text:
Water swellable polyacrylate articles are made from a solution of the polyacrylate having an effective amount of a soluble crosslinking agent therein by heating and/or drying the solution. The polyacrylate solution is made from a polyacrylate by saponification and the cross-linking agent is then added.
Claims available in
Description (OCR text may contain errors)
United States Patent 11 1 Gross et a1.
1 Dec. 16, 1975 [73] Assignee: The Dow'Chemical Company,
Midland, Mich.
22 Filed: -Mar. 13,1974
21 Appl. No.: 450,650
[52] US. Cl ..260/29.6 E; 260/296 TA, 260/78.5 R; 260/89.5 S, 260/296 SO [51] Int. Cl. C08L 31/02; CO8L 33/02 [58] Field of Search 260/785 R, 29.6 TA, 29.6 H, 260/296 E, 89.5 S, 29.6 SQ
[ 56] References Cited UNITED STATES PATENTS 2,649,439 8/1953 Brown 260/895 S 3,245,933 4/1966 Muskrat 60/296 N 3,514,419 5/1970 Darlow et all. 260/296 H 3,669,103 6/1972 Harper et a1 128/156 3,810,468 5/1974 Harper et a1 128/156 Primary Examiner.l0seph L. Schofer Assistant E.\'aminerPeter F. Kulkosky Attorney, Agent, or Firm-Benjamin G. Colley- [57] ABSTRACT Water swellable polyacrylate articles are made from a solution of the polyacrylate having an effective amount of a soluble crosslinking agent therein by heating and/or drying the solution. The polyacrylate solution is made from a polyacrylate by saponification and the cross-linking agent is then added.
9 Claims, No Drawings METHOD FOR MAKING A CROSSLINKABLE AQUEOUS SOLUTION WHICH IS USEFUL TO FORM SOFT, WATER-SWELLABLE POLYACRYLATE ARTICLES BACKGROUND OF THE INVENTION This invention relates to soft, water-swellable articles made from crosslinked polyacrylates, methods for their preparation, and to an aqueous solution of polyacrylates which is useful to make absorbent articles.
It is known from US. Pat. Nos. 3,669,103 and 3,670,731 that polymeric sorbents that are crosslinked during polymerization can be used to make disposable diapers, dressings and the like.
It is further known from Ser. No. 371,909, filed June 20, 1973, that water swellable articles can be made from post-polymerization crosslinked polyelectrolytes. However, these articles are generally stiff and brittle and generally require a plasticizer to make a film or casting soft enough to be useful in most applications, expecially in diapers. A disadvantage of using a plasticizer is that the most effective plasticizers are also humectants and make the polyelectrolyte article very sensitive to high humidity.
For example, if polyacrylates are converted through alkaline ester hydrolysis to the corresponding copolymer of the acrylate and acrylic acid salt, as in Ser. No. 371,909, approximately 80 percent or more of the acrylate mers must be so converted before the polymer becomes water soluble. This is attributed to alkaline attack on the polymer particle from the outside in, whereby the polymer molecules on the outside become much more altered by ester hydrolysis than those on the inside of the particle. At the high degrees of hydrolysis then necessary to solubliize all the polymer, the resulting polymer is more akin to a salt of polyacrylic acid than to a polyacrylate. The softness of the original polyacrylate has been replaced by the glassy brittleness of a salt. This brittleness is highly undesirable in water swellable (absorbent) articles.
SUMMARY OF THE INVENTION It has been discovered that the use of plasticizers can be eliminated in the known post-polymerization crosslinked polyacrylates by providing for the partial saponification of the alkyl acrylate mers in the polymer chains. Thus, when about 30 to about 70 weight percent of the alkyl acrylate mers are left intact in the polymer, the resulting crosslinked article formed from a solution of the partially saponified polyacrylate is soft and flexible without the necessity of adding a special water-soluble plasticizer such as glycerine.
The invention comprises methods of making crosslinkable aqueous solutions, methods of making soft, water-swellable crosslinked polyacrylate films and fibers as well as methods of making an absorbent article coated with a dry water-swellable soft polyacrylate and the products produced by the above methods.
Before the final products can be prepared, it is essential to'prepare a solution of the polyacrylate wherein an alkyl acrylate, or a mixture thereof with an alkyl methacrylate, is partially saponified with an alkali metal hydroxide solution. In general, the method of making this solution comprises A. forming a polyacrylate solution having about 30 to about 70 weight percent alkali metal carboxylates by dissolving in an aqueous alkali metal hydroxide solution a polyacrylate comprising 1. about 30 to about 92 percent by weight of an alkyl acrylate wherein the alkyl group has 1-10 carbon atoms, an alkyl methacrylate wherein the alkyl group has 4-10 carbon atoms, or mixtures thereoof; 2. about 8 to about percent by weight of an olefinically unsaturated carboxylic acid, and 3. about 0 to about 15 percent by weight of an omega hydroxy-alkyl acrylate having 14 carbon atoms in the hydroxy alkyl group; I B. heating the solution until saponification is complete,
and C. adding to said solution about 0.1 to about 10 weight percent based on the dissolved polymer of a watersoluble crosslinking agent which is reactive with carboxylate salt groups.
The final products of this invention are made by coating a substrate with the above solution or extruding the solution into non-solvents to form fibers both followed by heating and crosslinking the polyacrylates.
The final products of this invention are water-swellable and are useful wherever aqueous solutions need to be absorbed. The present invention is particularly useful to make disposable absorbent articles as an additive to increase absorbency while decreasing the articles bulk. Examples of the diverse utilities are surgical sponges, tampons, diapers, meat trays, litter mats for household animals and the like.
DETAILED DESCRIPTION The alkali-soluble polyacrylates useful to form the crosslinkable solutions of this invention can be made by known techniques such as emulsion, suspension, bulk, or solution polymerization techniques, so long as they consist of about 50 to 92 percent by weight of an alkyl acrylate with 1-10 carbon atoms in the alkyl moiety or an alkyl methacrylate with 410 carbon atoms in the alkyl moiety, about 8 to about 50 perccent by weight of an olefinically unsaturated carboxylic acid and about 0 to about -15 percent by weight of an omega hydroxy alkyl acrylate having 1-4 carbons in the alkyl moiety.
It is preferred to use alkali-soluble latices having about 15 to about 60 weight percent of non-volatile polymer solids as is set forth below.
Examples of useful alkyl acrylates are methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate and the like. Examples of useful alkyl methacrylates are butyl methacrylates, hexyl methacrylates, octyl methacrylate, decyl methacrylate and the like.
Examples of useful omega hydroxy alkyl acrylates are 2-hydroxyethyl acrylate, hydroxymethyl acrylate, 3- hydroxy-propyl acrylate and 4-hydroxybutyl acrylate.
The foregoing polyacrylates are then dissolved in an aqueous alkali metal hydroxide solution. Generally the equivalents of hydroxide solution used are from about 30 to about 70 percent based on the molar concentration of polymerized monomer and the preferred amount is from about 40 to about 55 percent. In any event, the amount of hydroxide solution added is sufficient to convert or saponify some of the acrylate esters to alkali metal carboxylates and to neutralize the carboxylic groups of the polyacrylate used into alkali metal carboxylates so that the converted polyacrylate has about 30 to about 70 weight percent of alkali metal carboxylates.
This solution is then rendered crosslinkable by adding about 0.1 to about weight percent based on the dissolved polymer of a water soluble crosslinking agent which is reactive or crosslinkable with carboxylate salt groups.
The foregoing aqueous solution can be used per se to prepare the final products of this invention. However, it is sometimes advantageous to add various amounts of volatile monohydric alcohols and/or ketones td control the viscosity of the aqueous solutions and increase the rate of drying. Examples of useful monohydric alcohols are lower alkanols such as methyl alcohol, ethyl alcohol and propyl alcohol. Examples of useful ketones are acetone, and methyl ethyl ketone.
Illustrative examples of the soluble crosslinking agents useful in this invention are polyhaloalkanols such as 1,3-dichloroisopropanol, 1,3-dibromoisopropanol; sulfonium zwitte rions such as the tetrahydrothiophene adduct of novolac resins; haloepoxyalkanes such as epichlorohydrin, epibromohydrin, 2-methyl epichlorohydrin and epiiodohydrin; polyglycidyl ethers such as glycerine diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether; and the mixtures of the foregoing.
The olefinically unsaturated carboxylic acids used in this invention can be mono or poly carboxylic acids.
Examples of the mono-olefinic monocarboxylic acids are acrylic, methacrylic, crotonic, isocrotonic, angelic, tiglic, senecioic or mixtures thereof.
Examples of the mono-olefinic polycarboxylic acids are maleic, fumaric, itaconic, aconitic, teraconic, citraconic, mesaconic, glutaconic.
Compounds containing two or more of the functional groups of the foregoing crosslinking agents would also be useful, as well as precursors which would form these functional groups under the conditions encountered in heating or drying the polyelectrolyte solutions.
Sulfonium zwitterions are known from U.S. Pat. No. 3,660,431, dated May 2, 1972; Ser. Nos. 205,754 and 205,755 both filed on Dec. 7, 1971. The disclosures of this patent and patent applications are incorporated herein by reference.
The crosslinking technique used in this invention to transform water-soluble polyacrylates into insoluble but water-swellable polymers is known as nucleophilic displacement on saturated carbon.
The carboxylate ion on the polyacrylate acts as the nucleophile while the cross-linking agent is the substrate for the nucleophilic attack. Typical leaving groups and their corresponding substrates are listed in Table I. Any combination of two or more of these leaving groups on the same substrate could act as a crosslinking agent for the polyacrylates of this invention.
Table II lists several illustrative compounds used as cross-linking agents in this invention and the operable limits to obtain insoluble but highly swellable polyacrylates according to this invention. Once insolubility is reached, higher levels of cross-linker give polymers which swell in aqueous media to produce firmer, less slippery gels but of lower actual absorbency.
TABLE I Leaving Groups in Nucleophilic Displacement (R alkyl or aryl) TABLE I-continued Leaving Groups in Nucleophilic Displacement R ulkyl or aryl) TABLE II Cross-linking Agents for Polycarboxylates Crosslinker Wt. of Polyelectrolyte l.3-dichloroisopropanol 04-10% epibromohydrin 05-10% epichlorohydrin l-l0% glycerine diglycidyl ether 0.10-457r novolac sulfonium ion l-l0% The rate of nucleophilic displacement is concentation dependent and is a factor in this invention. In solution, when the concentration of the cross-linker is very low, the rate of reaction is quite slow (pot life 10-48 hours before gelation). Once the solution is applied to a substrate Surface and evaporation of solvent begins, the rate of cross-linking accelerates. Applying heat at this time increases the reaction rate even more.
If the cross-linking reaction is allowed to proceed in the original solution as by heating, aging, or excessive amounts of cross-linker, the absorbent articles of this invention cannot be fabricated. The solution will become progressively more viscous and stringy until it forms a continuous gel which could not be spread,
sprayed or spun.
In the method of making water-swellable films by the present invention the above solution of the polyacrylates is spread on a flat plate or roller of metal, plastic, or other impervious substrate and heated to a temperature greater than 30C. to crosslink the polyacrylate and drive off the excess water and/or alcohol. The film is then peeled off the plate or roller by a scraper to recover the intact film for subsequent storage or use.
Similarly, when an absorbent article is prepared, the article which is to be the substrate is coated with the solution of the polyacrylate and then the coating is cross-linked. It is to be understood that for the purposes of this invention the coating step implies a complete coating or a discontinuous coating, thus when a fibrous substrate such as cellulose batting, paper, woven or non-woven cloth, and the like are usedas the substrate, the solution can be applied in a discontinuous manner, i.e. in a pattern of large dots, squares, or grid lines to retain the inherent flexibility of the fiberous substrate and at the same time vastly improve its water absorbency. Wood pulp can be coated by slurrying it in the polyacrylate solution followed by a fluffing operation.
If desired. the water swellable film prepared as above can be used per se as the inner absorbentlaye'r in baby diapers. It is sometimes advantageous that the film be disintegrated into flakes, stripso'r powders. This is accomplished by crushing or comminut'ing the film in a hammer mill, blenders, or the likejlf long flat strips are desired, the film can be sliced widthwise with appropriate slicers. I
In some instances, water-swellable fibers are desired. These can be prepared by extruding the above solution of the polyacrylates into a bath comprising lower alkyl ketones such as acetone, methyl ethyl ketone, diethyl ketone and the like. Alcoholic solutions may be extruded into a non-aqueous coagulant such as chlorinated hydrocarbons, i.e. methylene chloride, perchloroethylene and the like. The soft extruded fibers are then removed from the bath by any convenient means such as a three or five roll cluster and carried through a heated chamber at a temperature greater than about 30C. and preferably in the range from about 70 to about 150C. to dry and to crosslink the polyacrylate fibers.
The absorbency of the crosslinked polyacrylates (grams of solution gelled per gram of pol-yacirylate) is determined in the following manner using synthetic urine (0.27 N sodium chloride solution).
'A 0.5 gram sample of a crosslinked polyacrylate is weighed into a 250 ml. beaker, a 0.27 N sodium chloride solution (150 ml.) is poured into the beaker and allowed to soak for 2 hours at room temperature, with occasional'sti'rring. The swelled polyacrylate is then collected by filtration and the gel capacity is reported as grams of solution gelled per gram of polymer salt.
Thefollowing examples are presented solely to illustrate but-'not limit the invention.
EXAMPLE 1 Three mixtures were made up having the following compositions.
' Part B 2.1 g. Sodium 28 g. Methacrylic Persulfate Acid 8.4 g. Acrylic Cld 3. l g. t-Dodecyl Merca ptan "dioctylsodiurn sulfosuccinate (Triton GR-S) Part A was charged to a 2 liter reactor and brought to 40C. while under vigorous nitrogen purge. Eighteen milliliters of Part B was added to the reactor followed by all of Part C. The remainder of Part B was added over the next 2.5 hours while the temperature was held at 39-41C. The latex was then digested at 40 for 1.5 hours, cooled to 30 and bottled. The latex contained 39.5 percent non-volatiles.
Four hundred grams of latex prepared above was mixed with g. of sodium hydroxide dissolved in 120 g. of deionized water at 75C. to give a %-solution of polymer which was 31.4 percent by weight sodium acrylate and methacrylate. Ten grams of the above solution was mixed with 30 mg. of glycerine diglycidyl ether 1.0 percent curing agent by weight of polymer).
. 'A sheet was cast on mirror-finish chrome plate using a 25 mil draw bar, air dried, and oven cured for 15.5 hours at and 0.5 hour at This polymer sheet imbibed 23 times its own weight of synthetic urine (0.27 N NaCl solution) in the above absorbency test.
EXAMPLES 2-7 The procedure of Example 1 was repeated with varying amounts of sodium hydroxide and curing agent. The results are shown in Table 111 along with Example E. A. Ethyl acrylate Hydroxyethyl acrylate is present in the amount of 8 mole 'r; in all examples.
*Glycerinc diglycidyl ether 1 In g. 0.27 N NaCl per g. polymer These examples showthat softness and absorbency have an inverse relationship. The best all around product of these examples is one containing approximately 50 mole residual acrylic esters and cross-linked by approximately 0.15 weight glycerine diglycidyl ether.
EXAMPLE 8 Example 1 was repeated using the following monomer mix, and less initiator and no mercaptan chain stopper in order to raise the molecular weight.
The polymerization was carried out at 60C. and produced a latex of 40.6 percent non-volatiles.
1125 g. of the above latex was added in a-small stream over a period of 25 minutes to a slowly stirred solution of 187.16 g. 50% NaOH in 547.9 g. deionized water. After the polymer had all dissolved, the viscous solution was heated at 50C. for 22 hours to complete the saponification. The resulting solution (25.4 percent solids) had a Brookfield viscosity of 16,200 cps. at 25C. (No. 5 spindle, 10 rpm). The polymer is 50% ethylacrylate by moles with the remainder being sodium acrylate and methacrylate.
32 g. of the above solution was blended with 16 mg. (0.2 wt.%) of glycerine diglycidyl ether and cast on polished chromium plate with a 25 mil draw bar. After air drying, the film was lifted from the plate and placed in a oven. The absorbency (gel capacity) of the film in 0.27 N NaCl was 64 g. solution per gram polymer after a 20 minute cure. The film was strong and flexible right out of the oven and required creasing in order to tear it.
EXAMPLES. 9-12 Eight grams of the saponified solution prepared in Example 8 was mixed with various amounts of 1,3- dichloroisopropanol and films were cast and cured from these mixtures in the manner of Example 8. The gel capacities of the films are set forth in Table IV.
TABLE IV Wt.7( Mg. of D.C.|.P. Example D.C.I.P. Crosslinker Ahsorhenc v* D.(.l.P. 1.3-dichloruisopropanol gms 0.27 N NziCl per gm of polymer These examples show the optimum level of crosslinker using D.C.l.P. is near 0.5 percent by weight of polymer to be cured.
EXAMPLES l320 TABLE V Mole Wt.7( Example 71 E. A. G.D.E. Absorbency Softness 13 55 0.2 44.4 soft 14 52 0.2 48.8 soft 15 50 0.2 49.6 somewhat soft 16 40 0.2 57.2 brittle 17 55 0.175 52.4 soft 18 52 0.175 58.8 soft 19 50 0 175 58.4 somewhat soft 20 40 0.17 5 60.0 brittle E. A. ethyl acrylate G.D.E. glycerine diglycidyl ether These examples show that the unconverted ethyl acrylate portion of the copolymer can be increased to 52 mole without significant loss in absorbency and a desirably soft product is obtained.
EXAMPLE 21 Three mixtures were made up having the following compositions:
Part A 230 gms deionized water 0.3 gms Triton GR-5 1.0 gms Na S O (sodium persulfate) 10.0 gms itaconic acid Part B 20 gms methacrylic acid 170 gms ethyl acrylate Fart 70 s deionized water -.Part A was chargedto a 2 liter reactor and brought to 60C. while under a vigorous nitrogen purge. Then 20 ml. of Part B was addedfollowed by all of Part C. The remainder of Part B was added continuously over a period of one hour at 60C. Thelatex was digested for one hour at this temperature to obtain a final latex having 40.6 percent non-volatiles.
Then, gms of the above latex was mixed with 16.9 gms of a 50'percent aqueous sodium hydroxide solution and 49.1 gms of deionized water and heated at 55C. for about 10 hours to give a 25 percent solution of polyelectrolyte containing 52 molar percent ethyl acrylate. This polyelectrolyte also was calculated to have 51% by weight ethyl acrylate 30% by weight sodium acrylate 12.3% by weight sodium methacrylate 6.5% by weight disodium itaconate.
Twenty grams of the above polyelectrolyte was blended with 45 grams water and 7.5 mg. (0.15%) glycerine diglycidyl ether. A film was cast on a mirror finished chrome plate using a 25 mil drawbar and this film was air dried 6.5 hours at room temperature and then oven cured at C. for 16.5 hours. The absorbency of the final cured film was 41 gms/gms of polymer in the above absorbency test with synthetic urine.
Example 21 illustrates that the polymerization recipe and process can be significantly altered but still allow the preparation of highly absorbent polymer.
We claim:
1. A method for making a crosslinkable aqueous solution which is useful to form soft water-swellable polyacrylate articles which comprises A. forming-a polyacrylate solution having about 30 to about 70 weight percent alkali metal carboxylates by dissolving in an aqueous alkali metal hydroxide solution containing sufficient alkali metal hydroxide to saponify some of the acrylate esters and to neutralize the carboxylic acid groups a polyacrylate comprising I. about 30 to about 92 percent by weight of an alkyl acrylate wherein the alkyl group has l-10 carbon atoms, an alkyl methacrylate wherein the alkyl group has 4-10 carbon atoms, or mixtures thereof,
2. about 8 to about 50 percent by weight of an olefinically unsaturated carboxylic acid, and
3. about 0 to about 15 percent by weight of an omega hydroxy-alkyl acrylate having 1-4 carbon atoms in the hydroxy alkyl group B. heating the solution until saponification is complete, and
C. adding to said solution about 0.1 to about 10 weight percent, based on the dissolved polymer, of a water soluble crosslinking agent which is reactive with carboxylate salt groups.
2. The method as set forth in claim 1 wherein the unsaturated carboxylic acid is a poly carboxylic acid.
3. The method asset forth in claim 2 wherein the polycarboxylic acid is selected from maleic, fumaric, itaconic, aconitic, teraconic, citraconic, mesaconic, glutaconic or mixtures thereof.
4. The methodv as set forth in claim 1 wherein said unsaturated carboxylic acid is a monocarboxylic acid.
5. The method as set forth in claim 4 wherein the monocarboxylic acid is selected from acrylic. methacrylic, crotonic, isocrotonic, angelic, tiglic, senecioic, or mixtures thereof.
acrylic acid.
8. The method as set forth in claim 6 wherein the water soluble crosslinking agent is a polyglycidyl ether. 9. The method as set forth in claim 8 wherein the 5 polyglycidyl ether is glycerine diglycidyl ether.
1 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,926,891 DATED December 16, 1975 INVENT0R(5) James R. Gross et a1.
It is certified that error appears in the aboveidentified patent and that said Letters Patent is hereby corrected as shown below:
Q Column 2, line 38, "50 to 92" should read 30 b0 92 Column 8, line +6, 8 to about 50" should read 8 to about '70 Signed and Scaled this Eleventh Day of December I979 [SEALE Arrest:
I SIDNEY A. DIAMOND Attesting Oflicer Commissioner of Patents and Trademarks
Patent Citations
Referenced by
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text: Need your experienced input to elevate my game? I started playing pool about 7 years ago at age 48 by joing the APA. Got hooked on the game/competition and have worked hard to improve. I am now a 7 level and can beat probably 50% of other 7 levels(our city has approx 150 teams). The top players/gamblers in our city don't play league as expected so I gamble occasionally with them(small wagers)in ring games sometimes and on occasion come out ahead. Trying to further improve I have been playing a former top player and professional gambler at his house once or twice a week for affordable wagers(for me). We play even(9 ball)and he wins 90%+ of the time. My question is should I be playing him because each session we play and I lose depression sets in and I wonder why I even attempt to play this game. What should I do? A local former professional player told me when I started that I was too old to ever expect to be a top player (locally). Do you think he was right? I apologize for the long post.

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Another posting but I promise this will be the last for a while. Lately, I've been tempted to learn to knit hats, so after finding a simple pattern, I decided to go for it. This was made with some stash yarn I had when I first started knitting and didn't want to invest a lot on something I didn't know if I would like.
Okay, I'll be quiet now.
|Blue Mint hat.jpg
I think the hat's awfully damn good! NOW SPEAK LOUDER!!!!
Thanks, Gregory! There will be more postings soon.
Don't apologize for posting! It is the conversations that keep the community spirit alive.
Always willing to read about other peoples decisions, knitting, problems, choices, etc...
Thanks, MMario. Silence doesn't usually last too long with me. :o)
Great hat, Casey! Looks warm, and I love the color.
Thanks, Brent! I've had several requests from my Facebook friends for a hat.
A wonderful hat, please keep posting, I like to read and see what the others on here are doing.
Thanks, Dennis! I'm starting on new projects so will have somethings to post soon.
No need to be quiet about knitting like that! Keep on keepin' on. Well done!
Thanks, Tom!
Great hat. I love knitting hats (and mittens).
Thanks, Ron! I believe I am catching the hat bug myself.
Why be quiet?!? Celebrate your knitterliness! And doing it here is one of the best ways I know of.
Wholeheartedly agree with all the above comments. Being part of the community is what this site is all about. Keep up the good work.


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MMA News
White on Herb Dean: He Made a Mistake Tonight In Faber Stoppage
While Renan Barao looked as dominant as ever in his first-round TKO win over Urijah Faber, many, including Dana White, felt that the stoppage was premature. After getting dropped by Barao multiple times, Faber dove in on one of Barao's legs and covered up. While most of Barao's blows appeared to be blocked by Faber's arm, Faber's lack of movement was what seemed to prompt veteran referee Herb Dean to stop the fight.
"You know, you've heard me up here a million times, talking about Herb Dean, I think he's the best referee in the business. He rarely makes mistakes, but he made a mistake tonight," White said at the post-fight press conference. "Faber was blocking those shots, he gave the thumbs up, and, you know, the guy is the best in the business as far as I'm concerned, but tonight he made a mistake."
Faber, while clearly bothered by the stoppage, stayed professional. "It's unfortunate, being a guy that's very tough, and prides myself on that, in a big show like the one we had today, where I don't get to fight to the bitter end," Faber said at the presser. "But on the same note, Barao is getting better, and he caught me with a clean punch and went for the kill. I don't know-when he said 'intelligently defend yourself,' I'm holding onto a leg, I'm covering my head, I mean, if they're asking me to defend myself, I'm already defending myself, I have to do something, so I put my thumb up, but it is what it is… I feel great that we have a great champion, there's other challenges for me, I'll just get back on the horse and work my way towards being a champion again."
0 Responses to "White on Herb Dean: He Made a Mistake Tonight In Faber Stoppage"
His job is to protect the fighters and he does exactly that. He is a great ref and its better to be cautious and protect these fighters than let it go and then someone.get really hurt then they will be on him because he let it go to long. I stand behind herb dean.
Plus "do something" doesn't mean give me a thumbs up.
do something…..I would classify covering up and avoiding the brunt of the blows as doing something to protect yourself. What's he supposed to do…..look up at the ref and say he's fine, and take a shot in the face and go to sleep. Or move from a defensive position, and cause himself to take the brunt of the blows. What Faber was doing was smart, and Barao may have punched himself out had the ref not pointlessly stop it.
He was already covering up, and was told do something. That doesn't mean, keep getting punched in the arm, or hand, it means do something to improve your position, or I will stop the fight. Would it be any different if Faber were in a Crucifix and being slapped in the face instead of punched? Should we talk about a crime? Lets talk about Alan Patrick getting the nod over Mack.
Dude, Herb Dean doesn't stand behind Herb Dean on this one. He made a mistake, no biggie but trying to act like it was a good call is just silly. It happens yet acting like it was some "good insight" on Herbs part is dumb imo.
I've never seen anybody giving a thumbs up while getting his ass severely whooped. It just does not happen, you are too busy covering up. These are professional fighters and they should have the chance to recover if they are not in an unsafe spot. When someone is hitting your shoulder while you cover up in my opinion does not fit the bill of not being able to defend urself or being at risk. People who try to defend Herbs call by saying better safe then sorry…. This is a fistfight, not a fkn ballet display.
As for Faber getting shots, he earned those mf'ers. If you finish everyone else you get a shot, it's that somple no?
you don't watch enough MMA then…. because there's been plenty of fights where people gives a thumbs up while in a submission or getting ground/pounded to let the ref know they're fine.
I agree with you on the other points. Faber was covering up and "intelligently" defending himself. The fighters have a choice of tapping physically or verbally and the ref should only stop the fight when one of them is unconscious and unable to tap.
I watch the UFC events, is that "enough"?
And which fights are these "plenty"? I would like to watch them.
I've seen it quite a few times too, but not that extremely often. Everything else you said…..right on man.
It was a bad stoppage, imagine every fight would be stopped like that no more Trulillo – Varner ko's no more Sanchez – Melendez etc etc. So I don't really get how people try to defend such a stoppage, yeah you can come up with some bs arguments that might seem logical but I am pretty sure every legit fight fan was truly dissapointed and flabbergasted and felt a bit robbed from what seemed to be a great match on paper. That fact alone made it a bad stoppage.
Wheter or not Faber could have won or was in trouble or outclassed is not relevant imo. Let the man do his job and put on a fight.
UFC 149 – Brian Ebersol vs James Head –
i don't remember which round it was.
Bad stoppage! He deserves a rematch ASAP!!!
Are you serious??? Faber was getting WRECKED! he was on his way to getting knocked out… rematch? give me a break
How do you know. Barao landed nice early, and looked great. All them big swings that were doing little damage could have cost him later in the fight. It is a possibility he would have lost some steam.
Dude Faber was getting smashed… he was on his way to getting ko'd… Barao was picking him apart.. you sound like a butt hurt Faber fan to me
I think the majority are not taking into account, a REF's job you can hate them as you like, but let's face it when you're getting handled the whole fight, would you rather someone make a GOOD call on your behalf and be able to come back to fight another day, or whine about what if's. Clearly if Faber (who I do like as a fighter) was dominating and got caught, there would have been more consideration to how well and intelligently someone was fighting….even a trained monkey can cover itself, it doesn't mean you had a chance when you hadn't throughout the fight. I Believe a good stoppage….as in the past with most good fights, that's why you have a rematch. I like how Dana White is ran by the media and heavy dollar pockets; it's amazing how he no longer can stand by his own staff or his fighters any more, way to go sell out!
Dean isn't employed by the UFC.
That was the wrong call faber was recovered on the ground waiting for barao to slow down the hammer fists so he can try to get that single leg. Not one punch on the ground landed on fakers head hew as covered up and defending himself intellegently p. yes he was in what most would call a bad spot. But he was in no danger of getting seriously hurt. Barao was easily winning the first round caught faber with big shots on the feet but faber was intellegently defending himself. This is a fight I want to see again for the simple fact faber got robbed watch the fight again faber was not out of it and recovered during the hammer fists which not one landed horrid stoppage
Yeah bad stop…..You ever hear of covering to not only protect yourself, but to also let someone punch themselves out. Considering he wasn't taking much damage that could have happened. Many times great fighters weather a storm, let the other fighter wear themselves out, and then when they lose some steam, come back for the victory. If this was supposedly the way it's done, you haven't watched Lesnar defeat Carwin, or Ali vs Foreman.
First off Ali was the king of letting big fighters punch themself out. I'm very very educated on the fight game I very much train in different forms of martial arts. I'm telling you that fight was stopped early. When a guy is hitting your arms landing zero damage then yea I have a problem with the stoppage. Was faber hurt yes did he face plant yes was he intelligently diffending himself YES that was a horrid stoppage and the lesnar carwin fight lmao completely different carwin was way more one sided then barao was. Nothing I repeat nothing landed on the ground nothing. Completely different fights and sinarios
If it ain't the judges, it's the refs… It might get better eventually…
When you are told to do something, putting a thumb up wasn't what Herb was looking for. Faber is a bit spastic. Thinking that getting bombed on, and holding a leg is a good enough defense.
He wasn't getting bombed on a vital part of his body. He was well covered, and not taking much damage. Them bombs that were raining down and doing nothing could have worn down Barao and helped Faber later on. What's Faber supposed to do, move just to prove a point and start taking damage. You sir, are an idiot.
What fight were you watching? Faber was getting smashed.. Herb saved him from getting knocked out
Are you an idiot or do you just spew garbage every time you talk? One maybe two punches landed the rest were on Fabers hand. What would you like Faber to do? He has his arm wrapped around one leg and trying to protect himself? He can't just drop the hand and power thru the single leg and if he let go of the single leg barao would've been in a lot better position! Would things have changed if herb hadn't stopped it? I don't know but Faber didn't get that chance. He is one of the most durable fighters and he can scrap till the end he should've had that chance. What's done is done, Faber will be back!
What you want him to do pop up and say herb I'm okay he had to protect his head from damage and he was doing that not only did he give the thumbs up but he looked at herb and said I'm good twice bro not one hammer fist landed on fakers head it was all arms hits watch the fight again or maybe it's just you don't now what your watching
Bar none bad stoppage. I think it would not have factored the outcome, but it may have. Faber was not taking much damage, and Barao was swinging for the fences. Anybody who seen Carwin vs Lesnar, or Ali vs Foreman know what I'm getting at. In a 5 round fight, all the energy being extended by Barao, could go to Fabers advantage later in the fight, if he survives. A tired fighter can be submitted fairly easily usually. I think Barao's conditioning is too good for that, but now, since a ref is too blind to see a man getting hit in the shoulder, we will never know.
On another note….I think the UFC is rididng Brazilian cock. Theyll let Dos Santos get destroyed, almost seeming hopeful he can pull off a comeback, but stop over this.
Barao was a beast, as for faber, keep your head up budd and live to fight another day, youre a true champ, as for herb dean, hes a great referee, sadly he made a mistake but it happens, love for herb dean as well
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Home Depot is offering Early Black Friday deals with 8 pages of specially priced appliances. On top of already reduced prices, you can save up to an extra $500 on your appliance purchase through Dec. 4 (pg. 3). The more you spend, the more you save. You can also get up to 24 months of special financing. Save big on stainless steel refrigerators, washer and dryer sets, and more - free delivery included.
Featured deals include $1,164 off of a 4-piece stainless steel Whirlpool suite (pg. 1). Save up to $1,401 on a stainless steel French door refrigerator, like a Samsung model marked down to $1,898 (retail $3,299) (pg. 2). Clean up with an Amana tall-tub dishwasher for just $248 (retail $299) (pg. 3) and a Hoover Twintank Steam Mop for $48 (retail $99.96). Check out the back page for washers and dryers starting at $399 each (pg. 8).


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Special Reading Certification
Did you know that there are over 1,650 Special Reading positions in Missouri with approximately 200 openings each year (DESE, 2003)? The need for Special Reading teachers is growing as Missouri seeks to address the No Child Left Behind and Reading First initiatives. Teachers with this certification are qualified for such positions as: Remedial Reading, Title I Reading, Reading Development, Special Education, and Language Arts. Depending on your initial certification experience (BA/BS), this certification may require as few as 6 courses.
Below are the DESE requirements for acquiring Certification for Special Reading as well as the courses you can take at MU to complete these requirements.
Contact DESE to have them review your transcript and determine what courses you need to take.
For advisement of combining a master's degree with certification contact Dr. Betsy Baker or Dr. Carol Gilles.
*These may be met by courses taken as part of the baccalaureate degree.
**A combined course of at least three (3) semester hours in Child and Adolescent Psychology may meet these two (2) requirements.
MU Specifications Revised April 2008
II. PROFESSIONAL REQUIREMENTS* (These shall be met by courses of at least two (2) semester hours, unless otherwise specified.):
A. Foundations of Teaching:
1. **Child Psychology;
TDP Phase I
7300 Advanced Child Development
7310 Advanced Adolescent Dev.
2. **Adolescent Psychology;
TDP Phase I
7300 Advanced Child Development
7310 Advanced Adolescent Dev.
3. Psychology and/or Education of the Exceptional Child (including the Gifted); and
TDP Phase I
7300 Introduction to Special Education
4. Evaluation of Abilities and Achievement (instruction in interpretation of individualized
intelligence tests, formal and informal diagnostic procedures and in prescriptive instruction);
7320 Assessment and Evaluation in Special Education
B. Teaching Methods:
1. Reading (at least three (3) courses required, minimum total of twelve (12) semester hours,
one (1) of these courses shall be in Analysis and Correction of Reading Disabilities);
8670 Analysis and Correction of Reading Disabilities
Choose 9 hours from the following
TDP Phase II (Reading)
8620 Whole Language Curriculum
8640 Studies in English Education (when the topic focuses on reading instruction)
8660 Reading Miscue Analysis
8684 Integrating Literacy and Technology
8900 Curricular Decisions for Literacy in a Digital World
8900 Literacy and the Internet
8900 Nature of Literacy in a Digital World
8900 Strategies for Struggling Readers
8900 Theoretical Foundations of Literacy
2. Language Acquisition and Development or Language Development of the Exceptional Child;
7325 Language Development of Exceptional Students
3. Behavior Management Techniques; and
TDP Phase I
7310 Behavior Management for Exceptional Students
4. Counseling Techniques (to include communication skills with exceptional children and
families of exceptional children); and
7330 Collaboration & Consultation in Sp. Ed
C. Clinical Experiences:
1. Practicum in the Diagnosis and Remediation of Reading and Related Difficulties:
A minimum of six (6) semester hours is required for the practicum which should include
experience with students at both the elementary and secondary levels. The practicum should
require demonstrated competency in student management at both the elementary and
secondary levels.
8664 Literacy Practicum I
8665 Literacy Practicum II
8943 Practicum in Special Education


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|City Administration > Public Information Office
|Notice of Public Scoping Meeting for the Anaheim Regional Transportation Intermodal Center (ARTIC) Draft Environmental Impact Report
ANAHEIM, CA - (February 23, 2010) - The City of Anaheim is hosting a Public Scoping Meeting for the Anaheim Regional Transportation Intermodal Center (ARTIC) Draft Environmental Impact Report, and the public is invited to attend, review project information, and offer comments and feedback. The meeting will take place on February 24 from 4:30 – 6:30 p.m. at Anaheim West Tower (Gordon Hoyt Conference Room) in Downtown Anaheim (201 S. Anaheim Blvd., Anaheim, CA 92805).
ARTIC will serve as a hub for Orange County and the region, a landmark where freeways, major arterials, bus routes and Orange County's backbone rail transit system converge. The network of transit choices will continue to grow in the coming years as the number of Metrolink and Amtrak trains serving Anaheim and local and express bus routes increase. ARTIC will accommodate these services as well as plans for future high speed train service to destinations such as Los Angeles, San Francisco, Ontario and Las Vegas, in addition to the Anaheim Rapid Connection fixed-guideway system (www.anaheimfixedguideway.com). Completion date is expected mid 2013.
The City of Anaheim is responsible for preparing the Draft Environmental Impact Report (DEIR). This draft contains information regarding the construction/operation of the ARTIC Project. ARTIC is planned to take the place of the existing Metro link/Amtrak station located south of Katella Avenue and west of the Orange Freeway. The designated site for ARTIC is a 16-acre site owned by the Orange County Transportation Authority (OCTA) and the City of Anaheim, and is situated south of Katella Avenue, east of SR-57 and Douglas Road, and west of the Santa Ana River.
Parking for the meeting is located at the City of Anaheim Parking Structure (behind City Hall, 200 S. Anaheim Blvd.). The parking structure can be accessed from Anaheim Blvd., north on 42nd Street. Anaheim West Tower is located directly across the street from City Hall.
Media Contact: Ruth Ruiz 714.765.5060more city news
ABOUT ANAHEIM –The City of Anaheim, founded in 1857, is one of the nation's premier municipalities and is one of California's most populous and most visited cities. Anaheim covers 50 square miles with more than 351,000 residents and more than 2,900 City employees. The municipal corporation's annual budget is $1.7 billion. Anaheim supports a thriving business community with companies such as: Carl Karcher Enterprises, Inc.; L-3 Communications; Pacific Sunwear; and Disneyland Resort. Successful sports franchises call Anaheim home, including: Angels Baseball; Anaheim Ducks; the U.S. Men's National Volleyball Team, and the 2012 Olympic Games Silver Medal winning U.S. Women's National Volleyball Team. Anaheim also boasts world-class meeting and entertainment venues with: The Anaheim Convention Center, LEED-certified and the largest on the west coast; Honda Center; City National Grove of Anaheim; Anaheim GardenWalk; Angel Stadium of Anaheim; and ARTIC (Anaheim Regional Transportation Intermodal Center). In addition, Anaheim embraces its vibrant cultural arts community, including the world-renowned Anaheim Ballet. Annually, Anaheim welcomes more than 20 million visitors to the City, truly making it where the world comes to live, work and play. For more information, please visit www.anaheim.net.
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On Tuesday night I attended a benefit dinner in New York for the McCain Institute at Arizona State University. The star attraction was Bill Clinton, in conversation with John McCain. Like other attendees I was startled to hear Clinton come out in favor of aiding the Syrian rebels, but I wasn't planning to write about it because the event was off the record. However, Politico has obtained a tape recording of Clinton's talk and posted an article about it.
The article quotes Clinton as follows: "My view is that we shouldn't over-learn the lessons of the past. I don't think Syria is necessarily Iraq or Afghanistan — no one has asked us to send any soldiers in there. I think it's more like Afghanistan was in the '80s when they were fighting the Soviet Union … when President Reagan was in office [and] got an enormous amount of influence and gratitude by helping to topple the Soviet-backed regime and then made the error of not hanging around in Afghanistan."
Clinton also suggested that any president who refused to intervene simply because it would be unpopular to do so is not acting very presidential: "When people are telling you 'no' in these situations, very often what they're doing is flashing a giant yellow light and saying, 'For God's sakes, be careful, tell us what you're doing, think this through, be careful.' But still they hire their president to look around the corner and down the street, and you just think–if you refuse to act and you cause a calamity, the one thing you cannot say when all the eggs have been broken, is that, 'Oh my God, two years ago there was a poll that said 80 percent of you were against it.' Right? You'd look like a total fool."
The implication is obvious: Obama is in danger of looking like a "total fool."
On one level Clinton's criticism is not terribly surprising since his wife was in favor of aiding the rebels last summer. But Clinton, whatever resentment he may feel toward Obama, has been loyal in public. That he has chosen to break with the White House over Syria is significant. One hopes his comments, which he surely knew would leak, may presage a wider revolt among Democrats in Congress who, like Clinton, are disgusted with Obama's do-nothing policy on Syria.