Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1308512
Finely divided, aqueous polymer dispersions of
copolymers of vinyl halide, e-thylene and optionally additional
comonomer units are known in principle, bu-t no-t finely divided,
non-flocculated, monomodal protective-colloid-stabilizecl polymer
dispersions, preferably dispersions stabilized by polyvinyl
alcohol with a basic resin consisting of at leas-t 75~ by weight,
preferably at least ~5% by weight, of vinyl chloride and ethylene
units. of special significance ~or many applications of dispers-
ions is, in addition to the finely divided state, the absence of
partially flocculated aggregates. The absence of partially floc-
culated aggregates can be established unequivocally in this case
wil:h the disc centrifuge, whereas electron microscope pictures are
nnsuitable for this purpose.
The preparation of aqueous dispersions oE copolymers
from the monomers mentioned above by emulsion polymerization is
also known in principle. The substances necessary for the
stabilization of such dispersions such as emulsifying agents
and/or protective colloids u~ually are charged as starting
materials (cf. EP-B-590, U.S. Patent No. 4,189,415, DE-B 1,180,133
- ~ritish Patent No. 1,356,143 and D~-A-l, 770,395 -_ U.S.
Patent No. 3,816,363). Ilowever, there are also known processes
in which the polymerization begins in the absence of an emulsify-
ing agent or a protective colloid, and where these substances as
well as part of the monomers are gradually added over the course
of the polymerization (DE-s-1,520,849 3 sritish patent No.
991,536 DE-A 2,837,992 and U.S. Patent No. 4,247,438 as well as
DE-A 3,227,090 - U.S. Patent No. 4,528,315.
sut each of these su(~gested processes has the disadvant-
age that the onset of the reaction as well as the timely onset of
the various metered additions under practical conditions are often
.
~3 [)85~2
difficult to control. This causes many problems for the
adherence to important quality requirements of the application
technology. Mentioned as examples are compatiblity with cement,
behavior of t~.~ polymer film in water, the screening rejection due
to the content of coarse particles in the dispersions and other
properties controlled by the particle size or the p~rticle size
distribution such as vïscosity and shear stabi~ity.
Another frequently observed deficienc~ of the above-
mentioned processes consists of the relatively long polymerization
10 ~ times. For example, the average polymerization time of the process
examples disclosed in the DE-A-3,227,090 for pressure dispersions
e~ceeds 14 hours although, this disclosure claims "short" polymeri-
zation times as an advantage of the process. In contrastJ the
typical polymerization time of the process of the present invention
is between 7 and ~ hours.
It is an object of the invention to provide novel
improved finely divided aqueous polymer dispersions of copolymers
of vinyl halide and ethylene fr.~ of partially flocculated aggreg-
ages having improved properties.
20 ~ It is another object of the invention to provide a
very quick process for the preparation of the said aqueous disper-
sions having improved properties.
It is a further object of the invention to provide
improved adhesives, concrete additives and textile binders.
These and other objects and advantages of the inven-
tion will become obvious from the following detailed description.
-2~
13~)851Z
The novel products of the inve~tion are a finely-
divided, monomodal protective-colloid stabilized aclueous dispersion
of a copolymer o, at least 75~ by weight of units of vinyl chloride
and ethylene and optionally copolymeri~with up to 25% by weight
of units of additional monomers unsaturated at the ethylene bond
and having a solids content of 45 to 70~ by weight, characterized
in that the dispersions are not partially flocculated, the polymer
has a mean particle size of 150 to 500 nm measured as n~ean weight
in a disc centrifuge and a polydispersion index of not more than
1.8 and less than 50~ of the polymer particles are larger than
l,000 nm.
The novel process of the invention for the preparation
of the copolymer dispersions of the invention comprises: emulsion
polym0rizing: a) l to 40% by weieht of ethylene and b) 60 to 99%
by weight of at least one comonomer liquid, under the reaction
condition~ consisting essentially of: polymerizine bl) 60 to 100%
by weight of vinyl chloride, b2) 0 to 40% by weight of an
oil-soluble monomer with an ethyl0nicqlly unsaturated bond and
which is copolymerizable with a) and bl) and which is free of any
additional functional groups reactive under th0 reaction
conditions, and b3) 0 to 10% by weight of monomers having
ethylenically unsaturated functional groups and/or ethylenically
polyunsaturates in an aqueous mediu~ with a radical
initiator system in the presence of a protective colloid and
optionally an emulsifier of not more than 50% by weight of the
total weight of proteetive colloicl and emulsifier, charaeterized
in that I) the starting material charge is water, not more than
4% by weight of protective colloid andl not more than 10% by weight
based on total weight of component b) of comonomer, II) that the
earliest addition of the remaining comonomer component b) is
simultaneous to the start of pol~erization and the half-life of
--3--
13~)~151Z
of the initator is less than 10 hours, III) the earliest addition
o~ additional protective colloid and optional, emulsifier is
simultaneously with the start of polymerization and at the latest
6~ minu-tes after the start of polymerization and Iv) the polymeri-
zation is carried out at an ethylene presence of 10 to 150 bar
(1 to 1.5 MPa) and a temperature of 30 to 1009C.
One of the advantages of the process of the i~ve~tion
are the very short and reproducible inhibition times of norma,lly
3tg,,4 Fi~l~te~ and not more than 5 minutes, i.e. the period from the
addition of the initiator or from the beginning of the radical
formation to the start of the actual polvmerization reaction which
is known that it can be delayed, e.~., by cont~Nn~tion of the protective ~lloid,
the emulsifier, the monomers and other scavangers of the reaction
mixture. Comparison batches carried out according to the process
described in DE-A-3,227,090, in contrast, start with widely fluc-
tuating inhibition times. The correct point in time for the
beginning of the metering of the protective colloid or the monomer
metering becomes very difficult to determine because of this and
this leads to wide fluctuations in the quality of the final product
~c.f. the examples marked A infra). Such fluctuation~ have a
negative effect especially on a commercial-scale operation.
Although the process claimed in the DE-A-3,227,090 offers co~-
siderable advantages in comparison to conventional manufacturing
processes, one immediately recognizes the defi,ciencies of the
process because of the absence of emulsifiers andtor protective
colloids at the start of polymerization required there (e.g. with
amounts of several tons of monomers used). Examples A infra
illustrat~ the expected difficulties of this process which pro-
cess is nonetheless suitable for special scienti~ic studies on a
liter scale but not when applied on a commerical scale operation.
~3085~2
In comparison to DE-A-3,227,090, the ~ther extreme
with respect to the charging of protective colloid and emulsifier
agent as starting material are conventional polymerization processes
for dispersions stabilized with protective collids. In each of
these processes, at least a relatively l~rge amount of the
monomers and the protective colloid, or even all the protective
colloid, is charged as starting material. Here, the long and
fluctuating inhibItion periods also known to the expert occur, on
the one hand, with the dispersions claimed here based on vinyl
chloride/ethylene copolymers and, on the other hand, the control
of the reaction after the start of the reaction becomesdif~icult,
even with carefuI adherence to all usually controllable boundary
conditions.
Whilè stable, but ~ot finely d~i~ided dispersions in the
sense of the present invention can be obtained in some of such
batches, which axe satisfactory also with regard to the processing
parameters such as viscosity, the other, frequently predominant
portion yields completely unsatisfactor~ results, e.g. scatter of
important parameters such as viscosity i~ an uncontrollable manner
despite identical formulation, i.e., the dispersions become highly
dila~tor they coagulate.
Thus, dispersions based on copolymers based on vinyl
chloride and ethylene can be prepared in principle according to the
conventional processes, but these products lack in almost all
instances the elementary prerequisites for a technical application
since they do not meet the required spectrum of properties. In
many cases, the amount of coarse particles or the screen oversize
of the dispersion is too great and they cannot be reproduced in
uniform quality under commercial manufacturing conditions with the
necessary certainty.
--5--
13C~8~;~2
~ hese kno~n interrelations are one of the important
reasons for the infrequent commercial availahility of plastic
dispersions based on vinyl chloriae and ethylene stabilized with
protective colloid, especially PVOH-stabilized, despite their
technically interesting spectrum of properties and their favorably
priced raw material situation. These deficiencies have been
surprisingly well solved with the dispersi~s of the invention which
dispersions based on vinyl chloride and ethylene are stabilized by
protective colloids and have a l~scre~n oversi e, cvers, fail ~ and have the
required spectrum of properties also with commercial dimensions
and are characterized by a very unïform product quality. An~ther
advantage of the preferred process of the invention is the short
inhibition and polymerization times as well as the very good
control of the reaction conditions.
Finely divided means dispersions that have a mean
particle size (diameter), measured as mean weight in a disc centri-
fuge, of at least 150 nm and not more than 500 nm, preferably at
most 400 nm and especially preferred at most 350 nm. Dispersions
that have a maximum in the particle size distribution and have a
polydispersion index of not more than 1.8 are called monomodal.
The disc centrifuge is an analytical instrument for the
determination of the particle size distrib~tion of very small
particles manufactured and sold, e.g., by Joyce Loebl Ltd.,
Princesway, I.V.T.E., Gateshead NE 11 OU~, Englan~ (Gs1~ This
method utilizes the strong forces in the centrifugal field of a
disc-like hollow cylinder filled with the sample liquid and rotat-
ing at very high speeds. The action and evaluation of the disc
centrifuge are described in detail in the operating instructions
and application reports by ~oyce Loebl~
The disc centrifuge is an estab~ish~d and widely used
--6--
~3~35~2
method for the determination of the partiCle si7e distribution
of particles dispersed in liquids ~nd the disc centrifu~e measures
the hydrodynamic radius of the particles in the dispersed state
in the fluid and thus provides unequlvocal information about
possible associates and flocculates of individual particles.
Dispersïons of identical empirical compositions can have a com-
pletely different colloid chemical structure. An important point
in this context is the formation of flocculate structures or their
absence since this colloid chemical structure critically controls
many important application technological properties of dispersions
such as viscosity, setting power, wet abrasion resistance, to
mention just a few~ These structural differences turn seemingly
"identical" dispersions into respectively exactly specifyable,
individual systems of substances. Protective-colloid-stabilized
polyvinyl ester dispersions known to date are typically inter-
mediate to coarse-disperse and contain the polymer in the dispersed
state mainly as flocculates.
Electron microscope pictures are not suitable since it
always involvessamples dried under ultra-high Yacuum that naturally
no longer permit any information about the degree of flocculation
in the dispersed state and Figs. 5,6 and 7 illustrate these con-
nections clearly. Whereas the electron microscope picture of the
sample registers the individual particles at approx. 0.3 ~m, the
evaluation of the disc centrifuge recording showns that the dis-
persion itself is actually almost completely flocculated with
particle sizes of about 3 ~m. Thus electron microscopic pictures
(EM pictures) not only are unsuitable for the description of floc-
culate conditions, but they frequently give rise to misinterpretat-
ions (cf. the EM-pictures Figs. 2 and 3 or 6 and 7~ resp~, with the
corresponding disc centri~uge evaluations Figs. 1 a~d S, resp.).
-7-
~3~851 2
"Free o~ ~occulates or partial ~occulates" means a
cumulative frequency of the particle size in the disc centrifuge
in which less than 50~ by weight, preferably less than 20~ by
weight, of the particles exceed 1,000 nm and this particle size
limit lies preferably at not more than 700 nm, especiall~ not more
than 500 nm.
These correlations are explained graphically in Fig, 1.
The at first inspection, high va~ues for the admissibilit~ of
"coarse particles" result from the fact that in the cumu~ati~e
frequency of the particle weights even minute contents of coarse
particles cause a very strong shif t in the cumuIative frequenc~,
although the content is numerically so small that it can actual]~
be neglected. Fig. 4 illustrates this. The ratio of weight aver-
age to number average (the polydispersion index) of the disc
centrifuge can be used as an additional parameter for the group of
claimed substances. It is 1.8 at most, preferably 1.5 at most and
especially preferred 1.3 at most.
For dispersions with monomodal partïcle size distri-
bution, the NANO-SIZER(R) of COULTER ELECTRONICS LTD., Harpenden,
Herts, England (GB), is another instrument available for the
determination of the particle size which is independent of the
method of determination with the disc centrifuge, but particle
size distributions cannot be obtained with the NANO-SIZER. ~ith
a polydispersion index (PD) of more than 2, the recording of a
NANO-SIZER particle size loses its in~ormative power. POls >3
indicate~ fluocculates or bimodal distributions, but yield a "mean
value" of the particle size in the determination with the NANO-
SIZER IR) which no lon~er has an~ information content.
The substances o~ the invention can be definitively
characterized by the parameters shown above. Monomodal, finely
--8--
~3~8S~Z
dispersed PVOH-st~,bilized dispersions differ significantly in the~r
colloid chemical structure, e.g, in, their inter~al surface an,d
therefore in their nature and their properties from the known, at
least partially flocculated dispersions of ide~tical or similar
empirical composition (cf. e.g. Fig. 8).
A pre~erred, improved process for the preparation of
such aqueous copolymer dispersions by emulsio~ polymerization of
a) 1 to 40% by weight ethylene and
b) 99 to 60~ by weight of at ~east one comonomer liauid under the
conditions
in an aqueous medium with a radical initiator system in the
presence of a protective colloid and maximally 50% by weight, pre-
ferably at most 30% by weight and~especial~y preferred without
emulsifier, (amount of emulsifier calculated with regard to the
total amount of protective colloid and emulsifier)wherein the
comonomer phase consists of
b 1) 60 to 100%, preferably at least 85%, more preferred at least
95~, especially 100% by weight of vinyl chloride.
b 2) 0 to 40~, preferably not more than 15%~more preferred not more
20 ~ than 5% by weight of oil-soluble monomers unsaturated
at the ethylene bond and copolymerizable with a) and
b 1), which contain, with the exception of the one
ethylene bond double bond, no other functional
groups active under the reaction conditions~ and
b 3) 0 to 10%, by weight of functional monomers unsaturated at the
ethylene bond and/or monomers polyunsaturated at
ethylene bonds, i5 characterized by the polymeriza-
(tion being carried out in such a way that
I togethe~ with water and, if needed, at least a part
of the usual additives such chain transfe,r a~ents as re~ators)
_g_
;1Z
and buffer substances, not re than 4% by weight preferably
not re than 2.5% by weight, especially preferred not more
than 1.2% by weight and particularly maxi~lly 0.6% by weight,
calculated with respect to the total weightof component b),
of protective colloid, preferably, PVOH, especially without
any addition of ~lulsifier, in which case the charged amount
of protective colloid and emulsifier is preferably not more
than 40% by weight of the total an~unt of protective colloid
used and,optionally, of em~lsifier, and not more than 10%
by weight, calculated with respect to the total weight of com~
ponent b, preferably not re than 5% by weight and
especially no comonomer at all are initally placed in the
reactor.
II. The addition of the remaining amount of comonamer component
b begins at the earliest simLltaneously with the possible
start of the polymerization, which in the case of a redox
initiation is understood to mean the presence of reducing
and oxidizing component of the initiator system in the reac-
tion vessel and for the case of thermal initiation, the reac~
ing of a~ internal temperature in the reaction vessel by
exogenous heating, at which the half-life of the initiator
is less than 10 hours, preferably less than 5 hours.
III. the addition of additional protective colloid starts at the
earliest simultaneously with and not later than 60 nunutes
after the possible start of polymerization and that the
reactions' carried out at an ethylene pressure of
IV. 10 to 150 bar, preferably
-10-
~3 [)85~Z
o~ 30 to 80 bar, and temperatures of 30 to 100C,
prefer~bly 45~C to 80C~
The claimed process is performed as an emulsion poly-
merization and all conventional additives such as emulsifier!protective colloids, initiators, reducin~ agents and regulators
can be used in usual amounts for the emulsion pol~merization~ In
this case, they may be added either to the starting materials or
in portions or by a more or less continuous me-terïng, as desired~
unless it is excluded by the de~inition of the fnvention. H~wever~
- the polymerization is performed preferably in the invention i~ the
absence of emulsifier.
The polymerization is initiated by methods normally used
for emulsion polymerization. Especially suitable are at least
partially water-soluble, preferably completely water-soluble,
inorganic or organic peroxide compounds such as peroxo compounds
and hydroperoxides as well as water-soluble azo compounds. It is
understood that the radical formation ~c~ng place in the a~ueous
phase is crucial for the emulsion polymerization (cf. Kirk-Othmer,
Encyclopedia of Chemical Technology, 3rd edition, volume 18, pp.
742-743). The said peroxide initiators can also be combined with
reducing agents in a well-known manner, if needed and such redox
systems are preferred. Frequently, the known addition of small
amounts of heavy metal compounds, e.g. iron-lI-salts, is preferred.
The pH-range for the pol~merization, which generally
is between 2.5 to 10, especially 3 to 8, can be kept constant by
a well-known method using suitable buffer systems, e.g. phosphate
or carbonate bu~er.
The ratio of charged to subsequently added protective
colloid or emulsifier as well as the total amounts of these com-
ponents may vary. Both quantities ser~e to obtain the technolo-
gical application property spectrum required of the dispersion
-
~L3Q8S12
and may be adjusted according to these requirements. Usually,
0.1 to 4~ by wei~ht, preferabl~ 0.3 to 1~2% by wei~ht, ~f the
protective colloid and, if needed, emulsifier are charged as
starting material, calculated with respect t~ co~ponent b. Pre-
ferably, the protective colioid without emulsifier is charged and
the total amount of protective c~lloid ~nd emulsifier range from
5 to 18%; preferably from 7 to 13~L ~nd especially from 8 tQ 1?%
~y weight, ~alculated with respect t~ the CQmpO~ent b)~
The amount of emuIsifier Ica~cu~ated wit~ respect tQ
~ the total amount of protective colloid and emuIsifier used) is
at most 50% by weight, pre~erably not ~ore than 30~ by weight and
in an especially prefer~ed formul~tion, ~nly protective colloid
without emulsifier is used.
In the preferred practical example, the reaction vessel
contains only water, a small amount of protective colloid, a
small amount of an initiato~ component (generally 10 to 20% ~y
weight, calculated with respect to the total weight of this
initiator component) and optionally the stalts necessary for the
adjustment of the desired pH-value and for buffering and option-
ally catalytic amounts of salts of heavy metals prior to the
start of the polymerization reaction. In a specific practical example,
iner~ organic substances in total amounts of 0.1 to 15% by weight
calculated with respect to the total weight of component b)may be
added also to these starting materials. These inert organic sub-
stances possess water solubiliti.es of 10 3 to 200 g per liter and
molecular weight of not more than 1,000. Examples of suitable
compounds are mentioned, for example, in the EP-A 76,511, and
specific reference is made to the disclosure referring to this.
Possible, but not preferred, is also the addition of comonomers
in amounts of up to 10% by weight (calculated with respect to com-
ponent b), especially up to 5% by weight of the starting materials.
-12-
~ 3~Sl;2
The addition of the comonomerls), i.e, component b~
~egins preferably not ea~lier than simultanelusly with the in-prin-
ciple possible start of polymerizationr e.g. at constant meterino
rate or pre~erably ln relation to the consumption. Usually, the
reaction ïs complete 60 to 180 mlnutes a~ter thè end of the meter-
ing of the comonomers.
The addition of the protectivè colloid not added ~s start-
ing material and emulsifier begins also not ear~ier than simult-
aneously with and not later than 60 minutes after the possible
start of polymeriz'ation. The meteriny of p~otective collQid or
emulsifier and the metering of monomer d~ n~t have to begin or ~,,
stop simultaneously, but protective colloid an,d emulsifier are
preferably also metered in relat;o~ to their consumption in this
case. In a preferred practical example~ the comonomers and
protective collid and optional emulsi~ier are added in a premi~ed
form, e.g. especially preferred as pre-emu~sion,.
In the process of the in,vention, the ethylene can be used `
preferably in part or en,tirely as starting material i.e., the
intended ethylene pressure can be built up during the course of the
polymerization, however not later than tke complete polymerization
of the starting material, or by obtainin,g a conyersion correspo~d-
ing to the starting material, preferably not later than at the
beginning of the comonomer metering. The ethylene pressure can be ~ ,,
varied, i.e. increased and/or decreased, at will within the
mentioned limits during the polymerization, optionally ~so several
times. Preferably, hQwever, it is kept constant during most of -;
the time of como~omer mete~ . Subse~uently, the addition of -
ethylene is preferably stopped.
Especially vinyl chloride is'to be ~entioned as comonomer
(component b), which accounts for at least 60% by wei~ht, preferably
-13-
13C~8S~Z
at least 85~, especially at least 95% by weigkt, o~ component b).
As additional comonomers that are oil-soluble and copolymerizable
with ethylene and vinyl chloride ca~ be mentioned (component b 2)
are esters with unsaturated ethylene bon~ssuch as allyl and pre-
ferably vinyl esters of carboxylic acids that are not
ethyl~nically unsaturated,preferably saturated straight-chain~ branched
or cyclic, especially alkanoic acids o~ 1 to 20 carbon atoms such
as vinyl acetate, vinyl propionate, v~inyl butyrate, ~inyl 2-ethyl-
hexanonate, vinyl laurate, vinyl stearate, vinyl esters of hi~hly
branched carboxylic acids, which may be prepared, e.g., by the so-
called Koch synthesis from olefins and carbo~ monoxie (so-cal~ed
Versatic(R) acid vinyl esters) such as mono- and dialkyl esters of
carboxylic acids unsaturated at the ethylene bond~ especia~ly
those from alcohols of 1 to 18, preferably ~ to 8 carbon atoms,
with ~,~-unsaturated monocarboxylic acids of 3 to 8 carbon atoms
such as methyl esters of acrylic, methacrylic and crotonic acid,
the ethyl, propyl, butyl, 2-eth~lhexy~, lauryl and stearyl esters
of these carboxylic acids, dialkyl esters of dicarboxylic acid of
4 to 10 carbon atoms unsaturated at the ethylene bond, e.~. the
esters of the mentioned alcohols of 1 to 18 carbon atoms with
m~leic acid, fumaric acid, and itaconic acid, as well as ~-olefins,
e.g. propylene, butylene, styrene and vinyltoluene~ vinyl ethers
and vinyl ketones; vinyl halides such as ~inyl fluoride and ~inyl
bromide; and vinylidene halides, e~g. vinylidene chloride.
Preferred are the mentioned esters, especially the vinyl
esters, the esters of acrylic acid, methacrylic acid, maleic acid
fumaric acid and the halogen derivatives of ethylene. Especially
preferred are the mentioned esters. These monomers which are
monounsaturated at the ethylene bond an~d do n~t enter into any
further reactïons, e.g. do not have any cross~linking e~fect, which
-14-
- . ~
13 E)~3512
c~n be used singly or as mixtu~, are contained in the comonomer
component b) in amounts of not more than 40% by weight, preferably,
not more than 15~ by weight, especially not at all.
Further~ other addition~l monomers copolymerizable with
the other monomers can be contained in the comonomer component bJ
in amounts of o to 10% by weight. such mon,omers are those that
have functional groups or are polyunsaturated at the ethylene
bonds. Preferred are the functional monomers. These are under-
stood to include compounds that have in addition to an ethylene
double bond also carboxyl (-COO~Ior _-Coo lj, sulfonate, epoxide,
hydroxyl or, if needed, amide radicals substituted ~y e.g., alkyl,
hydroxyalkyl, alkoxyalkyl, alkanoyl,, or alkanoyla,lkyl.
Examples of these are: acrylic acid, methacrylic acid,
itaconic acid, fumaric acid and maleïc acid, their alkali or
ammonium salts, their glycidyl esters, their mono- or diamides~
especially acrylamide an,d methacrylamide which can be mono- or
disubstituted at the nitrogen by alkyl of 1 to 4 carbon atoms and/
or by methylol which in turn~ can also be etherified by alkyl
or esterified with alkanoic'acids,monoesters o~ the mentioned
dicarboxylic acids with alkanols of 1 to 8 carbon atoms, ~inyl and
allyl sulfonates, mentioned previously.
As ~xamples of polyunsaturated monomers are vinyl and
allyl esters of unsaturàted monocarboxylic'acids of 3 to 8 carbon
atoms, as well as m,ono- or di~inyl and allyl esters of saturated
or unsaturated dicarboxylic acids of 4 to 10 carbon atoms, triallyl
cyanurate and di-'and polyesters of ~ unsaturated aarboxylic
acids with polyfunctional alcohols.
Frequently such mon,omers of ~roup ~) ~, eSpecial~y those
readily soluble in water such as the carboxylic acids, their salts
and their amides and espe~ally preferxed the suI~onates are added
-15- '
~ L3 ~ ~ 5~LZ
preferably only in amounts of up to 2% by weight, since they are
used to improve the stability of the dispersion. Monomers through
which the later-cross-linking can occu~ such as N-methylol(meth~
acrylamide frequently are added preferably in amounts up to 5% by
weight. The mentioned figures in welght ~ are always calculated
with regard to the total weight of the respecti~e comonomer com-
ponent b).
Preferred as como~omers are mi`xtures of ~înyl acetate
with vinyl chloride and especially ~in~l chlori*e ~lone. An
addition of water-soluble monomers ;s often~ superfluous and is
therefore not m~de according to an especia~y preferred practical
example.
The em~lslfiers and protective colloids suitable for the process
of the invention are known to the expert. In principle, alnost all surEace
active substances are suitable for use in the emLlsion polymerization. Techno-
logical application requLrem~nts, mcnomers used and reaction conditions deter-
mine the choice in the individual case. Emulsifier and protective colloid,
especially PVOH without any em~lsifier addition, are used in am~unts of 0.5
t~ 15% by weight total, preferably of 3 to lO~ by weight, calculated with
respect to the monomers that are liquid at the reaction conditions (cc~ponent b).
~hen additionally, comonomers are used wnich are known to have a stabilizing
effect on the dispersion (e.g. vinyl sulfonate~, even the small addition of
approx. 1 to 3% by weight protective colloid and emLlsifier can give good
results. The addition of protective colloid and of emulsifier as starting
material is preferably not re than 40% by weight, re preferred not more
than 25% by weight, especially not more than 10% by weight of the total amount
of protective colloid and optional ~11 sifer.
The protective colloids are those generally used for poLy~
merizatiOn such as cellulose derivatives or water-soluble polymers
like partially saponified polyvinyl acetate (polyvinyl alcohol) or
-16-
13~1 !35~2
vinylpyrrolidone polymers. Preferred is polyvin~l alcohol with a
degree of hydrolysis of 70 to 99.8 ~ol% (correspondin~ to a saponi-
fication number o~ approx. 10 to approx. 257), preferably 74 to
99.5 mol% (corresponding to saponfication numbers of approx. 20
to approx. 240) and with a mean degree of polymerization of 200
to 300 (corresponding to ~ vlSCOsity of a 4~ by wei~ht a~ueous
solution at 20C o~ approX. 3 to approx. 50 mPa.s.).
The use of mixtures of ~i~ferent protective colloids is
possible such as mixtures of PYOH's of higher and lowe~ viscosities
or higher and lower saponification. Also possible is the addition
of one or several of these protective col~oids earlier ïn the pro-
cess and one or several other(s) ~ater. It is known that pol~mers
generally have a certain band width in theix composition~ i.e.~
a given polyvinyl alcohol characte~ized by the properties above
does not consist of a single molecular species only.
Although systems without emulsifiers are pre~erred,
anionic and/or nonionic emulsifiers in amounts of not more than 50%
by weight, preferabl~ not more th~n 30% b~ wei~ht and more pre-
ferably not more than 10% by weight, calculated with respect to
the total amount of emulsifier and pxotective colloid~ ma~ be used
as well, if needed.
A classification of emulsifiers acceptable for the pro-
cess of the invention according to their chemical nature can be
found, e.g. in Stache, "Tensid-Taschenbuch", pp. 159 ~f.,
Muchen 1979.
If emulsifiers are to be used at all, especially the
followinq types of a~ionic tensides are suitable for the emulsion
polymerization process of the invention-
1. Alkyl sulfates, especially those with a chain length o~ 8 to
18 carbon atoms, alkyl and alkylarylether sUl~ates of 8 to 18
-17-
~3Cl!85~2
carbon atoms in the hydrophobic group and 1 to 40 ethylene
oxide or propylene oxide units (EO- or PO-units).
2. Sulfonates, especially alkyl sulfonates of 8 to 18 carbon
atoms, alkylaryl sulfonates of 8 to 18 carbon atoms, taurides,
esters and semiesters of suIfosuccinïc acid wïth monovalent
alcohols or alkylphenols with 4 to 15 carbon atoms; iE desired,
these alcoho~s or a~kylphenols can also be ethoxylated with 1
to 40 ethylene oxide (EO-) units.
3. Alkali and ammonium salts of carboxylïc acids of 8 to 20 carbon
- atoms in the alkyl, aryl, a~kylaryl Qr aralkyl.
4. Partial esters of phosphoric acid and their alkali and a~monium
salts, especially alkyl or a~ka,ryl phosphates of 8 to 20 carbon
atoms in the organic radical, alkyl ether or a~kyla~l ether phos-
phates of 8 to 20 carbon atoms in the alkyl or a ~ La~yland 1 to
40 EO-units.
Suitable no~ionic tensides are especially~
5. Alkylpolyglycol ethers, preferably,wit~ 8 to 40 E~-units and
alkyl of 8 to 20 carbon atoms.
6- AlkylanyL~ glyc,ol ~ ethers, prefer~b~ ~ith 8 to 40 EO-units and
8 to 20 carbon atoms in the a,lkyi and aryl.
7. Ethylene oxide/propylene oxide (EO/RO) blocl~opol~Jmers mass. pre-
ferably with 8 to 40 EO- or PO-units.
As mentioned above, the polymerization, is initiated, pre-
ferably with so-called redox initiator systems which ~enerally
consist of a combin,ation of at least one peroxide compound and at
least one reducing agent. One of these components can be charged
entirely or partially as star~ material, the other component and,
if appropriate, the rest of the component partially used as starting
material or, if appropriate, both components, are then metered
during the course of the polymerization. Prefexred is the charging
-18-
13~851Z
of a small amount of the reducing component as starting material.
Generally, the reducing component is used in an amount
of approx. 0.01 to approx. 0.5% by weight, preferably 0.3 to 0.5%
by weight, and ~he oxidizing componen~ in an amount of approx.
0.01 ~o approx. 2~ by weight, prefer~bly 0.03 to 0.8% by weight.
Especially good results are often obtained when ~he molar ratio of
oxidizing component to reducing component is between 0.5 and 4.
When the polymerization is thermally ~utiate~, the rêc1uc~ agent can
be omitted. The above percen~ are calculated with regard to
the respective total ~eight of componet b~.
Preferred examples of the oxidizing components are the
following peroxide compounds: Ammonium and potassium persulfate,
ammonium and potassium peroxidisulfate, hydrogerl peroxide, alkyl-
hydrope~oxi~. such as tert-butyl hydroperoxide, peroxodiphos-
phates such as potassium, sodium and ammonium peroxodiphosphate.
Instead of the peroxide compounds, azo compounds can also be used,
e.g. azobisisobutyronitrile or azobiscyanovalerianic acid.
Preferred examples of the reducing component are com-
pounds of sulfur in which the sulfur is not present in its formal
degree of oxidation of +6. Especially mentioned are water-soluble
sulfites and sulfoxylates such as alkali metal (Na, K) or zinc
formaldehyde sulfoxylate or sodium and potassium sulfite and bisul-
f ffl ~. Frequently, the catalysis by the addition of traces of suit-
able salts of heavy metals, such as Fe2+, is indicated. Suitable
initiator systems are described, a.o., in "Fundamental Principles
of Polymerization", G.F. Alelio, John Wiley and Sons Inc.,
New York, 1952, pp. 333 ff and in DE-~-ll 33 130.- US-A-3145194)
The copolymers of the invention have preferably K-values
(according to DIN 53 726, measured in THF/H2O 95:5) of 20 to 100,
especially preferred 30 to 80, most especially 35 to 70. The
-19 -
~308s~
minimum film forming temperatures generally are not more than
25C, frequently not more than 0C, depending on the ethylene
content.
The polymer dispersions or polymers prepared
according to the invention and containing mainly vinyl
chloride and ethylene can find use in all areas for which the
known co- and terpolymers of vinyl ester/vinyl
chloride/ethylene are suitable. For example, the dispersions
of the invention can preferably be used for the preparation of
dispersion powders (redispersible powders), of wood glue,
adhesives for paper, plastic foils or leather which are
characterized by especially short reaction times, and as
binders for textiles or as concrete additives.
The invention is explained with the following
examples and comparison tests and the examples are separated
into three groups, of which Group A describes tests that were
~erformed according to DE-A-3,227,090 which examples should be
compared especially with exampels C8 to C12. Group B is used
as comparison with other protective colloid-stabilized vinyl
chloride/ethylene dispersions prepared by "classical" methods
and in Group C, the claimed invention is explained further.
The polyvinyl alcohol used in the examples is
described in leaflets of the company WACKER-CHEMIE GmbH, D-
8000 Munich, (DE) generally used for their POLYVIOL(U) types
with the number preceding the slanted line identifying the
viscosity in mPas (Hoppler viscosity of a 4% solution,
measured at 20C), the number following the slanted line being
the saponification number (according to the consumption in mg
of KOH/ 1 g of substance). The viscosity of the dispersions
is recorded in mPas together with the measuring equipment used
~BROOKFIELD* viscosimeter or EPPRECHT* rheometer) and the
characterization of the shear gradient known to the expert
(e.g. Bf 20 - Brookfield*20 rpm, Rheo C III =
JJ:jrc 20
*Trade-mark
~36~1851Z
Epprecht, beaker C, measuring stage 3~. D~s~ (1) etc. identifies
the various metered additions of reaction partners and additives.
Unless other~ise explained, data i~ % always refers ~o
the weight. Solutions are always aqueous solutions unless stated
otherwise. The following abbreviations and trademarks are
identified as follows:
APS = ammonium persulfate
VC = vinyl chloride
VAC = vinyl acetate
E = ethylene
KPS = potassium persulfate
Bruggolit(R) = sodium formaldehyde sulfoxylate
Rongalit(R) = sodium formaldehyde sulfoxylate
Arkopal(R)N 230 = nonylphenylpolyglycol ether with approx. 23 EO-
units
Genapol(R)X 150 = isotridecanol etherified with approx. 15 EO-units
t-BHP = tert-butylhydroxyperoxide.
In the following examples there are described several
preferred embodiments to il1~1~a~ the invention. However, it
should be understood that the invention is not intended to be
limited to the specific embodiments.
EXAMPLE A 1
1,300 g of completely demineralized water were placed in
a 16 liter autoclave and the pH was adjusted to 3.7. The chamber
was evacuated, the agitator set at 500 rpm, N2 was introduced to
rinse the autoclave which was evacuated again. Then,362 g of
~AC and 1,088 g of VC were added. The internal temperature regu-
lator was set at 43C and ethylene was added to a pressure of 55
bar. Once equilibrium was established, Dose (1) (an 8% solution
of APS) and Dose (2) (a 4% Bruggolit solution) were fed at a rate
30 of 65 g/hour. Twenty minutes after the start of the reaction,
-21-
13~3512which was difficuIt to observe, Dose (4) (a mixture of 1,430 g of
water, 2,047 g of an 8.5~/o Polyviol( ) W 28/70 sol.ution, 26 ~ of
a 25% vinyl sulfonate solution and 479 g of a 25% Arkopal(R)-N-230
solution) was added over 6 hours at a rate of 660 g~hcur. Starti~g at a
solids content between 25% and 30%, a more exact reading was not
possible because Of the difficultly to control the operation, Dose
(3) (1, 335 g of VAC and 4,000 g of VC) were metered for 5.5 hours
and the ethylene pressure was gradually increased to 60 bar over
this time.
The pH was maintained between 3.6 and 4.0 by addition
of ammonia and once the final solids content was reached, ap~rox.
4 - 5 hours after the end of Dose (3), the pH was adjusted to 7.5
and the pressure was released from the reaction mixture and the
residual manners removed.
EXAMPLE A 2
Example A 1 was repeated in an identical manner.
EXAMPLE A 3
Example A 1 was repeated in an identical manner.
EXAMPLR A 4
Example A 1 was repeated with the`following changes:
1,400 g of completely demineralized water, 7.5 g of VAC and 225 g
of VC and 0.6 g of allyl methacrylate were placed in the reaction
vessel. Dose (2) (a 5.5% Rongalite(R) solution) was metered at a
rate of 60 g/hour, Dose (3) consisted of 1,625 g of VAC, 4,875 g
of VC and 13 g of allyl methacrylate. Their addition began 10
minutes after the onset of the reaction and lasted 5 1/2 hours.
Dose (4) was a mixture of 2,916 g of an 8.5% by weight Polyviol(R)
W 28/70 solution, 1,258 g of a 20% Polyviol(R) G 04/140 solution
and 200 g of water. Its addition began 10 minutes afterthe start
of the reaction and lasted 5 1/2 hours.
-22-
~311D85~Z
EXAMPLE A 5
_ .
Example A 4 was repeated in an identical manner.
EY~MPLE A 6
A 16 liter autoclave was charged with 900 g of water
and 500 g of KPS and the pH value was adjusted to 3.5 and stirring
was started. Then, the autQclave was evacuated, rinsed with nitro-
gen,again evacuated and a mixture of 322 g of VAC and 968 g of VC
was fed in by suction. The temperature regulator wa~ adjusted to
40C and ethylene was added to a pressure of 55 bar. After
reaching temperature equilibrium, Dose (~) (a 1.5% Rongalit(R)
solution) was started at 50 g/hour. Twenty minutes after the start
of the reaction, Dose (4) (a mixture of 2,700 g of an 8.5V/o Poly-
viol(R) W 28/70 solution, 2,785 g of an 11% Polyviol(R) M 13/140
solution and 65 g of a 30% solution of GENAPOL(R) X 150) was metered
at a rate of 620 g/hour ~ver 9 hours. Starting one h~lr after the
start of the reaction, Dose (3) (1,225 g of VAC and 3,675 g of
vinyl chloride) was added over 8 hours at a rate of 600 g/hour.
The pH was maintained between 3.5 and 4.0 during the reaction.
After the completion of Dose (3), the metering of Dose (2) was
continued until the same solids content was reached twice and
after the pH was adjusted to 7, the pressure was released and the
resi~ual manner was removed.
EXAMPLES A 7 to A 9
Example A 6 was repeated in an identical manner and the
stirring was reduced from 200 to 140 and 120 rpm respectively, in
two trials.
The analysies of Examples A 1 to A 9 are recorded in
Table I.
EXAMPLE A 10
A 16 liter autoclave was charged with 100 mg of
-23-
~3085~Z
ferroammonium sulfate, 1,sso g of water and 1,150 g of VC and
the pH was adjusted to 4.5. The autoclave was evacuated and
rinsed with nitrogen. After another evacuation, the
temperature was increased to 500c and ethylene was added to a
pressure of 65 bar. This pressure was kept constant to the
end of metering component b), then the ethylene valve was
closed. Shortly before heating, 100 ml of Dose (1) (a 3% t-
BHP solution) were added. Five minutes after reaching
ethylene equilibrium, Dose (1) and Dose (Z) (a 3% RONGALIT~
lo solution) were started at 1~0 g/hour, respectively. Ten
minutes after the start of the reaction, which was difficult
to identify, but started approx. 30 minutes after the
beginning of both metered additions, a sample for solids
content was removed and it had a solids content of 13%. Then,
the metered addition of a mixture of 1,150 g of water and
4,200 g of a 20% Polyviol~) G 04/140 solution was started [Dose
(4), 900 g/hour]. Starting fifteen minutes later, Dose 3
(6490 g of VC) was added at a rate of 1,100 g/hour. Then, the
conversion was kept constant by adjusting the metered
additions of (1) and (2). After the completion of monomer
addition, Dose (1) and Dose (2) were added to the end of the
reaction. Then, the pressure was released and the dispersion
was freed of residual VC by evacuation.
Example A 10 is identical to Example C 12 in its
overall composition, but the process was adjusted to the
conditions of DE-A-3,227,090 in Example 10. At 51%,
relatively coarse, strongly speckly dispersion was obtained
and its analyses are recorded in Table 2. The entire spectrum
of characteristics for the dispersion did not meet the
standards of the present invention.
EXAMPLE_A 11
Example A 10 was repeated, but the beginning of
additions (3) and (4) was moved to an earlier time to adjust
to a more
JJ:jrc 24
;
~3~ Z
monomer-rich mode of operation than in comparison to Example
A 10. However, the batch started poorly despite the addition
of ferroammonium sulfate, i.e., only approx. 3 hours after the
beginning of the initiator addition. Des~ite the more monomer-
rich mode of operation, no product was obtained that had
characteristics comparable to those of Example C 12 of the
invention. The analyses of this also strongly dotted dispersion
are also found in Table 2. The disc centrifuge pictures of
Examples A 10 and A 11 that are not according to the invention
and of Example C 12 of the invention are found in Fig. 8.
EXAMPLE B 1
.
This example is a "classical" vcrsion for the prepara-
tion of PVAL-stabilized vinyl ester dispersions and the quantita-
tive composition again corresponded to Example C 12 of the inven-
tion. The method differed from ~h~ late eY~le in the foll~ng
points: The entire amount of PVAL was charged as starting
material and 15% of the total comonomer was charged as starting
material while 85% was added by metering. The details of the run
were carried out as follows:
20` A 16 liter autoclave was charged with 3,130 g of water
and 4,2Q0 g of a 20% Polyviol(R) G 04/140 solution and after
evacuation and rinsing with nitrogen, the evacuation was repeated.
Then, 1,150 g of VC were added by suction and the stirrer was
started. The temperature was raised to 50C and ethylene was added
to a pressure of 68 bar and this pressure was kept constant until
the end of the addition of the monomers. Then, the ethylene valve
was closed.and the pH value was adjusted to 4.3 and kept constant
during the subsequent reaction. The reaction was started with the
metered addition of a 3% t~BllP- solution (Dose (1~ at 150 g/hour
and a 5% RONGALIT(R) solution ~Dose (2)] at 150 g/hour. Thirty
-25-
~ 308~;~2
minutes after the start of the reaction, Dose (3) ~6,500 g of VC)
was started at a rate of 1>100 g/hour. Subsequently, the course
of the conversion was kept uniform by varying of Dose (1) and Dose
(2) accordingly. At a solids content of appro~. 46%, hydro -
static pressure was observed, a typical sign of a very deficient
copolymerization of ethylene. The reaction was then stopped and
even at this low solids constent the DISC eva]uation (Fig. 9)
showed that the dispersion did not meet the quality standards
EXAMPLE C 1
~ 16 liter autoclave was charged with 237 g of a 15%
polyviol(R) M 05/140 solution, 2,680 g of completely demineralized
water and 208 g of dioctyl sebacate (DOS) and the pH was adjusted
to 4.2. The autoclave was evacuated and rinsed with nitrogen.
After renewed evacuation, the temperature was raised to 50C and
ethylene was added up to a pressure of 68 bar. This pressure was
kept constant to the end of the metered addition of component
b and then the ethylene valve was closed. Before the start of
the reaction, 20 ml of a 5% Rongalit(R) solution were also charged
as starting material.
The metered additions of Dose (3) (vinyl chloride) at
a rake of 1,300 g/hour, Dose (1) (~l% t-BHP solution) at a rate
130 g/hour and Dose (2) (6% BONGALIT(R) solution) at a rate of
150 g/hour were started simultaneously and addition of Dose (4)
(a 15% Polyviol(R) M 05/140 solution) at a rate of 1,000 g/hour
was started 30 minutes later. The metered additions (3) and (4)
lasted for 4.5 hours at a constant rate and metered addition (1)
lasted for a total of 6.5 hours, and the rate of addition was at
the latter gradually decreased depending upon the conversion. The
reaction started within 8 to 10 minutes after the beginning of initiator
addition. The pH was maintained between 3.8 and 4.2 by addition
-26-
~308~;~2
of ammonia and after the end of the metered addition of
initiator, the batch was freed of residual vinyl chloride and
ethylene by releasing the pressure and evacuating for one
hour. The final dispersion had a solids content of 50.0% and
the polymerization time was 6.5 hours.
EXAMPLE C 2
Example C 1 was repeated with the following
changes: no DOS (dioctyl sebacate~ was used, 3 g of sodium
acetate were added to the charged starting material for
buffering of the pH, the metered addition of Dose (4)
consisted of 1,130 g of water, 2,830 g of a 20% solution of
Polyviol~) G 04/140 and 907 g of a 25~ solution of a
nonylphenylpolyglycol ether with approx. 23 E0-units (ARKOPAL(R~
N 230). the final dispersion had a solids content of 53% and
the polymerization time was 8.5 hours.
EXAMPLE C 3
Example C 1 was repeated with the following
changes: in metered addition of Dose (4), the Polyviol(R) M
05/140 was replaced by Polyviol(R) M 05/180 and a 49.8%
2G dispersion was obtained.
EXA~PLE C 4
Example C l was repeated with the following
changes: in metered Dose (4), the Polyviol(R) M 05/140 was
replaced by Polyviol(R) M 05/60 and a 49.4% dispersion was
obtained.
EXAMPLE C 5
Example C 1 was repeated with the following
changes: a 5.5% ammonium persulfate solution was used as Dose
(~), the pressure was 82 bar, the internal temperature was
78C and Dose (2) was omitted without substitution.
EXANPLE C_6
Example C l was repeated with the following
changes:
JJ:jrc 27
1 3~i12
no DOS was in the charged starting material, a mixture of 6,450 g
of VC and 1.140 g of VL (vinyl laurate~ was used as Dose (3) and
Dose (4) contained, in addition, 126 g of 30% vinyl sulfonate
solution and 76 g of dibutyl maleinate.
EXAMPLE C 7
A 16 liter autoclave was charged with 724 g of a 20%
Polyviol(R) G 04/140 solution, 731 g of an 8.5% Polyvi.ol(R) W
28/70 solution and 1,510 g of completely demineralized water and
the pH was adjusted to 4.5. The autocla~ewas evacuated and rinsed
with nitrogen. After renewed evacuation, the temperature was
raised to 45~ and ethylene was added to a pressure of 60 bar.
This pressure was kept constànt until tl~e end of the metered
addition of component b) and then the ethylene valve was closed.
Before the start of the reaction, 20 ml of a 5% RONGALIT(R)
solution were also charged with the starting material. The
metered addition of Dose (3) (a mixture of 1,380 g of vinyl
acetate and 5,520 g of VC) at a rate of 1,100 g/hour, of Dose (1)
(a 10% t-BHP solutio~) at a rate of 70 g/hour and of Dose (2)
(a 10% RONGALIT(R) solution) at a rate of 70 g/hour were started
simultaneously. Thirty minutes after the beginning of the said
additions`,(the reaction had an induction period of approx. 15
minutes~ metered Dose (4) (a mixture of 1,030 g of water, 1,690g
of a 20% Polyviol(R)G 04/140 solution, 1,700 g of an 8.5% Poly-
viol(R) W 28/70 solution, 431 g of a 48% N-methylol acrylamide
solution and 34.5 g RONGALIT(R))was started. Metered Dose (1)
was reduced to 45 g/hour and varied over the subsequent course
of the conversion; metered addition (2) was completed. Metered
Dose (3) lasted for 7 hours, Dose (4) for 6.5 hours and Dose
(1) for 8.25 hours. Then the pressure on the reaction batch was
released and the residual vinyl chloride was removed by
evacuating for one hour. A characterization of the dispersions
-28-
1 3Q~3~;12
obtained in Examples C 1 to C 7 is found in Table 3.
EXAMPLE C 8
A 600 liter autoclave was charged with 5.6 k~of a 20%Polyviol(R) G 04/140 solution and 52.8 kg of completely deminera-
lized water and the pH was adjusted to 4.7. The autoclave was
evacuated and rinsed with nitrogen. After renewed evacuation, the
ternperature was raised to 50C and ethylene was added to a pressure
of 68 bar. This pressure was kept constant to the end of the
metered addition of component b) and then the ethylene valve was
cbsed. Before the start of the reaction, 7 kg of a 5% RONGALIT(R)
solution were charged with the starting material. The metered Dose
(Vinylchloride) (3)WQS added at a rate of 28 kg/hourm (Dose (1)(4% t-~P solu-
tion at 4.8 kg/hour, Dose (2) (5% RONGALIT(R) solution) at 4.8
kg/hour and ~ose (4) (a mixture of 117 kg of a 20% Polyviol(R)
G 04/140 solution with 33.6 kg of water) at a rate of 19 kg/hour.
During the polymerization, the Doses (3) and (4) were fed at a
constant rate for 8 hours and Doses (1) and (2) lasted for a total
of 9 hours. The metering rate was then adjusted according to the
conversion to guarantee a uniform reaction. The pH was maintained
between 4.5 and 4.7 by the metered addition of ammonia. After
the end of the addition of the initiator, the pressure on the
batch was released and residual vinyl chloride was removed by
evacuating for one hour. The result is shown in Table 4.
EXAMPLES C 9 and C 10
Example C 8 was repe~ted twice. The charged amount of
water was only slightly varied which explains the somewhat dif-
ferent solids contents and viscosities. Table 4 shows the very
good reproducibility and the determination with the disc centri-
fuge and the nano-sizer were within the limits of error.
-29-
~ 30~35~Z
EXA~PLE8 C_ll nd C 12
Example C 8 was repeated and the amount of charged
water was increased to 72 kg. The consumption of initiator
was distinctly increased in comparison to Example C 8 which
explains the lower minimum film-forming temperature (MFT).
Example C 11 was then repeated on a 16 liter scale as Example
c 12. No differences were found between Examples C 11 and c
12, although a scale adjustment by a factor of 50 had been
made. In adddition, the experimental equipment showed no
geometrical similarities. The pertinent values are recorded
in Table 4.
TABLE 1
Reproducibility of batches of DE-A-3,227,090.
Example Solid~ Bfl Bf20 Struc- Settling Comment~
Content tural
factor
Al 55.6 8200 2160 1.96 0.8
A2 54.4 4000 1230 2.59 0.9
A3 54.5 1240 566 0.87 1.6 finely
speckled
Reaction Bf20
Example After
minute~
A4 5 dilatant
A5 15 8560
JJ:jrc 30
I ~
~3Q~512
Example Agitation sOlid~ Bf 10 Rheo CIII Reaction Final
rpm C~ntent~ After Pre~ure
Minut2~
A6 200 52 17760 5300 90 65
A7 200 48.6 3S680 15476 30 > 90
A8 140 45 13600 1281 120 > 90
A9 120 48.7 10760 3274 60 62
TABLE 2
Examples A 10 and A 11 dispersions according to the process
of DE-A-3,227,090 and Example C 12 is accordi.ng to the
invention
Example A 10 A 11 C 12
Solids content (%) 51 52 51.3
MFT (C) 10.5 0 3
K-value - - 45
Screen oversize (g/kg)
160 ~m screen 1.1 8.6 0.2
Screen oversize (ppm)
60 /lm screen 110 129 42
Bf 20 (mPa.s.) 208 360 3800
Structural factor 0.44 0.7 3.1
Disc weight average t~m) 1.87 1.35 0.3
Disc number average (~m) 0.2 0.19 0.27
Nano-sizer (~m) 0.75 0.44 0.284
PD 5 6
35 Comments strongly strongly clear
speckled speckled
(ppm = mg/kg)
MFT = Ninimum film forming temperature
JJ:jrc 31
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.'' 130~3512
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Referring now to the Figures.
Figure 1 describes particle size distribution
(weight distribution curves) of the dispersion of Example C
11 measured with the disc centrifuge and plotted on two
different scales of the particle diameters.
P. Diameter (~m)
MEAN: WEIGHT: 0.25 ~m
NUMERICAL: 0.22 ~m
MAXIMUM: WEIGHT: 0.25 ~m
NUMERICAL: 0.21 ~m
SPEC. SURFACE: 20.532 M7/G
Figure 2 is an evaluation of the electron
microscope pictures of the dispersion of Example C 11.
VOLUME DIAMETER
L5 DISTRIBUTION DISTRIBUTION
.251 interval width 0.15
maximum .285 mean .235
maximum .225
distribution from .06 to .39
~0 sigma .064
JJ:jrc 33
SlZ
Figure 3 is an electron microscope picture of the dispersion of
Example C 11 and Fig. 4 is a Disc centrifuge determination of a
vinyl chloride-ethylene copolymer dispersion of Example C 1
plotted analogous to Figure 1
WEIGHT DISTRIBUTION CURVE
MEAN: WEIGHT .40 ~m
NUMBERS: .35 ~um
MAXIMUM: WEIGHT: .36 ~m
NUMBERS: .36 ~
SPEC.SURFACE: 10.269 m2/g
Figure 5 is a disc centrifuge determination of a vinyl chloride-
ethylene copolymer dispersion prepared by conventional method
(Example B 1) plotted analogous to Figure 1.
WEIGHT DISTRIBUTI~N CURVE
MEAN: WEIGHT: 3.83 ~um
NUMBERS: 2.36 ,um
MAXIMUM: WEIGHT: 2.71 ~m
NUMBERS: 2.22 ~m
SPEC. SURFACE: 1.651 m2/g
Figure 6 is an evaluation of the electron microscope picture of
the same dispersion as in Fig. 5
VOLUME DIAMETER
DISTRI3UTION DISTRIBUTION
mean .289 interval width .02
maximum .26 mean .26
maxlmum .26
distribution from 0,Q8 t~ .64
sigma .069
- Y.t
~3~8~i~2
Figure 7 is anelectron microscope of the PVOH-stablized VCE
dispersion of Figure 5 and Figure 6
Figure 8 is a comparison of the partic~e size distributions of the
dispersions of Examples C 12, A 10 and A 11 plotted analogous to
Figure 1.
EXAMPLE C 12 EXAMPLE A 10 EXAMPLE A 11
weight O.25 ~m MWweight 1.35 ~m MWweight 1.87~m
MWnumber 0.22 ~m MWnumber 0.19 MWnumber 0.2~m
Spec. surface 2 Spec. surface 2 Spec. surface
20.5 m /g 6.042 m /g 4.5 m2/g
Figure 9 is a particle size distribution of the dispersion of
Example B 1 plotted analogous to Figure 1
MEAN: WEIGHT: 8.70 ~m
NUMBERS: .25 ~m
MAXIMUM: WEIGHT: .27 ~m
NUMBERS: .22 ~um
SPEC. SURFACE: 1.540 m2/g
Various modifications of the products and process of
the invention may be made without departing from the spirit or
scope thereof and it should be understood that the invention is
intended to be limited only as defined in the appended claims.
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