Note: Descriptions are shown in the official language in which they were submitted.
CA 02236992 1998-05-07
W O 97/17180 PCTAJS96/18403
"HALOHYDANTOIN FORMS AND METHOD BY MELT EXTRUSION"
This application is a c~ in-part application of U.S. application
15 Serial No. 08/554,476 filed November 7, 1995.
BACKGROUND OF THE INVENTION
A distinct need exists for halogen~tP~ hyd~louls in the form of high
integrity gr~n-llPs, pellets and shaped forms, such as tablets, briquP,ttPs, and the lilke.
20 These halohydantoin forms are useful in a variety of appli-~ti-n~, such as hlP~ching,
dishwashing, toilet bowl disinfection, and water tr~tmPnt applications such as swi~ ;..g
pools, cooling water systems, and spas.
~ "High il~ y" refers to solidl products having a pred~ shape,
which are hard, shape-retentive, and dust-free. Dust-free products are desirable because
25 halogen donor co.llpuullds are i~ g in nature. Fu~ re, high dusting i.-lPi~;riPS
the halogen odor associated with these collll.uunds, which is also irrit~ting
Halogenated derivatives of dimethylhyd~tou~ are used in a variety of
applications, such as ~wi.. i~-~ pool ~.. ili,~,,~ (bromochloro-dimethylhydantoin) and
blP~-hing (dichlorodirnethylhydantoin). These halog~n~tP-d dimethylhydantoins are fine,
30 dusty powders which are difficult to obtain in solid forms. In the past, comp~ction has
been sugg~.ste~1 (see U.S. Patent No. 4,242,216 issued to Daugherty et al.); however,
many of the compounds require binders in order to compact well and some compounds
- do not compact at all. The use of binders to produce a commercial form of halodimeth-
ylhyda~ increases costs, and can require additional proce~ing steps, e.g., a blending
35 operation. Moreover, the binders do not alleviate the dust problem to the degree of the
CA 02236992 1998-05-07
W O 97/17180 PCTrUS96/18403
present invention. Many of the forms made by comr~rtion are dusty and friable, and lack
true i"legliLy.
- Briquettes, which are useful for water tr~tmP.nt, can be made by
cnmp~rti~ n. However, applications such as toilet c~e~nin~ require the halohydantoin to
S be in tablet form and the problems of producing larger forms by compaction techniques
are increased in this form. Further, halogenated hyrl ~ oi.~ for pool disinfection need to
be in a dirrGl~.lL for n because of the high ~ oll~til~n rate of the co...~ led briquettes.
The forms neces~ ~ y for pool disinfection also cannot be made by comr~rtinn
The production of forms by melt teçhniques (i.e., casting a molten m~t~.ri~l
10 into a form, solidifying the m~teri~1) and diSc~ sh~g the product by convçntil n~l means)
is well known in other inf~ustriPs, such as candy making. Melt ter-hniqlles provide
particular advantage in the making of foIms in that viItually any form of any SizG can be
made, lu~ only a mold of the specific size and shape, and that only limited by the
cl~liviLy of the desi nPr. "neSignP~r~ i~orms that might i.lcol~ol~.le a logo or specific
15 shape are possible. In some in~t~nres, the mold itself may serve as a ~li~P.n~Pr for the
colllpuu,ld, e.g., in~tituti~nal dishwashing applir~tinnc
None of the traditional active halogen compositions (i.e., those based on
cyanuric acid, succinimi~le, dimethylhy-l~ntoin, or the inorganics) are good c~n~ tP.s for
melt ter-hni~lues of ~ p;.~ because the melt lellll)GlaLulGs of the culllpounds are high
20 ( ~100~C) and very close to decomposition LG1IIP~ U1GS. However, halogen~tP,-l
methylethylhyd~Loill is an excellent ç~n~ te for melt te~hniquP,s because of its low melt
range and the great dirrGlGIlLial bGLweGll its melt ~ pP~ e and decomposition
G. It has been found that, when halog~n~te~l methylethylhydantoin is mixed
with halo~~~-~l~ dilllGLllyllly~ oh~, the Il~i~LulG can be shaped via melt techniques The
25 low mPltin~ methylethylhyd~ulloil~ derivatives serve to disperse ~mm~P.ltP~cl components to
give the overall mix flow p~Gllies. See U.S. Patent No. 4,560,766 issued to Girard et
al.
The melt te~hni~lue set forth in Girard et al. and used in the art for
halohy~loh~s consists of a melt pot with a feed to a molding system. This system has
30 several disadvantages. For one, it is very ~lifficult to u~lilollllly heat melt pots of
halohy~iloill, due to poor heat transfer in powders of this nature. In order to melt the
material enough so that flow is established, the m~t.o.ri~l near the heat source will
neces~rily be heated to a higher lelll~elaLulc than the m~t.ori~l In the middle of the pot.
CA 02236992 1998-05-07
W O 97/17180 PCTrUS96/18403
Moreover, while these halohyd~ oi.-e have a rather large IG. .~GldlulG
dirrGlGl~Lial between their melt lGlllpeldLul~ and their de~l~osiLion lelllp~ldlul~;, some
breakdown-and loss of m~t~ i~l does occur in the melt pot technique when the m~t~ri~l
is left at the required high lGllll~GldlulGs for too long. The breakdown of the m~tP.ri~l is
5 ~ Psi.,.hle for a ~ )G1 of reasons. For one, the fumes which will result from the
breakdown are toxic. Further, the breakdown of the m~tP~i~l can lead to a less pure and
less effective compound. Further, the halohydantoin m~ttori~l being heated in
the melt pot will have a long heat history. When making a mold using this terhniq~-e,
more halohy~ntoin than is needed in the form is cooled and hardened. This means that
10 the extra m~t~ri~l has been repeatedly melted and cooled, in an effort not to waste the
haloLy~lLo~l. However, after several times, the halohyda~lLuill will break down and be
r~tory for use.
Finally, using this melt pot terhniqlle, hardened residue will often be left
in the melt pot after the mnltlin~ which l~Uil~_S extensive clean-up.
RR~li' I)ESCRIPll~ON QF THE INVENI~ON
It has been ...~ e~;~e,~lly found that the method of melt extrusion, normally
used in plastic appli~-~tione, can be used to make halohy.l~Loh~ forms and avoids the
problems associated with conventional melt ter-hni~ e,e. Por Pl~mple, unlike traditional
20 melt te~hniqnes, melt extrusion technillues melt only the discrete, exact amount of m~tf-.ri~l
needed for the mold. Also, the m~tPri~l is subjected to elevated le~ eldlulGs for only
short periods of tirne due to large surface area contact with the material in an extruder.
Moreover, a large change in tGIllpeldlul~ is not required to achieve the desired melt.
Further, because melt extrusion te~hni-lues can cause m~tP~i~le to flow that are not readily
25 flowing, only partial mP1ting of the m~tP~i~l is ~ es.s~.y. This reduces heat input.
The use of this techni~ e for mol~lin~ halohyrl~ oi~-~ is quite novel and
produces ...~ e~ l adv~nt~s. As noted previously, melt extIusion techniques are not
~ norm~lly used with these systems. In fact, ~lthough the Girard et al. patent issued almost
ten years ago, no one has applied melt extmsion te~hniq~le.s to produce forms of30 halohy.l~ oin~ The rP,sllltin~ halohyd~ for ns made by the melt extrusion process
are dust-free, of high h~legli~y, and ~L~ol~ger than forms made by conventional commercial
m~*h~
CA 02236992 1998-05-07
WO 97/17180 PCTAJS96/18403
An additional advantage of extrusion te~hniq~es is that additives can be
fonn~ tP~l into the halohydantoin at the extruder itself because of the ability of the
extruder t~ mix m~teri~l~, particul~rly with twin screw equipment. There is no need for
pre-blending equipment and, thus, cost and pr~!ces~in~ bener,L~ are re~li7~
S The present invention relates to the pr~ cfi~n of a solid h~logp~n~tpA
hyd~llo~ product by extruding a melt or a partial melt of the halohyd~n~oil" cooling the
extrudate to solidify the halohyd~loill, and l~v~,l u~g the solid product. This process
can be used to produce a variety of halohyddllloihl forms.
One embodiment of the invention relates to the production of halohyd~loi,l
10 forms by extruding a melt or par~l melt of the halohy.l~ .h- into a mold of apre~leLP....il-f~ size and shape, cooling the mold to solidify the halohydantoin, and
recovering the SQ~ ifiP~I form from the mold in traditional techniques ~ltP.rn~tively, the
mold may serve as a dispenser for the chemical in its final application. Any form that can
be produced in a mold or a die can be produced by this method, in~ 1ing tablets, pucks,
pastilles, briquettes, pellets, gr~ml1~s, and so-called "-IP~ignPr" forms such as Chri.~tm~
Another embodiment of the iu~/t;nLioll relates to a method of malcing
~mllPs of halo}ly~ oi.~ by extruding a melt or partial melt of the halohydal~loih~ into
sheets, cooling the sheets to solidify the halohy~ , and grin-1ing the sheets to obtain
gr~mllP~.
A further embodiment of the invention is a method for m~king pellets of
halohy~lluJI~ by extruding a melt or partial melt of the halohy~ullu~u through a die or
screens to form strands, which are ~ul~s~uently cut by convention~l tP~hniq~es into
pellets, and cooling the reslllting pellets.
A further embodiment of the invention is a method for producing an
"~ggk~mPr~tP." from the original dusty powder by subjecting the powder to suf~lcient heat
in an extrusion process to melt only a small portion of the powder (the melt acting as a
"binder"), extruding the mix, and recovering the agglomerate by conventional means.
This product has much better h~n~l1ing ch~t~Pri~ti~S and minim~l dust colllL,al~,d to the
origin~1 powder, and would serve as a more effit~i~nt fee~lstor~ for traditional comp~ction
processes used to make large forms, i.e., tablets for ;~ e toilet bowl app1i~ti--n~.
In a pl~r~ d embo-liment the extruder used in t_is method is a twin screw extruder.
CA 02236992 1998-05-07
W O 97/17180 PCT~US96/18403
s
The illvt;nLioll also relates to the solid halohy~l~,ll product producedl by
the methods described above in~ ding forms, gr~mll~s, pellets, and feedstocks.
In a further embodiment of the invention, this extrusion techni~ e can be
applied to compositions CO..~ i.-g the halohydl~lloills along with additives.
Another embodiment of the present invention are the extruded solid
halogen~tPA hyd~lloill products co...~ ed of halohyd~loi.ls alone or with an additive.
Dl; TAILED DESCRIPIION OF TIIE INVI~TION
The halohy~loill colll~uui~ds co..l~ tPA for use in this invention are
10 ~1esçrihed in U.S. Patent No. 4,560,766, which is hereby incol~u,~Led by l~f~ ce.
These halolly~ O;,- compounds have methylethylhyd~loin ~H) as a sole c~ n~ P..
or are an ~.I.,,ix~-.c: of M~ and a halogenated di~ ylllyd~lloill (D~I).
The halogenated methylethyl~lyd~loill for use in this invention has the
follûwing structure:
C~H5 o
Hg,~
X~ ~ X~
0
wherein Xl and X2 may be the same or dilr~ ,~ .,l and are chlorine and bn""ine.
The halogenated dimethylhy.l~..lQi.-~ for use in this invention have the
following structure:
C: Hs 0,
H~ rh
X ~ 'X
CA 02236992 1998-05-07
W O 97/17180 PCT~US96/18403
whGl~l Xl and X2 may be the same or ~lirr~ ,.,l and are chlorinP. and blu~ e.
Halogenaled M~I co",pounds, as co~ ~d to their corresponding
halogenated DMH cvlll~uunds, have signifi~ntly dirrGlGl-l th~rm~l properties. One such
~lO~.~. Iy is the tc.lll~elalul~, dirr~ l;al between the m~ltin~ point and the decomposition
IG111l)G1~UIG of halogenated M~I coll~.ullds. These M~I colllpuunds melt from about
60~ to 70~C, whereas they decompose from about 150~ to 170~C. This large tellll)el~ture
dirrGlG~ILial allows these compounds to be melted and formed without decomposing.
Further, Illi~lulGs of the dihalo DMH and M~I have the melt
ch~r~c-t~ til s of the M~I derivatives such that fluid systems, con~ ing of unmelted
10 di~ ed solids in a molten m~ m, can be formed at low IGI11~G1~LU1~S. TG1~e~a~U1'GS
~ignifiç~ntly below the thP,nn~l decolll~o~ilion point of the mix are lltili7~
Table 1 shows a range of products with melt and decomposition data. The
products are listed in terms of their m~k.s.l-p relative to DMH, M~I and blu~ e (moles).
For example, Dd-llobrulll~ is - Q~ DMH + 0.2 M~I + 0.5 NaBr and is thus referred15 to as product "8-2-5". Since each molecule of the hydantoin final product COIll lS 2
moles of halogen, the moles of chlorine in each final product is 2.0 minus the moles of
NaBr added.
Each of the products listed in Table 1 is made by first mixing M~I and
DMH. The composition is then halogen~t~l using conventional techniques. Two (2)
20 moles of chlorine are added to every composition. If a bromochlorohydantoin or
dibromohy~ oil- is desired, bromine, in the form of NaBr, is added in the desired molar
amount. In a sirïlple oxidation/reduction reaction, the chlorine oxi~i7es the bromine in
the NaBr to Br+, which then halogenates the DMH and M~I. Since each product has
two moles of halogen, the rem~in-ler is halogen~tecl by chlorine.
For example, in m~k;ng D~11~ 5-5-5,0.5 mole of NaBr and 2.0 moles
of chlorine are used to halogenate the ~EI and DMH. The chlorine (0.5 mole) oxidizes
the 0.5 mole of NaBr to Br+, which halogenates the D MlEI/M EH, and the ,i;...~ i.-g
clorine (1.5 moles) halogenales the M~I/DMH. Thus, the final product contains 1.5
moles of chlorin~- and 0.5 mole of l,~ e. No NaBr is added to make the
30 dichlorohy.l~..lo;.~. Two moles of NaBr are added to make the dibrornohyd~loil~s.
While 2 moles of chlorine are also added to make the dibromohy-l~ntoin~, all of the
~.hl~rin~o. is used to convert the 2 moles NaBr to Br+.
CA 02236992 1998-05-07
W O 97/17180 PCT~US96/18403
TABLE 1
(A) DICHLOROHYDANTOINS
GENEP~AL ~CLASS ~ PROD:~JCT:~AKEUP ~MELT
RANGEt, ~-. DECOMPOSITION
- DMH - MEff : ::B r ~4C i~C
S DCDMH 1.0 0.0 0.0 132-145 191
DCMEH 0.0 1.0 0.0 52-64 170
60-642
Dantochlor~ 0.8 0.2 0.0 40-122 150
Dantoin~
~ 5-5-0 0.5 0.5 0.0 53-95 170
~ 6-4-0 0.6 0.4 0.0 54-1 oo2
42-119
~ 7-3-0 0.7 0.3 0.0 40-130
(B) BROMOCHLOROHYDANTOINS
15 GENERAL CL~SS~ : ~ .: PRODUCT.: :~ MEl~T
MAKEUP ~ RAN~iE~DECOMPOS!TION
:DM~ ME~ Br:: ~
. . . . . . . . .
Dantobrom~' 0.8 0.2 0.5 50-142 180
Dantoin~' 180
5-5-5 0.5 0.5 0.5 54-110
65- 1212
~ 6-4-5 0.6 0.4 0.5 53-132
~ 7-3-5 0.7 0.3 0.5 53-146
BCDMH 1.0 0.0 1.0 158-1652 160
BCI\/IEH 0.0 1.0 1.0 74-79 148
Dantoin'~
~ 6-4-10 0.6 0.4 1.0 60-160Not available
~ 7-3-10 0.7 0.3 1.0 57-170Not available
Dantobrom'!9 BTB 0.0 1.0 1.5 57-91 144
79_982
Dantoin~
~ 5-5-15 0.5 0.5 1.5 79-1652 144
CA 02236992 1998-05-07
W O 97/17180 PCTAUS96/18403
(C) DIBROMOHYDANTOINS
OENERAL CLASS PRODUCT MELT
MA:KEUP RAN~iE', DECOMPOSITION
~ DMH MEH Br
DBDMH 1.0 0.0 2.0 179~C2 Decomp
DBMEH 0.0 1.0 2.01 17-1 192 148
Dantoin'l'
~ 8-2-20 0.8 0.2 2.0158-1802 177
Melt range data based on dirr~G~Lial sc~ ng calo~ eLly.
15 2 Capillary Melt Data
The LGlll~ LaLUlGS the halohyd~lLoi~ col.,~unds begin to melt (measured in
20 most cases by dirre,~el.Lial sc~nning calorimetry which provides a clearer picture of early
melt phenomena) in Table 1 are the lowest IGIII~lalUlGS in the melt ranges shown. The
data in Table 1 show that, with the exception of the dibromo derivatives, products
co..~ g greater than or equal to 20% M~ in the hyLul~ill m~k~up have dirr~,r,nces
bGIweell start of melt te~ e~ Gs and decomposition temre.,.l~ Gs greater than or equal
25 to 65~C and typicahy 70-100~C. Halohydd.,Loil-s with dirr~,lG"ces greater than 60~C,
eldbly greater than 70~C, between their start of melt and decomposition IGlllpeldLUlG
can be used in the metho~l of the presen~ invention.
Halohy~l~..lo;o~ with no more than 95 mole % of DMH and at least S mole
% M~I can be used in this invention, with 0 to 90 mole % DMH and 10 to 100 mole
30 % M~I being ~l~f~ d. The most ~lGr~ d halohy~ in~ used in tbis invention
contain 0 to 80 mole % DMH and 20 to 100 mole % M~I. Halohy-l~..l~.;..~ made of 50
mole % DMH and 50 mole % M~I are l~lcfGll~d for melt extrusion of molded forms and
graanules. Halohydantoins made of 80 mole % of DMH and 20 mole % of MEH are
~lGre l~d for making pellets. Halohy~l~ntoin~ made of no more than 95 mole % of DMH
and at least 5 mole % M~ are ~lGre.-c;d for making agglomerate. t- Halog~.n~t~ M~ co~ c ul~ds can be ~lG~ed as described in U.S. Patent
No. 4,560,766 or, ~11.. ,.1 i~ely, are available commercially from Lonza Inc., Fair Lawn,
NJ, such as D~ u~n~ BTB (M~IH with 3:1 active l~lu..li~le to chlorine).
CA 02236992 1998-05-07
W O 97/17180 PCT~US96/18403
g
The ~ lult;s of halo M~I and halo DMH used in this invention can be
made by mixing DMH and MEH in a ~r~lel~ cl quantity prior to halogenation.
Mixtures can also be pr~a-~d in situ from the COll~ ~onding ketones, e.g., acetone and
methylethyL~etone, using the Bucherer-Berg SynthPsi~, and then halogen~ g the product.
S Methods for obtaining these ~ ul~s of halo M~I and DMH are set forth in U.S. Patent
No. 4,560,766. ~11 r. ..A~ ely, Ill~lul~s of halo M~I and DEH are available from Lonza
Inc., under such trade names as Da-l~oill~ 5-5-0 (50/50 molar ratio of MEH to D~H, all
chlorine) and DAUIlO;11~ 5-5-5 (50/50 molar ratio of M~I to DEH with 3:1 active chlorine
to l,l.~ll,u~e).
Furthermore, the compositions used in the invention also include a IIIL~U1~
of halollyd~,l(jills with additives. Examples of additives which can be used in the present
invention include solubility modifiers, comr~ction aids, f~ers, sl-rfactAnt~, dyes,
fr~ran-,çs, di~e~ , lnbri- Ant~, mold releases, del~ ,n1 bnildPr~, corrosion inhibitors,
~:hPl~nts~ ~tAhili7Prs, biocides, bromide sources, and oxi~li7ing halogen compositions. The
15 additives provide an additional function or serve as a ~n~crc~ g aid in the ~ .AI;-)n of
the form. The only requirement is that the mAtPriAl be co...l.AIihle with the halol.ydanloill
composition. Products made of halohy~lAn~oi.-~ with no more than 95 mole
% of Dl!~I, at least 5 mole % MEH, and certain additives in the amounts given below
are a further embodiment of the present invention. Any of the additives listed above
20 could be used in these products, with solubility modifiers, compAçti- n aids, fillers,
frag~nce, mold releases, and o~i~i7ing halogen compositions being the most p-erel-.,d.
Solubility- modifiers which may be added to the halohydl~loill described
herein include, for eY~mI)IP" sodium bic_l,onale, Al.~ .. hydloxide, mAgnP~ m oxide,
barium hydroxide, and sodium carbonate. See United States Patent No. 4,537,697.
25 Solubility modifiers can be used in the compositions in an amount r~n~ing from 0.5 to
50% by weight.
Examples of comp~ctir~n aids include inorganic salts comprised of lithium,
sodium, pot-A~i--m, mAgnPCil-m and ÇA1S~;Utn cations associated with carbonate,
bicall,ollale~ borate, silicate, phosphate, pe~ l,ollale and perphosphate. See United States
30 Patent No. 4,677,130. ComrA~tinn aids can be used in the compositions in an amount
nging from 0.5 to 50% by weight.
Fillers added to the halohydantoins include, for example, inorganic salts,
such as combinations of lithium, sodium, potassium, mAgnesi~lm and calcium cations with
CA 02236992 1998-05-07
W O 97/17180 PCTrUS96/18403
sulfate, and chloride anions, as well as other inorganics such as clays and zeolites. Fillers
are used in the compositions to reduce product costs and can be added in an amount
r~nging fro}n 1 to 50% by weight.
Examples of s~lrfact~nt~ include Aerosol OTB (sodium dioctyl
5 sulfos-lct~-in~tP,), disodium lauryl sulfosl~ccin~tP, sodium lauryl sulfc-~P~t~tP,, and sodium
cocvyL;seLllionate, as well as other sulfonates. S~ ct~nte are used in the compositions
to çnh~nce clP~ning pe ~,l..&nce and can be added in an amount ~nging from 0.5 to 40%
by weight.
Dyes and pigmPnte can be added to the compositions in an amount of 0.1
10 to 10 % by weight. Examples of dyes and pigm~nt~ are copper phthalocyanine
tetr~e~llfonic acid tetra sodium salt, all derivatized and underivatized phthalocyanines such
as Pigment Green 7, Pigment Blue 15, and Pigment Blue 86, as well as inorganic
pi~mPntc, such as l~7~lritP.
F.,.g.,.l~es can also be used as additives and can be added in an amount
15 .,...g;..g from 0.1 to 10% by weight.
Di~el.,a~ may be added to inhibit scale deposition in treated waters in an
amount ,angih~g from 0.1 to 20% by weight. PY~mI)lçs of dis~e~Ls include all
polyacrylate based polymers in~ ltlin~ seconJdly and tertiary polymers and some
phosphonate dis~ , such as Bayhibit S'l9, 2-phosphono-1 ,2,4-but~nP,tlric~rboxylic acid
20 tetra-Na salt (PBTC).
Lubricant/mold releases which may be added to the hydantoin include
Acrawax'~9 C, m~gnP,eillm, c~lcillm, and sodium stP~r~te. These lubricant/mold releases
are added to the compositions in an amount l~ngin~ from 0.1 to 20% by weight.
D~ler~,enl builders are added to the compositions in order to enh~nce
25 cl~P~ning perfo,-~ ce. An example of a d~ lll builder is sodium tripolyphosphate.
They are added in an amount ranging from 1 to 50% by weight.
Chelants are used in the compositions to seq~le.ster metal ions and enh~n~e
hard water p~ro,ll,allce and are added in an amount ranging from 1 to 50% by weight.
~xamples of chPl~nte include sodium gluconate, ethylene ~ mine tetr~ tiC acid (EDTA),
30 citric acid, and sodium nitrilotri~t~et~te (NTA).
N-hydl~gen stabilizers are added to the compositions in order to e~nh~nc
tablet stability and increase additive c~-.,.p~lihility and are added in an amount r~nf~inf~
from 0.5 to 20 % by weight. 1: Y~mrlPs of N-hy&ugen stabilizers include
CA 02236992 1998-05-07
W O 97/17180 PCTnJS96/18403
11
dimethylllydall~oihl, 5,5-dimethyl}lydallL~ (DMH), S,S-methylethylhydantoin (MEH),
~;y~.-.;c acid, slllf~mic acid, sull.-n~ lç, s--lfam~tPs, glycoluril, and succiniînide.
- Examples of inorganic biocides which may be added to the compositions
include molybdates, copper sulfate, se1~n~t~s, ~ s, and cl~,.,a~es. See United
S States Patent No. 4,995,987. These biocides are added in an ~rno~-nt r~nging from 0.1
to 10~6 by weight.
Bromide sources may be added to provide biocidal bromide (Br+) in the
es~llce of active L~hlorinP.. Bromide sources may be added in an amount r~nging from
to 30 % by weight. 1;Y~mr1çs of bromide sources include sodium bromide and
10 pot~inm bromide.
Oxitli7ing h~logt-.n compositions may be added to u~Lil".~e product
p.~ n~e by ~!;..~ g Br/Cl and DMH/MEH ratios. An example of an oYi-li7in~
halogen composition is bromochlorodimethylhy~ They are added to the
compositions in an amount r~nging from 1 to 95 % by weight.
It has been une~rpectPAly found that melt extrusion processing is an ideal
t~hniqlle for exploiting the melting pl~e ~ies of the halohydantoin compounds and
ob~illing halohydantoin forms without the problems of the prior known processes.The halohydantoin powder of choice is introduced into the extruder. The
extruder is zone-heated and controlled to achieve the sper-ifi~ temperature for the
20 particular halohydantoin. By using this teçhni~lue, only small q~l~ntiti~s of m~tPri~1~ are
subject to heating and for only limited periods. Other advantages of using extruders are
the high throughput and the con.~i~t~ncy of output. The ability to blend additives at the
extruder, thus eli...i~ ;.-g pre-blen-ling equipment, is a further advantage.
A single extruder can provide wide flexibility in producing forms. The
25 molten slurry extrudate can be directly flowed into molds for tablets, briquettes, or other
shapes, in~ln-ling "designer" shapes. Alternatively, the slurry can be extruded to sheets
for subsçqllent ~mll~ti~n or through dies for pçllPti7~tion. Any extruder used in a
~ commercial setting can be used for this invention. It has been found that a screw
extruder, either single or twin, is particularly useful in practice of the method of the
30 present invention.
A system for cooling and solitlifir~tic)n of the product is required. Belt
systems, used for flaking operations, can be used. Other systems known in the art can
be used in this method.
~ CA 02236992 l998-05-07
SENT BY:Xerox Telecopier 7020 : l-28-98 : 2:59PM : 2127536237' 7033057718;# 3
,
i?1 1998
12
Any rnethod ~mown ln thc art can be used for ~ecovering tl~c foIm froln tho
mdL. Mor~over, t~hn;qu~ ~own inthe art for ~m~ , cutt~ng ext~udate, and cooling
CaL X u~od Llthi~ m~th~ for ob~ po~s and gJ~mll~
The ~ollowing ~YYmrl~ are ill~t~tive of the p~ent invention; however, it
S wiL ~e uud~,lalOOd that thc 4~ JtiOl~ is not limited to the s~ details set ~oIth ~n tbe
~Y~p1es. R~9~plec 1-7 use a s~gle scrow extrudor ~d ~smpl~-s 8~10 use a 50 ~-
corLnerc~ twLn ocrew extruder in the r~ O~c ~p~h~A ~herein.
uDle 1
A 50150 ~lu~ of ul.,~l~ylhy~ nd ~ , all cl~
1~' halol~ c~ meltrange--53-9S ~C DSC) (r ~ ~ S-5-0~..d-,r,~nza)vvaofed throu~h
the hopper of sn ~ftrud~r (C.W. R~hc~rler, p~?ctrgllir Pla~ti-Co~ Torque Ph~mP-te~,
~ Type EPL-V302, with Rr~ r c~ e scre~ e,.4udu, 3-zone, l~pc 2S23 ~vlth a s~inl~g~
ste~l ~cre~ 25:1LII~, 2~ u~ sion Iatio and rod d~o with no ~ert (Ihf~ l col~ar
e~), wrew ~pced - 60 RPM). Ibc folIowi~lg ~ gr wero madle oQ the cAlnld~
1' Zore 1, 2, 3: 70~C, Die: 6S~C (~ u~); and melt~ r~ : 64 65~C. The a~!p~ ;...
reei's ~ timc of th~ haloL~ ;.. in the Isxtrudcr wa21 30 to 4{~ g~nt19, The out~ut wa~
a~p ~ t~ly 62 grams/miml~.
The extrudate had the Concir' ry of light, well-mixed pancalce batter and wa~
col1~ the fo~iwing molds~ ~
a) 70 n~n smooth p~ niml~ weight d~hes (~ u~ t~ 1OO gnu~s);
b) sm~ ice cubo ~ay8, ~" X ~(ay~ ;n~ y 16 gnUn8);
~ c) small al~ .. CUp8 l~$n X 7A.", ~?p,,~"~;".~tnly 45 gIam~); andd) varlous pla~tic molda Of anim~ eeS and rh~ dccu,~lions
~ ~n-.r" fonns).
25 The,~t~A~l was al-so "spilled" into tTays for cventu~l b~ak-up ~nd screening to form
g~nu es.
Aftor cooling to room ~ o~ e, the molr1ed products werc recovered by
conventinnnl labUl~,tUl,~ tec~nique~. ~or eY~mpl~, 100 glam table~ ~ere simpl~r popped out
of th~ 70 mm al~min~lm dishes by e~c~tin~ finger ~les:.u-~ on tho outsid~ bottom center of
30 the di h. The recovered tablet m~int~inP-1 full integnty (hard, ~miforrTl surface) and was
completely ~ tl~sF. ~easurement of the force ~ui,~cl to f~acture the tablet was ~lrv~
by c~rt~tine a vertic~l blade acro~s the face of a sn~ A tablet (Inst~on'~
r
CA 02236992 1998-05-07
W O 97/17180 PCT~US96/18403
13
Instn-mPnt~tion). The force required to fracture the tablet was 125 lb. as opposed to an
average of 83 lb. for commercially produced tablets of similar weight and shape.- The co~ ial tablets used for co.~ on are ~;ullGlllly made by any
number of standard comr~tion terhni~ es and equipment, such as rotary tablet presses,
in which a powder or granule is injecte~l into a mold and subjected to colllpr,ssion forces
of al)l)r~ Ply 10,000 pounds.
Example 2
A 50/50 mib~lul~G of methylethylhydantoin and dimethylhydantoin, 3:1
10 chlorine to l~ lllh-e halohydantoin (melt range ~ 54-110~C, DSC) (Dantoin0 5-5-5
powder, Lonza) was processed as described in Example 1.
The 100 gram tablets obtained m~int~inP~I full i lLe~;lily and were d~lstlPss
Breaking of the tablets required 135 lb. force.
15 l~ ple 3
A halohyd~,loill comprising 100% methylethylhydd,~loul with 3:1 active
blul~ le to ch10rin5 (melt range 57~-91 ~C, DSC) (Dal.LOl,l~ Q BTB powder, Lonza) was
proce.ssP~A as desclil,ed in Example 1, except the extruder had the following settings
Zones 1, 2, 3: 70~, 75~, 70~C, respectively; Die 80~C; melt te~ ~dLul~;: ~ 81~C.The output had the con~i~t~n~y of thick p~nr~kt~ batter and was discharged
onto a tray for ~rin~ling and conversion to granule products. The resolidified mass had
good integrity and ground readily with minim~l dust.
~.Y ~WI~ 4
Dantobroma9 BTB used in Example 3 was processed as descrihed in
Example 1, except the extruder had the following settings and die: Zones 1, 2, 3: 70~C;
Die: 65~C; melt temrpr~hlre: 65~C; and a 3/16" plug die. A strand of extrudate was
produced which had good illleglily at the die face, and which could be cut at the die face
lly into pellets. The pellets hardened rapidly into h~nrllP~hle form.
~m~ le 5
A dry blend of 70% DdllL~ 5-5-0, 20% dimethylhydantoin (stabi~izer),
and 10% copperphthalocy~nin~tetra~nlfonic acid, tetra sodium salt dye was processed and
CA 02236992 1998-05-07
W O 97/17180 PCTAJS96/18403
14
extruded as ~ s~rihecl in Example 1, with die and melt l~ dl,U~ at approximately70~C. A flowing melt was produced which was readily cast into 30 and 100 grarn molds.
The cooled-tablets were blue, hard, non-dusting forms.
S ~Y~ ?le 6
nDntochlnr~ an 8-2-0 composition, was fed into the extruder as descrihed
in Example 1. Zones 1, 2, and 3 were 70~, 65~, and 60~C, respectively; die: 55~C; melt
~lU~ dul~,: 61~C. A strand-like extrudate was o~ d which on cooling had an
agglo--leldled/g~mll~r a~e~ ~d~e. It was r~adily broken into a ~dmll~r powder with
10 good flow properties and minim~l fines.
~nple 7
Various additives were tested for their colll~JdLil)ility with halohydantoins
for use in melt extrusion. Mixtures were ~lG~ ~ comprising 90% by weight of a
15 halohydantoin and 10% by weight of the additive. The halo~ly~allloil~s used were either
Da~Oi.lQ 5-5-0 or Da,lLoi~ 5-5-5. The ~rerifi~ additives are listed in Table 2, colurnn
3 and t~e ~ltguly of the additive is listed in Table 2, column 2.
TABLE 2
,,,, , , ,. - -, , ,, , , , ~ .. .. ........ . . . ........ . .................. .
~talohydantoin: :: Additive : Category ~ Additive : Example
5-5-O Solubility Modifier Alurninum Hydroxide
5-5-O Compaction Aids Sodium Bicarbonate
5-5-O Filler Sodium Sulfate
5-5-O Surfactant Aerosol'!D OTB
5-5-0 Dye Sulfonated copper
phthalocyanine
5-5-0 Dispersant Polyacrylic acid
5-5-O Dispersant Bayhibit~' S
5-5-O Lubricant/Mold release Acrawax~ C
5-5-O Detergent Builder Sodium Tripolyphosphate
5-5-O Corrosion Inhibitor Sodium Silicate
5-5-O Corrosion Inhibitor Sodium Benzoate
5-5 4 Chelant Sodium Gluconate
CA 02236992 1998-05-07
SENT BY XerOX TeleCOPier 7020 ; 1-28-98 ; 2:59PM ; 212753B237~ 7033057718;# 4
PCT/US 96/ 184CI3
1~ 3 1998
; ~ ~AiBI~L 2
5-~-0 Solubility l~;flAr ,~l.j.. ;... Hyd~xide
5 ' 0 St~ 7~ Diu,-LLylhyr1~qntnin
5-~-0 Ri~;A............... Coppor Sulfate
S-"-O ~v~dG Sourco SoAillm ~v.. idc
5 S O OY;~j~n~ bslogen B~n~
co .~11;nn
S 5-'-5 Soln~ Aifi~r ,~1~.. l;.. ~ Hydr~xide
5- 1 5 Filler ~:o~ m Sulfate
5-S-S , Dis~l~ Polyacrylic acid
The ~LL~LU~G~ were hP~ted to a range of 8S~ to 95-C ~n ~n oil ba~ Jpon
lC m~-i~, th~ ~lu~ ~v~ pou~d into a small h~Ya~nn~1 plasdc mold and allowod to co. ol.
In e~h ca~c, thero wa~ no vlwal r~ lo~i ~n and tlle forms wcre ~ol~d and du~ fi~o.
r ~,t~ v.~l~, an 8-2~ co~ on ~ , was fod through tho hopper o~ a
.15 Worn~r/Pfldderer ~ 3OJ Co-rotating TwJn Scrow ~I,u~, set up wîth four heatlng zone~,
a die .nd die faco plate. The scre~ cl~ mPr~t~ con~iC~e~ of convey~ng, lcnieading, and ~u~
de~iO 15. The follow~ng o tt;~ie~ were made on the extruder: ZoDe l; 40~C; Zones 2, 3, 4:
sooc die: 50~C (Trsr~nnt); alsid die facc plate: i~)~C. r-~nto~-.hlr~~ ~U fed at 4 ~ate of 50
I lbO/hr~
20; i Thoextrudatehada u.lilur~ t~and-lilce consiatoncywit~ an oYr~ 1 tcpl;ly.
The dle holc ~as 3.5 mm. ~rlitjs~rl and ope~ation of a ~cnife blade pPlleti7~r at the die facc
~:~u:t~d in tho form~tinn of pellots in h~n-ll~hle, ps~ E erhl.~ fo~m~. The size of the pelle~
could b~ modifiod by- adju~ting the ~eed of the pell~i7~plr~ The pollet~ cooled rapidly on the
conve3~or Ixlt.
2S
~Y~
.
, ~ ~ , .... , . . .. ~ .. . . .
CA 02236992 1998-05-07
~ENT BY:Xerox Telecopier 7020 ; 1-28-93 ; 3:00PM ; Z127536237~ 7033057718;# 5
9 6 ~ 1 2 '~ 0
1998
! 1 16
r~n~ UJ~ an 8-2-5 ~ nn~ wa8 fed ~nto the eyt~ Ar ~ ~~-q nh--d in
PY~rlrl~ 8; Zones l, 2, 3, and 4 were 3S~, 45~, SO~, and 55~C, .~pecLi.~dy; die: 6S~C; d~e
fa~ plaee: 75~C. PeJlet~ wit} cYccll~nt il~ L~ wore ol~t~;ned.
S a~ rle 10
nrnt~ r~ BTB us8d ~n FYDmrl~ 3 w~8 prwes~i a~ de~ in FY~mr4
8, oxcept the extTudcr had the following ~etti~gs, die and die face pl~tc t ~ Zone
1: S'~C; Zones 2~ 0~C; die: 65~C; di8 face plate: 60~C. The extmdate producod gave
a ~iIy formed ~ el.
lC
Ahl$E,'''r,3 ~ET
r~ ~n~ .r~
