but it is preferable to remove same. The platinum content of the unsaturated polysiloxane-polyether product can be in the range 0.5-100 ppm, but is typically 5-50 ppm.
The compositions comprise unsaturated polysiloxane-polyether copolymers having general formulae and polymer architectures set forth hereinbelow.
(A) R.sup.1 --SiR.sub.2 O(SiR.sub.2 --O).sub.n --(SiR.sup.2 Z--O).sub.m --SiR.sub.2 R.sup.1
(B) R.sup.1 --SiR.sub.2 O(SiR.sub.2 --O).sub.n --(SiR.sup.2 Z--O).sub.m --SiR.sub.3
(C) R.sub.3 SiO(SiR.sub.2 --O).sub.n --(SiR.sup.2 Z--O).sub.m --(SiR.sup.2 R.sup.1 --O).sub.p --SiR.sub.3
(D) R.sup.1 --R.sub.2 SiO(SiR.sub.2 --O).sub.n --(SiR.sup.2 Z--O).sub.m --(SiR.sup.2 R.sup.1 --O).sub.p --SiR.sub.3
(E) R.sup.1 --R.sub.2 SiO(SiR.sub.2 --O).sub.n --(SiR.sup.2 Z--O).sub.m --(SiR.sup.2 R.sup.1 --O).sub.p --SiR.sub.2 R.sup.1
(F) Z--SiR.sub.2 O(SiR.sub.2 --O).sub.n --(SiR.sup.2 R.sup.1 --O).sub.p --SiR.sub.2 R.sup.1
(G) [Z--SiR.sub.2 O(SiR.sub.2 --O).sub.n ].sub.q --(SiR.sub.2 --O)--(SiR.sup.2 R.sup.1 --O).sub.p --SiR.sub.2 R.sup.1
(H) (R.sub.2 Si--O).sub.n --(SiR.sup.2 Z--O).sub.m --(SiR.sup.2 R.sup.1 --O).sub.p
(I) R.sup.1 Si[(O--SiR.sub.2).sub.n --Z].sub.3
(J) RSi[(O--SiR.sup.2 R.sup.1).sub.p --(O--SiR.sub.2).sub.n --Z].sub.3
(K) [R.sup.1 SiR.sub.2 O(SiR.sub.2 --O).sub.n ].sub.v --(SiO.sub.2)[(O--SiR.sup.2 R.sup.1).sub.p (O--SiR.sub.2 Z).sub.m ].sub.4-v
R, R.sup.1 and Z are as above. The groups R.sup.2 may be the same as R or as R.sup.1. Thus, for example, they provide for the presence of methyl and vinyl groups on the same silicon atom, or for the existence of geminal divinyl substitution.
The subscript, n, has a value of 0 to 100, and preferably 0 to 50 inclusive. The subscript, m, is greater than zero, but less than 50 and is preferably 1 to 12 in value. The subscript, p, has a value of 0 to 25 and is preferably 1 to 6. The subscript, q, is 1 up to about 100 and is preferably 10 to 50. The subscript, v, has values of 0 to 3.
One preferred embodiment of the invention is compounds of any of the foregoing formulas (A) through (K), and particularly (A) through (G), wherein the total number of silicon atoms in the molecule is 3 to 5, i.e., R.sup.2 R.sub.2 SiO(SiR.sub.2 O).sub.n (SiR.sup.2 ZO).sub.m (SiR.sup.2 R.sup.1 O).sub.p SiR.sub.2 R.sup.2 wherein +m+p=0 to 3, each n. m, and p are 0 to 3, with the proviso that there is at least one Z and at least one R.sup.2 per molecule and R.sup.2 is R, R.sup.1 or Z. Even more preferably, this a vinyl endblocked siloxane, with p=0 and R is methyl.
Specific examples of the inventive structures are in the following figures. ##STR2##
Hydrophilicity may be determined by measuring the contact angle of a water drop on the surface of interest (see W. Noll, Chemistry and Technology of Silicones, Academic Press, NY, 1968, pp 447-452). A value less than about 60.degree. after 2--3 minutes wetting time denotes a hydrophilic surface. It is known in the art that unmodified polysiloxane surfaces are very hydrophobic and yield water contact angles greater than about 80.degree.. Commercially available hydrophilic dental impression materials yield values in the range, 40-60.degree.. However, these hydrophilic values increase to the hydrophobic range following washing and/or disinfection of the dental impression. The unsaturated polysiloxane-polyether copolymers of the instant invention confer permanent hydrophilicity characterized by water contact angles that are less than about 50.degree. before and after washing and/or disinfection.
The contact angle is a thermodynamic quantity and should have a unique value for a particular system under special conditions. However, hysteresis is often found in contact angle measurements depending on the direction of movement of the interface relative to its interacting surface. When an interface advances along a fresh surface, the advancing contact angle (typically designated .theta..sub.A) is larger than the receding contact angle (typically designated .theta..sub.R). In general .theta..sub.A .gtoreq..theta..gtoreq..theta..sub.R. Advancing and receding angles may differ byas much as 60.degree.. .theta..sub.A for water in contact with silicones is greater than 120.degree.. For measurements made on fresh surfaces under dynamic conditions, hydrophilicity is indicated by .theta..sub.A less than about 100.degree..EXAMPLES
The following illustrative examples describe the instant invention in more detail. They are not intended to limit the scope of the specification and the claims. Abbreviations used in the description of the illustrative examples are defined in the following table.
______________________________________ ABBREV. MEANING ABBREV. MEANING ______________________________________ M (CH.sub.3).sub.3 SiO.sub.1/2 ICP inductively coupled plasma spectroscopy D (CH.sub.3).sub.2 SiO.sub.2/2 gpc gel permeation chromatography D' CH.sub.3 SiHO.sub.2/2 .theta. water contact angle M' (CH.sub.3).sub.2 SiHO.sub.1/2 gc/ms gas chromatography/ mass spectrometry M* H.sub.2 C.dbd.CH(CH.sub.3).sub.2 SiO.sub.1/2 MVC mixture of cyclic methylvinyl-siloxanes EO ethylene oxide ICP inductively coupled plasma spectroscopy PO propylene oxide gc gas chromatography BO butylene oxide ______________________________________
Trimethylsiloxy terminated polysiloxane-polyether copolymers shown in Table 1 were prepared by hydrosilylation using the procedures of the patents cited in the table.
TABLE 1 __________________________________________________________________________ POLYSILOXANE - POLYETHER COPOLYMERS USED AS STARTING MATERIALS SILOXANE SYNTHESIS PRODUCT BACKBONE POLYETHER METHOD __________________________________________________________________________ A MD'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.7.5 OCH.sub.3 U.S. 3,299,112 B MD'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.5.5 (PO).sub.2.8 OH U.S. 5,191,103 C MD.sub.4 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3.23 OCH.sub.3 U.S. 4,847,398 D MD.sub.8 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3.23 OH U.S. 5,191,103 E MD.sub.8 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3 OCH.sub.3 U.S. 3,507,815 F MD.sub.8 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.12 (PO).sub.3 OH U.S. 5,191,103 G MD.sub.12 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3.23 OH U.S. 4,847,398 H MD.sub.12 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3 OCH.sub.3 U.S. 3,507,815 I MD.sub.12 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.12 (PO).sub.3 OH U.S. 5,191,103 J MD.sub.16 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3.23 OH U.S. 5,191,103 K MD.sub.16 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.3 OCH.sub.3 U.S. 3,507,815 L MD.sub.16 D'M H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.12 (PO).sub.3 OH U.S. 5,191,103 M D.sub.4 D' H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.7.5 OCH.sub.3 U.S. 3,507,815 N D.sub.4 D' H.sub.2 C.dbd.CHCH.sub.2 (EO).sub.5.5 (PO).sub.2.8 OH U.S. 5,191,103 __________________________________________________________________________
1,3-Divinyltetramethyldisiloxane (M*M*) was purchased from Gelest, Inc. A methylvinylcyclosiloxane mixture, [H.sub.2 C.dbd.CH(CH.sub.3)SiO].sub.p, p=3 (4.3 wt %), p=4 (76.54 wt %), p =5 (17.68 wt %), p=6 (1.4 wt %) was prepared by hydrolysis of H.sub.2 C.dbd.CH(CH.sub.3)SiCl.sub.2. Cyclo(dimethylsiloxane-co-methylhydrogenosiloxanes) of the type D.sub.n D'.sub.m (n=1-5, m=1-4, n+m<8) were prepared by the acid-catalyzed equilibration of polydimethylsiloxanes and polymethylhydrogensiloxanes as described by Chang and Buese in Polymer Preprints, 33 (1992) 160-161.
SILWET.RTM. L-77 is a siloxane-polyether copolymer with terminal trimethylsiloxy groups.
V-2K is an .alpha., .omega.-divinylpolydimethylsiloxane having 0.22 wt % vinyl and a viscosity of 2000 cSt at 25.degree. C.
V-200 is a .alpha., .omega.-divinylpolydimethylsiloxane with 0.7 wt % vinyl and a viscosity of 200 cSt at 25.degree. C.
V-XL is a crosslinker with SiH content 40 cc H.sub.2 /g
VCAT-RT is a platinum complex of 1,3-divinyltetramethyldisiloxane dissolved in 500 cSt silicone oil. Its Pt content is .about.2 wt %.
SILWET.RTM. L-77, V-2K, V-200, V-XL and VCAT-RT are products of Witco Corp.
BANICIDE.RTM., a glutaraldeyhde-based, sterilizing disinfectant manufactured by Pascal Co. Inc., was used as the disinfecting medium in accordance with the manufacturer's instructions. Disinfection time was overnight (.about.16 hr) in most cases and in others as long as 64 hr. Commercial dental impression formulations were mixed and cured as directed in the manufacturer's product literature.
(CH.sub.3).sub.4 N.sup.+- OSi(CH.sub.3).sub.2 [OSi(CH.sub.3).sub.2 ].sub.58 Si(CH.sub.3).sub.2 O.sup.-+ N(CH.sub.3).sub.4 (N-CAT) was prepared by charging 216 g [(CH.sub.3).sub.2 SiO].sub.4, 18.1 g (CH.sub.3).sub.4 NOH.5H.sub.2 O and 250 g toluene to three-neck 1 L round bottom flask fitted with a temperature-controlled heating mantle, mechanical stirrer, Claisen connection, water cooled Friedrich condenser, thermometer, and vacuum take-off line. The mixture was heated to 65-70.degree. C. at 100-200 torr to remove the water-toluene azeotrope. When no additional azeotrope distilled over the water and toluene were separated and the weight of water (.about.8 g) recorded. The vacuum was released, the temperature was lowered and another 100 g toluene added to the flask. Final stripping of residual water (.about.1 g) and all of the toluene was accomplished by heating to 90.degree. C. at 50 torr. The product is a viscous, hygroscopic liquid.
General Synthesis Procedure
Equilibration and ring opening reactions were performed in a three-necked 500 mL round bottom flask fitted with a temperature-controlled heating mantle, mechanical stirrer, Claisen connection, water cooled Friedrich condenser, thermometer, and nitrogen sparge line. Weighed quantities of polysiloxane-polyether copolymer, vinylsiloxane and N-CAT were charged to the flask and the stirring contents heated to 90.degree. C. for 4 hours. The temperature was then increased to 140.degree. C. for 1 hour to decompose N-CAT and the reaction mixture was later stripped in vacuo at 100.degree. C./4 torr for 4 hours. Condensate was collected, weighed and analyzed by gc and gc/ms. The stripped product was weighed and analyzed by .sup.13 C and .sup.29 Si nmr, gpc and ICP. It was used as a hydrophilic additive and as a silicone surfactant.
Evaluation of Hydrophilicity
Hydrophilicity was evaluated by measuring the water contact angle, as a function of time, on the surfaces of cured polysiloxane discs containing the unsaturated polysiloxane-polyether copolymers of this invention. Contact angles were also measured on control discs made without the inventive hydrophilic additives and on samples made from commercial compositions advertized as being hydrophilic. All measurements were made with a Rame-Hart goniometer (Model 100 00 115). Standard deviations of the measured angles were .+-.5.degree..
Dynamic contact angle measurements were made with a Cahn DCA-315 dynamic contact angle analyzer. The two part formulation was mixed and applied to the glass plate of the analyzer. Measurements were taken while the formulation was curing. Calculation of the advancing and receding contact angles were made automatically by the analyzer software.Examples 1-14
Examples 1-14 illustrate the synthesis of vinyl-containing polysiloxane-polyether copolymers by the general procedure described above. Reaction stoichiometry was varied as shown in Table 2 using the quantities of saturated polysiloxane-polyether copolymers of Table 1 and 1,3-divinyltetramethyldisiloxane (M*M*). All reactions were run at 85-90.degree. C./4 hr prior to catalyst decomposition and separation of volatiles.
TABLE 2 ______________________________________ SYNTHESIS OF VINYL-CONTAINING POLYSILOXANE - POLYETHER COPOLYMERS Copolymer, STRIPPED g MM, N-CAT, PRODUCT, EXAMPLE (see Table 1) g g g ______________________________________ 1 A, 120.9 36 0.5 112 2 B, 132.6 36 0.5 124 3 C, 67.7 17.5 0.1 64.2 4 D, 82 15 0.1 83.5 5 E, 85 15 0.1 83.2 6 F, 53 10 0.1 55.1 7 G, 53 12 0.1 55.4 8 H, 55 12 0.1 57.2 9 I, 63 10 0.1 68.4 10 J, 86.5 10 0.1 92.1 11 K, 51.2 6 0.1 52.2 12 L, 50 4.3 0.1 52.5 13 M, 98.4 24 0.4 96.5 14 N, 98.6 21 0.4 100.2 ______________________________________
The reaction products varied in color from colorless to yellow to dark brown.Example 15
This example illustrates the composition of the unsaturated polysiloxane-polyether copolymers of synthesized in Examples 1, 2, 13 and 14. The platinum content of the products was analyzed by ICP and found to be 10-40 ppm as shown below.
TABLE 3 ______________________________________ Pt, EXAMPLE ppm ______________________________________ 1 15 2 10 13 37 14 30 ______________________________________
.sup.29 Si and .sup.13 C nmr spectra of the reaction products of Examples 1 and 2 were recorded on a BRUCKER ACP-300 spectrometer. The molar ratio of vinyldimethylsilyl endgroups (M*) to trimethylsilyl endgroups (M) in the product of Example 1 was 0.32 and in Example 2 was 0.24. It is clear from these analytical data that not all of the (CH.sub.3).sub.3 Si endgroups of the starting copolymer were converted to H.sub.2 C.dbd.CHSi(CH.sub.3).sub.2 endgroups. For example in Copolymer M, the ratio of silicon bound methyls to SiCH.sub.3 groups was 11.24, as compared to a theoretical value of 9.0. However, it will be illustrated below that the level of conversion realized was sufficient to impart permanent hydrophilicity to addition cure polysiloxane compositions.Examples 16-24
This example illustrates the permanent hydrophilicity of selected unsaturated polysiloxane-polyether copolymers when they were incorporated into addition cure polysiloxane compositions. The unsaturated polysiloxane-polyether copolymers were tested in commercial two part dental formulations and in an unfilled formulation suitable for encapsulating electronic components or coating textiles and medical devices. Descriptions of the formulations and the quantities of hydrophilic additives used are given in Tables 4-6.
TABLE 4 ______________________________________ LIST OF COMMERCIAL DENTAL IMPRESSION MATERIALS TESTED DENTAL FORMULATION MANUFACTURER DESCRIPTION ______________________________________ 3M EXPRESS .TM. 3M Dental Products Type I impression putty material. Very high viscosity Bisico S1a/S1b Bisico 72 Shore A impression putty material Blu-Mousse Parkell Biomaterials Thixotropic impression material J/P Q.sup.3 .TM. Universal Jeneric .RTM./Pentron .RTM., Type I high viscosity Inc impression material J/P CORRECT .TM. VPS Jeneric .RTM./Pentron .RTM., Type III Light Extra, Inc. Light Viscosity COMPARATIVE Bisico S4i hydrophil Bisico Type I low viscosity, light body IMPREGUM .RTM. F Espe Type I polyether impression material ______________________________________
TABLE 5 ______________________________________ COMPOSITION OF UNFILLED FORMULATION PART A, PART B, INGREDIENT wt % wt % ______________________________________ V-2K 86.8 91.53 V-200 -- 8.18 V-XL 13.2 VCAT-RT -- 0.12 MVC -- 0.17 ______________________________________
The unfilled formulation of Table 5 was cured by mixing either equal weights of the two parts, or by mixing in the weight ratio 1.5 PART A to 1.0 PART B, pouring the mixture in a cylindrical mold and heating in an oven at 120.degree. C. for 15-30 min. Water contact angles of the cured formulations with and without the hydrophilic, unsaturated polysiloxane-polyether copolymers were measured before and after disinfection of the cured discs. Comparisons were made with commercial hydrophilic dental formulations (Bisico S4i hydrophil and IMPREGUM.RTM. F).
TABLE 6 __________________________________________________________________________ CONTACT ANGLE DATA FOR POLYSILOXANE COMPOSITIONS PREPARED WITH UNSATURATED POLYSILOXANE - POLYETHER COPOLYMERS AND FOR COMPARATIVE CONTROLS Formulation Contact Angle Contact Angle (wt %) Additive Additive Before Disinfection After Disinfection Example A Part B Part (Table 2) (wt %) 3 min 10 min 3 min 10 min __________________________________________________________________________ Ex. 16 3M Express .TM. 49.4 49.4 Ex. 2 1.2 15 12 25 15 3M CONTROL 50 50 none -- 81 78 80 79 Ex. 17 J/P Q.sup.3 .TM. 49.125 49.125 Ex. 1 1.75 29 15 48 35 Ex. 18 J/P Q.sup.3 .TM. 49.3 49.3 Ex. 2 1.4 18 14 48 33 J/P CONTROL 50 50 none -- 86 85 86 86 Ex. 19 Blu-Mousse 49.75 49.75 Ex. 1 0.5 24 17 32 18 Blu-Mousse 50 50 none -- 84 83 85 84 CONTROL Ex. 20 Bisico S1a/S1b 49.25 49.25 Ex. 2 1.5 26 15 34 16 Bisico CONTROL 50 50 none -- 76 76 77 76 Ex. 21 Unfilled 59.55 39.7 Ex. 2 0.75 13 10 16 12 Ex. 22 Unfilled 59.16 39.44 Ex. 1 1.4 16 10 24 20 Ex. 23 Unfilled 55.7 37.12 Ex. 8 7.2 38 25 50 28 Unfilled CONTROL 60 40 none -- 88 87 88 88 Ex. 24 J/P 49 49 Ex. 1 2.0 23 11 27 15 CORRECT .TM. J/P CORRECT .TM. 50 50 none -- 78 63 88 82 CONTROL Impregum .RTM. F 88.89 11.11 -- -- 48 42 52 45 Bisico S4i, hydrophilic 50 50 -- -- 64 58 75 68 wash __________________________________________________________________________
Table 6 shows that IMPREGUM.RTM. F is permanently hydrophilic in that its 3 minute water contact angles are 48-52.degree. before and after disinfection. However, the Bisico S4i hydrophilic wash and J/P CORRECT.TM. Type III Light Extra samples all showed post-infection increases in contact angles indicating loss of hydrophilicity. Contact angles increased to >60.degree.. All of the control polysiloxane compositions were hydrophobic; they yielded 3 or 10 minute water contact angles that were greater than 75.degree.. There was little change in the values following disinfection.
Addition of 1.2 wt % of the unsaturated copolymer of Example 2 to the 3M dental putty in Example 16 effected a lowering of contact angles to <20.degree. before disinfection and to .ltoreq.25.degree. afterwards. This dramatic and durable contact angle lowering compared to the control (.about.80.degree.) was effected by unsaturated copolymer product containing 10 ppm Pt and the functional groups idenified by nmr spectroscopy in Table 3. The data confirm that the unsaturated polysiloxane-polyether copolymers in the product of Example 2 were permanently bonded to the cured matrix. Similar evidence for permanent hydrophilic modification with this product is seen in the data for J/P Q.sup.3 Universal (Ex. 18), for Bisico S1a/S1b (Ex. 20) and for the unfilled formulation (Ex. 21). The effective quantity of unsaturated polysiloxane-polyether copolymer employed in these Examples was 0.1-0.3 wt %.
0.5-2.0 wt % of the unsaturated polysiloxane-polyether copolymer product of Example 1 also imparted durable hydrophilicity to the commercial dental formulations in Examples 17, 19 and 24 and the unfilled formulation of Example 22. The effective quantity of unsaturated copolymer in these experiments was only 0.05-0.35 wt %. Thus, both the high efficacy and effectiveness of the inventive compositions in affording permanent hydrophilicity to polysiloxane compositions are established.Examples 25-32
This example illustrates the durable hydrophilicity imparted to cured polysiloxane compositions by the unsaturated copolymers prepared in Examples 13 and 14.
The unfilled formulation of Table 5 was used in the weight ratio 1.5 PART A to 1.0 PART B. Use levels of the hydrophilic, unsaturated copolymers of Examples 13 and 14 were varied as shown in Table 7. Weight percent values shown are based on the total weight of PART A, PART B and hydrophilic additive in the experiment. Control samples without the hydrophilic additive were prepared and measured as a comparison.
Table 7 shows the 3 minute water contact angles on the cured elastomer before and after disinfection. Above 1.5 wt % use level of the hydrophilic additive of Example 13, there was no change in the contact angles after disinfection. For 0.6 wt % use level, the cured polysiloxane was still hydrophilic after disinfection, but the contact angle had increased from 13.degree. to 49.degree.. The hydrophilic additive of Example 14 gave similar results, except that no changes in contact angle were now observed above .about.2 wt % use level.
TABLE 7 ______________________________________ PERMANENT HYDROPHILICITY OF CURED POLYSILOXANES CONTAINING HYDROPHILIC ADDITIVES OF EXAMPLES 13 AND 14 USE .theta., .theta., LEVEL, BEFORE DIS- AFTER DIS- EXAMPLE ADDITIVE wt % INFECTION INFECTION ______________________________________ 25 Example 13 0.6 13.degree. 49.degree. 26 1.5 12.degree. 13.degree. 27 2.0 12.degree. 12.degree. 28 3.0 11.degree. 12.degree. CONTROL NONE -- 84.degree. 85.degree. 29 Example 14 0.5 32.degree. 63.degree. 30 1.1 15.degree. 48.degree. 31 2.2 14.degree. 15.degree. 32 2.8 12.degree. 14.degree. CONTROL NONE -- 84.degree. 85.degree. ______________________________________
1. A process for making a copolymer comprising
- (a) adding to a polysiloxane-polyether copolymer an alkenyl or alkynyl silane or siloxane capable of undergoing an addition or redistribution reaction with the polysiloxane-polyether
- (b) adding to the mixture formed in step (a) a catalytically effective amount of a basic catalyst; and
- (c) heating the mixture formed in step (b) to a temperature up to about 200.degree. C., to effect reaction to form unsaturated polysiloxane-polyether copolymer product.
2. A process in accordance with claim 1 wherein said basic catalyst is selected from the group consisting of KOH, CsOH, Ca(OH).sub.2, (CH.sub.3).sub.4 N.sup.+- OSi(CH.sub.3).sub.3, (CH.sub.3).sub.4 N.sup.+- [OSi(CH.sub.3).sub.2 ].sub.s.sup.-+ N(CH.sub.3).sub.4 (wherein s=4-100) and K.sup.+- OSi(CH.sub.3).sub.3.
3. A process according to claim 1 wherein the polysiloxane-polyether copolymer of step (a) is a cyclic structure which is ring opened with a disiloxane of the structure R.sup.1 R.sub.2 SiOSiR.sub.2 R.sup.1 or R.sub.3 SiOSiR.sub.2 R.sup.1 with R.sup.1 is a C.sub.1 -C.sub.20, unsaturated monovalent organic group that can be hydrosilylated to yield silicon-carbon bonds and R is a C.sub.1 -C.sub.20 saturated, monovalent organic group.
4. A process according to claim 3 wherein R.sup.1 is a vinyl group.
5. A process according to claim 1 wherein the polysiloxane-polyether copolymer of step (a) is of the formula[R.sub.3 SiO.sub.1/2 ].sub.m [ZR.sub.2 SiO.sub.1/2 ].sub.n [O.sub.1/2 Si(R.sub.2)O.sub.1/2 ].sub.o [O.sub.1/2 SiRZO.sub.1/2 ].sub.p [SiO.sub.3/2 R].sub.q [SiO.sub.4/2 ].sub.r wherein R is a C.sub.1 -C.sub.20, preferably C.sub.1 -C.sub.12, saturated, monovalent organic group, Z is a polyether-containing group that is linked to the polysiloxane block by a silicon-carbon bond, m=0 to 5, n=0 to 3; o=0 to 100, p=0 to 30; q=0 to 4; r=0 to 2 and if p=0, then n>0 and if n=0, then p=0 and m+n+o+p+q+r=3 to 100.
6. A siloxane of the structure: R.sup.2 R.sub.2 SiO(SiR.sub.2 O).sub.n (SiR.sup.1 ZO).sub.m (SiR.sup.1 RO).sub.p SiR.sub.2 R.sup.2 wherein n+m+p=0 to 3, each n. m, and p are 0 to 3, with the proviso that there is at least one Z and at least one R.sup.1 per molecule and wherein R.sup.1 is a C.sub.1 -C.sub.20, unsaturated monovalent organic group that can be hydrosilylated to yield silicon-carbon bonds, R is a C.sub.1 -C.sub.20 saturated, monovalent organic group; Z is a polyether-containing group that is linked to the polysiloxane block by a silicon-carbon bond and R.sup.2 is selected from the group consisting of R, R.sup.1 and Z.
7. A siloxane according to claim 6 wherein Z is C.sub.x H.sub.2x O(C.sub.a H.sub.2a O).sub.b R" or --C.sub.x H.sub.2x OG[(C.sub.a H.sub.2a O).sub.b R"].sub.r wherein x is an integer in the range 1-20, G is a polyhydroxy group capable of being alkoxylated, a is 2 to 4, b=3 to 12, R" is hydrogen or a polyether capping group, and r, represents the number of alkoxylated hydroxyl groups on the G group.
8. A siloxane according to claim 7 wherein R.sup.2 is vinyl and p=0.
9. A siloxane according to claim 8 wherein each R is methyl.
|4259467||March 31, 1981||Keogh et al.|
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|4752633||June 21, 1988||Aasen et al.|
|4847398||July 11, 1989||Mehta et al.|
|4857583||August 15, 1989||Austin et al.|
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- Noll, Chemistry and Technology of Silicones, Silicones, 446-453, Ch. 9, Chemistry and Technology of Silicones (1968). Chang, P. et al., Synthesis of Cyclo(dimethylSiloxane Co-methylhydrogensiloxane), Polymer Preprints, vol. 33, No. 2 (Aug., 1992). Aoki et al., Poly(divinylsiloxyethylene glycol)--synthesis and photoresist characteristics, J. Macromol. Rapid Commun. 18, 31-36 (1997).
Filed: May 21, 1998
Date of Patent: Aug 15, 2000
Assignee: Witco Corporation (Greenwich, CT)
Inventors: Kenrick M. Lewis (New York, NY), Hua Yu (White Plains, NY)
Primary Examiner: Melvyn I. Marquis
Attorneys: Edward K. Welch, II, Andrew S. Reiskind, Timothy X. Witkowski
Application Number: 9/82,563
International Classification: C08G 7706;

domain: chemistry


My 1968 Romy underfolder kit had a trunnion with a visible slant to the bottom surface. It was bad enough that I had to hammer the rear trunnion into the receiver, and had to hammer the receiver some to fit. Part of the trunnion was also chipped off at the time I had received it (looked to have occurred during the demilling process). It remains crooked and has a minor gap.
I did what any diligent builder would and totally ignored the problem. Now it looks great and has handled about 1000 rounds with no issues.


text:
Holiday Stuffed Squash Recipe
Slow roasted butternut squash rounds filled with a lightly spiced chestnut, quinoa and lentil stuffing scattered with dried cherries, this Christmas main is vegan, gluten-free and so wonderful.
My mouth is watering as I write this. I haven’t made this recipe but I am sharing it because I plan to make this with our thanksgiving dinner. Then probably again at Christmas. I love squash and if you are anything like me, I have so many stored I need new recipes to try with them all.
Let me know if you make these too. I always like to see my readers food!

domain: food


text:
News published August 2017
Statement on reports of Libya trial
31 August 2017
Greater Manchester Mayor Andy Burnham responds to reports of Libya trial:
Proudly celebrating Pride this weekend
25 August 2017
CELEBRATIONS of diversity and equality will be taking place throughout this weekend as part of Manchester Pride.
Mayor backs new body to speak for the North
23 August 2017
Today's transport summit in Leeds has agreed that a representative body of political, business and other leaders should be set up to speak with one voice for the North.
Unprecedented gathering of Northern leaders demand a fair deal from Government
23 August 2017
Political and business Leaders from across major Northern cities are to meet for the first time in Leeds on Wednesday to demand a fair deal on transport from the Government.
'Take a seat' in age-friendly Greater Manchester
22 August 2017
Improving the lives of older people in Greater Manchester.
Next steps in Greater Manchester Spatial Framework announced
16 August 2017
A timeframe for the development and publication of the second draft of the Greater Manchester Spatial framework has been discussed.
Millions invested to help create jobs in Greater Manchester
15 August 2017
MORE than three million pounds has been invested in Greater Manchester businesses thanks to funding from the Greater Manchester Combined Authority (GMCA).
Flawed report ignores creative, digital revolution sparked by BBC relocation
10 August 2017
Greater Manchester has rejected a flawed report from the London-based Centre for Cities which claims the BBC’s move to Salford has had a “negligible” impact on the city region’s economy.

domain: news


text:
Timeline of 2G spectrum case
With the bail plea of former Tamil Nadu chief minister M Karunanidhi's daughter Kanimozhi being rejected, the second generation 2G spectrum case has taken another turn. A timeline of the case:delhi Updated: May 20, 2011 20:30 IST
With the bail plea of former Tamil Nadu chief minister M. Karunanidhi's daughter Kanimozhi being rejected, the second generation 2G spectrum case has taken another turn. A timeline of the case:
- Oct 22, 2009: The CBI files a first information report (FIR) against unidentified officials of the department of telecommunications on the 2G spectrum (airwaves) auction, based on a reference from the Central Vigilance Commission.
- November first week, 2010: Media publishes contents of the Comptroller and Auditor General (CAG) report on the 2G spectrum auction. The CAG said that the public exchequer suffered a notional loss of Rs.1.76 lakh crore ($40 billion) due to faulty auction procedure under Raja in 2008.
- Nov 9, 2010: Parliament's winter session begins. Protests by the National Democratic Alliance (NDA), the Left parties and other parties - demanding a joint parliamentary committee (JPC) probe into the spectrum scandal - wash away the five-week session.
- Nov 14: Raja submits his resignation to Prime Minister Manmohan Singh in New Delhi. Claims he did no wrong.
- Nov 16: CAG report on 2G spectrum allocation tabled in both houses of parliament amidst uproarious scenes.
- Dec 8: The CBI raids the house of Raja and premises of former aides Siddharth Behura and R.K. Chandolia in New Delhi. It also raids houses and offices of Raja's relatives, associates and some journalists and social workers in Tamil Nadu linked to the DMK and Raja. The CBI claims recovering incriminating documents.
- Dec 15: The CBI raids the houses and offices of Niira Radia, a corporate lobbyist linked with Raja. She is subsequently questioned by the CBI several times.
- Dec 24: The CBI questions Raja in New Delhi.
- Dec 25: Raja's questioning continues for the second day.
- Jan 31, 2011: The CBI questions Raja again.
- Feb 2: The CBI arrests Raja, Chandolia and Behura.
- April 2: CBI filed charges against nine people and three firms -- Raja, Chandolia, Behura, Swan Telecom promoter Shahid Balwa, director Vinod Goenka, Unitech director Sanjay Chandra and three officials from the Reliance Anil Dhirubhai Ambani Group -- Gautam Doshi, Hari Nair and Surendra Pipara.
April 20: Special city court denies bail to Goenka, Chandra, Doshi, Nair and Pipara.
April 25: In a major embarrassment for Karunanidhi, daughter Kanimozhi named co-conspirator, along with Sharad Kumar of Kalaignar TV, Karim Morani of Cineyug Films, and Asif Balwa and Rajiv B. Agarwal of Kusegaon Realty.
May 6: Morani had got exemption for appearance as he was admitted to Mumbai's Lilavati Hospital. He again got exemption May 10 on the same grounds. Pipara is in All India Institute of Medical Sciences for treatment, but continues to be in judicial custody.
May 20: Kanimozhi's bail plea rejected. Sent to judicial custody in Tihar Jail. Sharad Kumar also to go to jail.
First Published: May 20, 2011 20:26 IST

domain: politics


text:
You would think it might rain from the gray morning skies in northern Peru but in all likelihood it won’t. The clouds will give way to a scorching sun that glares down on threadbare pebbly plains of shrubs, the dirt that wafts in the air, the hoods of motorbike-taxis and a scattering of houses in construction. Locals are not used to having much water in Olmos, but their region now has a complex system of dams, canals and pipes channeling Amazonian water to smallholder farms and swathes of unused land. If successful, this network could expand and pave the way for similar developments across the country.
“I think it’s very necessary,” says Maria, an elderly woman on the plane, when asked about the changes Brazilian company Odebrecht has brought through the Olmos Irrigation Project.
Her children had left the rural area to find better opportunities in Lima and Buenos Aires, but she believes the project will now breathe new life into the regional economy and its young population.
“The amount of water had been in decline for a long time.”
With US$350 million spent on the project works with a tunnel through the Andes and a further US$280 million invested in the agricultural element, the name Odebrecht resonates with most people in the nearby city of Chiclayo, where airport officials are on a first-name basis with company representatives.
This comes as no surprise considering the initiative’s implications, activating 38,500 hectares of new agricultural land that is expected to trigger 40,000 direct jobs, complemented by 5,500 hectares for local Olmos smallholder growers.
“The Olmos riverbed was dry and the population had not been accustomed to having water there, but today thanks to this project that transfers water from the Huancabamba River by crossing the mountains through the Transandino tunnel, this natural riverbed is flowing,” says Odebrecht Infrastructure commercial sales manager Juan Carlos Urteaga, adding the project draws on around 45% of the Huancamba’s water resource.
“We are in charge of the irrigation system but for those smallholder growers the regional government is seeing how to make the minor investments to provide water to each grower.”
The diverted water is first stored in the 44-cubic hectometer Limon Dam before passing through the 20km tunnel, where it then flows through a ravine to reach the Olmos River. From there it passes through a series of reservoirs and catchments with filtration systems to ensure the water is of high quality for farming.
“The Palo Verde reservoir has a capacity of one million cubic meters as a regulating storage area, and this is where the two pipelines start to deliver water to each of the 51 lots of new land,” says commercial services representative Jose Manuel Lecaros.
“In the glass-reinforced pipes (GRP) the diameter reduces as you go down the line delivering water, so as to not lose pressure. It starts with a diameter of 2.3 meters and finishes with 60cm – we are talking about close to 45km of pipes installed.”
Of the total amount initially offered only 5,250 hectares remain on sale, across six individual lots of which one covers 250 hectares at a price of US$8,500 per hectare, and five 1,000-hectare lots selling for US$7,500 per hectare.
In addition to a wide range of local fruit and vegetable producers including Complejo Agroindustrial Beta, Danper and AQP, international investors have also come on board such as Denmark’s Ingleby Farms, while Grupo Arato has planted avocados that will be ready for harvest by 2016 to supply U.S. multinational Mission Produce.
Urteaga added that Grupo Gloria had the largest amount of land on the project, growing sugarcane for processing in a plantation that would help reduce Peru’s reliance on sugar imports.
Another company that has come on board is U.S. entity AgroVision, through its Peruvian subsidiary.
“As a group the company already has production in the area outside of the project, and we saw it as a good opportunity to get involved in the Olmos project,” says farm manager Renato Nagaro.
“We have the issue of delivering water which is essential, and adding to the infrastructure that comes with this like roads and energy, this complements an ideal situation for developing an agricultural business with good climate and favorable soils.
“In other words we could say this is an ‘agricultural condominium’ – all the services are at hand and guaranteed, which doesn’t happen in other areas where you have to build wells or the water available is limited and access to energy is sometimes complicated when you consider the investment of bringing it to the fields.”
The company just recently started planting grapes, and has licensed a few patented U.S. blueberry varieties for a trial on 30 hectares of land.
“What is certain is that the grapes are already planted and there is not much more analysis needed; it’s simply about adjusting the final area and choosing the varieties,” he says, adding the first crop will be ready for harvest in 13 months.
“We also have a small lot for blueberries to see how the crop goes in the zone, and if it’s positive we’ll develop more in that area; Other trials in the area are on two or three hectares each, but we have 30.
“The crops to develop here for the medium to long-term are permanent crops, and in the interim we’ll do rotation crops like quinoa, cotton and peppers.”
He says target markets include the U.S., Europe, Asia and Russia.
Like most companies involved in the project, Nagaro’s crop will be exported from the port of Paita 200km away, while Lecaros adds northwestern Brazil may be an option for market development once the Yurimaguas port is developed in the Amazon.
The big challenge now will be access to labor, but as part of the initiative the government has been tasked with developing an adjacent town to house workers.
“I think it will be interesting with some complicated moments. We have formed an association of property holders so that in a way we can coordinate and establish certain meetings, but the competition for labor will be significant,” says Nagaro.
“At the level of the association, we have had meetings with the Ministry of Agriculture and the Ministry of Work. There has been a lot of conversation and relations with the government.
“They have to support the issue as private companies can’t do it alone. It’s also planned that there’ll be the creation of a new city that should alleviate the labor force demand in the area.”
Can Olmos set a standard for the rest of Peru?
While Urteaga and Lecaros are focused on selling the remaining land to agricultural users, the long-term vision is much grander.
“It is planned to expand this project to 110,000 hectares which is part of the concession. For that we’d have to build new irrigation channels for the following lands, in the next stage of Olmos,” says Urteaga.
“It would use the same Limon Dam, but what has to be built is a new irrigation system with more independent channels and for that you have to transfer from other rivers using the Limon Dam.
“This will depend on time and the success of this project. Our interest is not just on selling land but we’ll stay as concessionary for 23 years, accompanying our users and being in charge of the infrastructure for maintenance and operation.”
If Olmos proves successful, he says Odebrecht hopes to replicate the project in other parts of Peru, whether it be in Ica, Areqipa or elsewhere.
Stay tuned for an update with the views of a Chilean farmer who started growing grapes and established a packhouse in Olmos prior to the project’s completion.

domain: agronomy


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Confident young sports leaders in Mbekweni, in the Western Cape, put their communication skills into practice by embarking on a four-day door-to-door campaign to increase community involvement at the Mbekweni Community Sport Centre, as part of an outreach campaign by sport and development organisation, SCORE.
Seventeen year old Sisanda Masila from Ihlumelo High School was joined by other sports leaders in Mbekweni, near Paarl, to talk to residents about the benefits of using the facility.
The state of the art indoor sports facility has an artificial pitch, seating capacity for over 300 spectators, changing rooms and conference facilities. It opened just over a year ago, during the 2010 FIFA World Cup and was funded by United Kingdom charity, Hope Through Action. The centre continues the legacy of the event by engaging more community members to get active in sport and develop skills they can use away from the pitch. One of the centre’s most successful programmes is the Mbekweni Community futsal league. The 5-a-side indoor variation of football gives teams the opportunity to practice ball control in a smaller area and learn new rules to the popular sport which hails from Brazil. The league currently has twenty teams and is an opportunity for different community teams to meet and compete against other keen players. The centre also hosts community celebrations and sports festivals which encourage older members of the community to visit the centre and take part in the activities.
Sisanda believes that engaging residents at the Mbekweni Community Sports Centre is a crucial step towards lowering crime rates, “thanks to the sports centre, we have seen more people getting involved in sport and now there is no time to do nothing. Crime rates are lower, and people take pride in the community.”
Offering coaching clinics and life skills development workshops for all groups in the community, SCORE hopes this campaign will increase participation and help develop more young leaders like Sisanda. “As young leaders we are recognised for doing the right things. We want to see more young leaders in our community helping youth make the right decisions.”
To help SCORE continue to build young leaders of the future, donate to the SANGONeT “No Pain No Gain” campaign today, by making a donation at www.givengain.com/activist/55367/projects/1333.

domain: sociology


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The national activist group RootsAction.org announced today that it is launching a grassroots campaign aimed at “swing voters on the left” to persuade supporters of Bernie Sanders and other progressives in swing states to “Vote Trump Out – and Then Challenge Biden.”
The Vote Trump Out swing-states initiative will include a highly-targeted social-media program and other digital outreach, utilizing messages from national and state progressive luminaries – people who are widely respected on the left in ways that establishment Democrats are not. The campaign will urge progressives in the dozen battleground states to vote for Joe Biden rather than sit out the election or cast a third-party protest vote. Directed heavily toward young people, the effort will be entirely independent of – and often in opposition to – corporate Democratic leaders.
The RootsAction campaign has assembled a group of national endorsers who are likely to be persuasive to progressives on the fence about voting for Biden. They include: Ady Barkan, Medea Benjamin, Leslie Cagan, Noam Chomsky, Marjorie Cohn, RoseAnn DeMoro, Barbara Ehrenreich, Daniel Ellsberg, Bill Fletcher Jr., Jim Hightower, Rep. Ro Khanna, Jamie Margolin, Bill McKibben, Annabel Park, Linda Sarsour, Winnie Wong and James Zogby.
The #VoteTrumpOut campaign will assert that – while President Trump is unfailingly immune to progressive persuasion or protest – the fight for a full progressive agenda (ranging from major climate initiatives and anti-racism to universal healthcare, free public college and taxing the wealthy) would have the potential to win some victories with Biden in the White House.
The campaign’s mission statement declares: “We are not going to minimize our disagreements with Joe Biden. But we’re also clear-eyed about where things stand: supporting the Democratic nominee in swing states is the only way to defeat Trump…. If Biden wins, we’ll be at his door on day one, demanding the kinds of structural reforms that advance racial, economic and environmental justice.”
Renowned linguist, author and political activist Noam Chomsky contributed this comment to the initiative: “I live in the swing state of Arizona, and I’d vote for a lamp post to get Trump out.” Chomsky is featured in a campaign-launch video on the Vote Trump Out website.
“Our organization fought fiercely in the primaries for Bernie and against Biden,” said RootsAction.org cofounders Jeff Cohen and Norman Solomon. “But the general election is far less about Biden than it is about Trump – the most dangerous president in modern U.S. history, who opposes virtually every policy and principle that progressives are fighting for.”
Founded in 2011 as an independent progressive force, RootsAction.org now has 1.2 million active supporters online in the United States.
Reader Supported News is the Publication of Origin for this work. Permission to republish is freely granted with credit and a link back to Reader Supported News.


Green Light Given To Lake Wyangan Flood Pump And Pipeline Project
Thursday, 12 Jan 2023Griffith City Council will reallocate funds in the 2022/23 budget to address unprecedented water levels at Lake Wyangan following last year’s floods.
The water level in Lake Wyangan has reached a record height due to continual rainfall events in 2022 and additional runoff from the catchment to the north. This has resulted in flooding of two residential houses, Jones Road causeway and associated buildings and infrastructure around the foreshore of the North Lake.
At the Extraordinary Council Meeting held on Tuesday 10 January 2023, Council resolved to divert funds from the Lake Wyangan foreshore improvements fund into a new Lake Wyangan Flood Pump and Pipeline Project. This will enable water to be pumped out of Lake Wyangan into the drainage channel along Slopes Road that eventually drains into Barren Box Storage and Wetlands system.
Griffith Deputy Mayor, Councillor Glen Andreazza said this action would allow Council to reduce the water level from around the inundated homes, the Jones Road Causeway and infrastructure on the foreshore of the North Lake.
“Given that Lake Wyangan, both North and South Lakes, are closed catchments there is no natural drainage outlet to allow any water out of the Lakes,” he said.
“After investigating suitable options, we’ve determined that the only way of extracting water is by mechanically pumping the water to another location using a new pipeline.”
On 4 August 2022 and 14 September 2022 the Griffith Local Government Area, along with numerous other Local Government Areas, was declared a disaster on the basis of severe weather and flooding. Given the emergency nature of the flooding situation and the urgent need to take action to address several issues at Lake Wyangan, the Extraordinary Council Meeting was called in order to deal with the matter.
“In late 2022 we already took steps to pump approximately 1,000 ML water into Tharbogang Wetland and water is also currently being pumped into Campbell Wetland,” Councillor Andreazza said.
“Murrumbidgee Irrigation have given permission for Council to pump water for a limited period out of Lake Wyangan up to the drain which discharges into Barren Box Swamp.
“Once water has been pumped out, Jones Road will then be assessed to determine the scope and cost of repairs with a view to resuming access to the Lake via Jones Road.
“We anticipate there will be long term benefits from installing this new infrastructure. It will enable future discharge of water from the Lake when opportunities present.”
The proposed pump will provide an output of approximately 20 ML per day when operated for 24 hours per day. Around 4,000 ML is needed to be extracted out of Lake Wyangan so it is anticipated it will take approximately six and half months of continual pumping to reduce the water level to enable Jones Road causeway to be exposed.
The total estimated cost of the pipeline project is $1.4M, which will include a new flood pump, 1.5km of high density pipe, assembly and installation, excavation and removal of the old outdated pipe and running costs.
Dump For Free Event A SuccessFriday, 31 Mar 2023
Local residents flocked to Griffith City Council landfill sites recently, dumping more than 1,400 loads of rubbish.Read more
Spend Good Friday At Pioneer Park Museum’s Action DayFriday, 31 Mar 2023
Looking for something to do on Good Friday? Action Day at Griffith Pioneer Park Museum is a popular event attracting thousands of visitors and is a great family day out!Read more
New Destination Website For Griffith TourismThursday, 30 Mar 2023
The new Visit Griffith website has been unveiled inspiring potential visitors to pack their bags and head to Griffith immediately!Read more
Huge April School Holidays In GriffithThursday, 30 Mar 2023
Local kids and visitors alike are in for a jam-packed few weeks these April school holidays. From April 7 - 24, with so much on offer from art workshops, roller skating, animals, and music, there is something for all ages to enjoy.Read more
Griffith Groove And Graze A Huge SuccessFriday, 24 Mar 2023
Griffith got its ‘groove’ on at Griffith’s first Groove & Graze Music Festival held on Saturday 18 March! National and local bands took to the stage in front of more than 900 attendees at the Burley Griffin Community Gardens to celebrate Griffith’s newest one-day music & food festival.Read more
Council Receives Two Accolades At The Ipwea Nsw & Act State ConferenceThursday, 23 Mar 2023
Griffith City Council was recognised at the 2023 IPWEA NSW & ACT State Conference Engineering Excellence Awards held in Sydney last week, for two Council projects.Read more
Griffith City Council Launches Exciting New Youth ProjectWednesday, 22 Mar 2023
Do you want to have a greater say in the events and programs being delivered for young people in Griffith? Griffith City Council is launching the exciting new ConnectYOUth2680 project to give local youth a stronger voice.Read more
The Wedding Singer Is On The Way!Friday, 17 Mar 2023
Rehearsals for Griffith Regional Theatre’s upcoming production of the musical The Wedding Singer have kicked off with the local cast having a wonderful time learning the songs and dances that will entertain audiences in September.Read more
Over $90m Worth Of Council Projects Across Griffith LgaThursday, 09 Mar 2023
More than $90M worth of major projects are underway, recently finalised or in the planning stages across the Griffith LGA.Read more
Brisbane’s Globally Renowned Circa Returns To GriffithTuesday, 07 Mar 2023
Patrons will experience an exhilarating night at the Griffith Regional Theatre on Thursday 23 March with On by Circa.Read more
Drop Off Pens No Longer In Use At Griffith Pound And Rehoming CentreFriday, 03 Mar 2023 Read more


LOS ANGELES – Most major-league pitchers will never throw harder than they do their rookie year. It’s an established fact. They learn to live with less and less velocity – learn to “pitch, not throw” – as they age.
Thousands of men have experienced that trajectory over the past century, with a select few exceptions.
Brandon McCarthy is one of them. The Dodgers right-hander, 32 in July, is throwing harder than he ever has in 2015. It’s a velocity gain that began a year ago and played a significant role in the Dodgers’ decision to sign him to a four-year, $48 million deal in the offseason.
“It’s kind of like he learned how to pitch backwards, almost,” said Dodgers catcher Yasmani Grandal. “When guys have velocity, they rely on the velocity early in their career. And then, once they lose it, they go back and start working on movement. It’s actually really good for a guy to not throw that hard when he comes up and then all of the sudden start pumping 95 and 96.
“Whenever he needs movement, he can throw for movement, and whenever he needs velocity, he can reach back and throw hard.”
At a point where most pitchers are learning how to accommodate less oomph, McCarthy is learning the benefits of more.
In 2007, the first year PITCHf/x data was kept, Angels right-hander Jered Weaver averaged 90 mph with his fastball, and McCarthy averaged 89.4 mph, according to Fangraphs.com.
Now, there’s a massive gap between the two. McCarthy, nine months the younger, averages 93.6 with his four-seam fastball, while Weaver averages 84.3.
For McCarthy, the added velocity emerged during spring training before the 2014 season, strictly as a byproduct, he says, of a workout regimen that increased in intensity.
Two MLB scouts, employed by teams in either league, said they could not recall recent parallels to McCarthy’s uptick at his age. It was more common during the PED-fueled era of the early aughts. Grandal couldn’t recall catching or facing anyone who exhibited such a significant increase.
“Usually it’s the other way around,” Grandal said. “They come up because they have velocity and not movement. It’s kinda weird that he picked up that many miles throughout the course of his career. At the same time, that could mean a lot of things. That could mean he changed his workout routine. That could mean a lot of things. I guess it works out in his favor.”
It’s not as if the only reason McCarthy is second in the major leagues in strikeouts this season is that he’s throwing significantly harder than he was when he first reached the major leagues. He has long had above-average, sometimes superb, control. When he’s hitting the desired location with his sinker, it’s a ground-ball-getting machine.
But the velocity is hard to ignore.
“I thought he was more of a slower-pitching guy before,” Dodgers left-hander J.P. Howell said. “When you add velocity, that makes the job a lot easier. He must’ve been doing it wrong earlier.”
Howell himself hasn’t thrown a pitch clocked at 90 mph or above since 2008. Asked what it’d be like to pitch with four more miles per hour than the 88 he came up averaging, he opened his mouth and left it open for a few seconds to simulate an effect.
“Oh my God,” Howell eventually said. “That would be heaven. That would be amazing. I threw hard like that a couple times in high school, and I still remember those moments.”
In 18 innings, McCarthy’s tied for third in the majors with 25 strikeouts, trailing only teammate Clayton Kershaw and Cleveland’s Trevor Bauer. After allowing six home runs in his first two starts this season, McCarthy permitted three singles and no runs to the Rockies on Sunday, striking out six in six innings.
“He was a lot better,” Colorado shortstop Troy Tulowitzki told reporters afterward. “Take a look at his velocity when we faced him last year in Arizona. He was 90, 91. Today he was 95.
“He’s a completely different pitcher.”
Tulowitzki and the Rockies didn’t actually face McCarthy at Chase Field last year. But the previous September, they did, and Tulowitzki is right. The sinkers McCarthy threw that day averaged 91.51 mph, according to BrooksBaseball.net, which differs somewhat from Fangraphs’ data. Per Brooks, his sinker was more than 2 miles per hour faster on Sunday. His four-seam fastball averaged nearly 95 mph.
Fangraphs.com calculates velocity a bit differently. Still, by their calculations, McCarthy’s fastball is the seventh-fastest among National League starters. Only the likes of Stephen Strasburg and Matt Harvey live above him in the rankings.
He is a completely different pitcher, and a pretty good one, it seems.
Three Dodgers minor-leaguers were honored Monday. Triple-A right-hander Mike Bolsinger, who could make his next start for the major-league club Thursday in San Francisco, was named Pacific Coast League Pitcher of the Week. And top Double-A prospects Julio Urias and Corey Seager were named the pitcher and player of the week in the Texas League. The 18-year-old Urias struck out 14 hitters in two starts spanning 102/3 innings, striking out 14, walking none and allowing no runs on six hits. Seager entered Monday hitting .500 in 42 at-bats this season. … Monday was Dodgers manager Don Mattingly’s 54th birthday.
Contact the writer: email@example.com


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The upper house of Nepal’s Parliament approved a new map of the country on Thursday including land controlled by India, in a row that has strained ties between the South Asian neighbours.
India, which controls the region – a slice of land including the Limpiyadhura, Lipulekh and Kalapani areas to the west of Nepal – has rejected the map, saying it was not based on historical facts or evidence.
Members in the National Assembly, or upper house, voted 57-0 in favour of a constitutional amendment bill seeking to replace the old map, Chairman of the House Ganesh Prasad Timilsina said. The bill was passed by the lower house over the weekend.
“We have enough facts and evidence and we’ll sit (with India) to resolve the dispute through diplomatic negotiations,” Law Minister Shiva Maya Tumbahamphe told Parliament.
The new map was approved by President Bidhya Devi Bhandari, a presidential palace statement said, hours after it was cleared by the Parliament.
A spokesman for India’s Foreign Ministry declined to comment on Nepal’s decision.
The row over the map began last month after India inaugurated an 80 km (50 mile) road from the northern state of Uttarakhand to Lipulekh on the border with the Tibet region of China, about 19 km of which passes through the area Nepal says belongs to it.
The road cuts the travel time and distance from India to Tibet’s Mansarovar lake, considered holy by Hindus.
Nepal says the land belongs to it as a river in the region formed its western border with India under an 1816 treaty with the British East India Company.
Nepal, which was never a part of British India, and New Delhi differ over where the river originates.
The disputed land, about 372 square km (144 square miles) in area, is strategically located at the tri-junction between Nepal, India and the Tibet region of China. India has kept a security presence in the area since a border war with China in 1962.


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The information available to help control engineers detect locate and diagnose faults in Power distribution networks is very limited. The project aims to identify measurement techniques to pinpoint and diagnose faults. Intelligent multi-agent based software will be developed to assist the control room engineers to take appropriate action to maintain supply to customers This research programme involves staff from the Intelligent Autonomous Systems (IAS) laboratory and the Power Systems and Electronics Research Group (PSERG) in providing supervision and technical support for two bursary funded students.
Developments in Switchgear:
This programme involves a number of projects aimed at improving the performance reliability and durability of electro-mechanical switches. A mathematical model of the arc which exists between electrodes when switches operate is being developed. The amount of arc energy received by an electrode has been measured from the electrode's surface temperature and, most recently, using the ANSYS Finite Element computer package. The distribution of the arc energy as heat to each electrode has been estimated through simulation for a condition where the arc power is distributed equally between the two electrodes. Other projects in this area have involved investigations to determine the optimum switching point's opening and closing for minimising contact erosion.
Application of FACTS to Maintenance of Power System Integrity:
In an electrical power system consumer demand must always be met by generator supply. With the privatisation of the electricity supply industry in the early 1990's maintenance of system integrity has become significantly more complex. Transmission and distribution companies must devise methods for dealing with the effects of short term mismatch between supply and demand. This programme seeks to identify situations in which power system oscillation and/or voltage collapse could potentially occur and offer remedies using Flexible Alternating Current Transmissions Systems (FACTS) devices.
Other projects in which the Group has been or is involved include:
DC regeneration onto the AC grid by forced commutated inversion.
Power quality of wind turbine generating systems integrated with the grid.
Supercapacitors as energy storage devices in hybrid electric vehicles, in collaboration with BP Research,
Facilities available to the group:
The Power Systems & Electronics Research Group laboratory houses a number of electric motor/generator machine sets with industry standard variable speed drive, obtained from previous research projects, simulation of electric vehicles, power distribution systems and wind-turbines.
Computer-aided design tools include EMTP and PSCAD/EMTDC for electrical transient simulation, ERACS for power systems modelling, ANSYS for Finite Element Analysis, MATLAB for control system modelling and design, and VISSIM for traffic flow simulation. These packages allow modelling of complex electro-mechanical and transport systems and investigation of system control strategies.


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Click the "View Income Limits" link to determine if you are eligible for rental subsidy; contact the associated management Agency listed at the bottom of the web page for application information; Click the "View USDA/Rural Development Servicing Office" link to determine a point of contact for additional help
USDA Rural Development’s Rural Housing Programs offer a broad range. sc.egov.usda.gov/eligibility/welcomeAction.do to determine if they are within the established income limit based on household.
Rural Development Single Family Housing guaranteed loan program Select a state to see the income limits for the counties in that state. WV OH PA ME VT NH MA NY MD DC DE NJ CT RI VA NC SC WA CA NV ID MT WY ND SD NE KS OK MN IA MO AR MS AL WI MI IL IN KY TN GA FL LA TX UT AZ AK HI WP PR VI NM CO OR
Rural development Income limits do not factor future income or earning potential, only current income as at the time of closing. 6. Income limits are applicable for both purchase and refinance mortgages Visit this link to check current SFH Guaranteed Income Limits.
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Your USDA loan eligibility varies according to your financial situation.. the USDA also offers rural development loan and grant programs that.
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The map displays guaranteed loan income limits based on region.. a real- estate agent or by visiting the USDA Rural Development website.
USDA Rural Development offers a variety of programs to purchase. who in turn are in regular contact with USDA’s Guaranteed Loan Specialists in Utah. Loan limits and income eligibility are dependent.
The Rural Development loan was created to spur homeownership in rural areas, especially among home buyers who would not otherwise qualify. As such, usda publishes income limits. Maximums are set at.
U.S. Department of Agriculture received 15 applications requesting $258 million in loans in the first round of the reconnect pilot program. aid for Disaster Recovery. Rural Development has a number of resources that can help assist those in need of disaster recovery aid.
With the USDA Rural Development Loan program homeownership is possible even if you aren't able to make a. Must meet Rural Development income limits.

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