Note: Descriptions are shown in the official language in which they were submitted.
10~5i~71
This invention relates to a process for making
emulsion polymerized preplasticized vinyl resins.
It is well known that vinyl resins may be plasticized
or changed from the hard, horny and stiff state to a soft,
plastic, workable condition by the addition at elevated tempera-
tures of certain plasticizer, such as dioctyl phthalate, and the
like. It has also been suggested to prepare vinyl resins by
polymerizing the monomers in the presence of a plasticizer.
However, such suggestions and the disclosures thereof have
been general in nature with no suggested details of how this
objective might be specifically accomplished.
One of the problems encountered heretofore when mixing
a plasticizer with a vinyl resin has been the poor colloidal
stability of the resultant composition. Further, there is a low
limit as to the amount of plasticizer that can be used and still
obtain a product that is workable and not a sticky mass. In-
addition, the plasticizer is easily extractable from the vinyl
':'
resin and also has a tendency to migrate. Due to all these
poor properties, vinyl resin latexes have poor shelf-life.
Merely preparing vinyl resins by polymerlzing in the
presence of a plasticizer is not enough. Certain important
steps must be followed in order to achieve the desired result,
namely, to incorporate sufficient plasticizer to give the
.~ .
~ i desired result with good colloidal stability and good heat and
,: i
;rl light stability.
~ We have unexpectedly found that preplasticized vinyl
; ~i .
resins can readily be made by polymerizing the vinyl monomer or
monomers while in intimate admixture with a plasticizer therefor
using an emulsion polymerization system. Most importantly, and
particularly when significant amounts of plasticizer are
~ employed, the vinyl monomer or monomers and the plasticizer
`, are homogenized prior to introduction into the reaction vessel.
p~ -1-
~,
',' . : . -: .
;
1()45271 -`
Thorough mixing prior to starting the polymerization reaction
is imperative, otherwise coagulation will result. This new
- process is referred to throughout the present application as
; .:
~ "plastimerization" for purposes of convenience.
i: `
The invention relates to a process for producing
preplasticized polymers of vinyl and vinylidene halide and
, ~ copolymers thereof with each other or either with one or more
vinylidene monomers having at least one terminal CH2=C<
grouping, comprising forming a monomer premix of the monomer
or monomers to be polymerized, from about 5 parts to about
100 parts by weight of a plasticizer for the finished polymer
~; based on 100 parts by weight of the monomer or monomers being `
;~ polymerized, a suitable emulsifier for the polymerization re-
`~l action, and the aqueous reaction medium, homogenizing said
premix to a particle size in the range of 0.5 to 15 microns
with most of the particles being left at 2 microns, passing
' said homogenized premix to a reaction zone, emulsion polymeriz-
,~ ing said homogenized premix in said zone in the presence of
:; catalytic amounts of a suitable catalyst therefor and at a
`~, 20 temperature below the glass transition temperature of the
,- l.
polymer or copolymer being produced, and thereafter recovering
the preplasticized polymer or copolymer.
In the present invention, "vinyl resin" refers to
polymers and copolymers of vinyl and vinylidene halides, such
as vinyl chloride, vinylidene chloride, and the like. The
vinyl halides and vinylidene halides may be copolymerized with
each other or either may be copolymerized with one or more
vinylidene monomers having at least one terminal CH2=C~
grouping. As examples of such vinylidene monomers may be
mentioned the ~ olefinically unsaturated carboxylic acids,
~t. -2-
.... ~,
- ,: . : . ,, ~ ,
- 104S27~
.
such as acrylic acid, methacrylic acid, ethacrylic acld,
~-chloroacrylic acld, ~-cyanoacryllc acid, and the like
esters of acrylic acid, such as methyl acrylate, ethyl
acrylate, butyl acrylate, octyl acrylate, cyanoethyl
acrylate, and the llke, esters of methacrylic acid, such :
as methyl methacrylate, butyl methacrylate, and the llke,
nitriles, such as acrylonitrile and methacrylonltrlle,
acrylamide, such as methyl acrylamide, N-methylol acrylamide, ~ :
N-butoxy methacrylamide, and the like; vinyl ethers, such as
ethyl vinyl ether, chloroethyl vinyl ether, and the like, the
vinyl ketones, styrene and styrene derivatives including ~- :
1~ 1
methyl styrene, vinyl toluene, chlorostyrene, and the like,
vinyl naphthalene, allyl and vinyl chloroacetate, vinyl acetate, ~.
vinyl pyridene, methyl vinyl ketone, diolefins, including buta- -~
~:i diene, isoprene, chloroprene, and the like, and mixtures of any
.:; . .
.~' of these types of monomers and other vinylidene monomers copoly-
merizable therewith including esters of maleic and fumaric
~ acid, and the like, and other vinylidene monomers of the types
.1 known to those skilled in the art. The present invention is
particularly applicable to the manufacture of resinous latices ~-
.':,. -. :
s ;~ :
, ~
,, . .~
.. ,~ :~
: - :
:~' ~ -3
.
.
. ,. "
- - : ~ :~
,
1~4SZ71
made by t~e polymerizatlon, ln the presence of ~ sultable pla8-
ticlzer there~sr, of vlnyl chloride or vlnylldene chloride alone
:
; or in admixture with one or more vinylidene monomers copolymer-
izable therewith in amounts as great as about 80~ by weight,
based on the weig~t of the monomer mixture. The most preferred
vinyl resin is polyvinyl chloride and the invention, for sim-
plicity and convenience, will be described in connection there-
with, it being understood that this is merely intended in an
illustrative sense and not limitative.
The present process for preparing vinyl polymers or
resins is by means of an emulsion polymerization technique in
an aqueous medium in the presence o~ a plasticizer for the par-
ticular vinyl polymer being prepared. Among the various plasti-
,, . .~
ciæers that may be employed in making the vinyl polymers are
. .
the organic phosphoric esters such as tricresyl phosphate,
: ~i
" triphenyl phosphate, isodecyl diphenyl phosphate, tributoxy
ethyl phosphate, and the like; phthalic esters, such as dioctyl
:i phthalate, dimethyl phthalate, dibutyl phthalate, dilauryl
`-~ phthalate, dimethyl tetrachlorophthalate, butyl phthalyl butyl
glycollate, and the like. In fact, any known plasticizer for
polymeric vinyl halides may be employed in the polymerization
i;~ reaction. It has been found that from about 5 parts to about ~-
- ~
100 parts by weight o~ plasticizer, based on 100 parts by weight
of monomer or monomers being polymerized can be charged as a
polymerization ingredient. Usually an amount o~ plasticizer in
the range of 15 parts to 90 parts by weight is suf~icient. When
:$ amounts of plastlcizer greater than 100 parts by welght are em-
ployed, the polymerization rate and the degree of conversion
are adversely a~fected.
While the amount of plasticizer employed in the plas-
timerization process is limited for practical purposes, further
plasticizer can be incorporated in the ~inished plastlmerized
-4-
, ~
, ~; . . . . . .
1~4S~71
vlnyl polymer or resin. The polymers produced by the process
of the present inventlon have an unusually high afflnity to
plasticiPers. Thls is believed to be due to the microstructure
of the polymer particles and they seem to be nDre open struc-
tured. In any event, it is possible to incorporate further
plasticizer in the finished polym~r, by usual means, in varying
amounts up to as high as 150 parts by weight of total plastici-
zer based on the weight of 100 parts of monomer or monomers ori-
ginally polymerized. By totaI plasticizer is meant the plasti-
cizer in the polymer from the plastimerization process plus
that added to the finished polymer. This feature of the poly-
mers produced by the present invention makes them particularly
attractive as blend resins, such as in polyblends with nitrile
rubbers.
i 15 The aqueous medium used in making the vinyl polymers
by the present inventive emulsion polymerization system usually
contains an emulsifier. When emulsifiers are used to prepare
the vinyl polymer latices, the general types of anionic and non-
ionic emulsifiers are employed. Excellent results have been
obtained when using anionic emulsifiers. Useful anionic emul-
sifiers include alkali metal or ammonium salts of the sulfates
of alcohols having from a to 18 carbon atoms, such as sodium
lauryl sulfate, ethanolamine lauryl sulfate, ethylamine lauryl
sulfate, and the like; alkali metal and ammonium salts of sulfon-
ated petroleum and paraffin oils; sodium salts of aromatic sul-
fonic acids, such as dodecane-l-sulfonic acid and octadiene-l- -
sulfonic acid; aralkyl sulfonates, such as sodium isopropyl ben-
zene sulfonate, sodium dodecyl benzene sulfonate, sodium iso-
butyl naphthalene sulfonate, and the like; alkali metal and
ammonium salts of sulfonate dicarboxylic acid esters, such as
sodium dioctyl sulfosuccinate, disodium-n-octadecyl sulfosuc-
cinate, and the like; alkali metal and ammonium salts of free
-5-
1045Z7~
acld o~ complex organlc mono- and dl-phosph~te esters, and the
like. Nonionic emulsifler8, such as octyl- or nonylpnenyl
polyethoxyethanol, may also be used. Vinyl polymer latices
having excellent stability are obtained when employing the al-
kali metal and ammonium salts of aromatic sulfonic acid, ar-
alkyl sulfonates and long chain sulfonates.
:
The amount of emulsifier employed may range in amount
up to about 6% or more by weignt, based on the weight o~ 100
parts of monomer or monomers being polymerized. Tne emulsifier
. ,
is pre-mixed with the monomer and plastlcizer prior to the start
of the polymerization, particularly when the premix is nomogen-
; ized, as explained more fully hereinafter. However, tne emul-
. .
; sifier may be added incrementally or by proportioning through-
out the polymerization reaction.
`~l 15 In carrying out the emulsion polymerization of vinyl
`;~ monomers in accordance with the present invention in the presence
~ of a plasticizer for the polymer being produced, the polymeriza-
. ,1 .
tion temperature is not critical. However, it is imperative
that the reaction be conducted at a temperature below the glass
transition temperature (Tg) of tne polymer being produced. If
the temperature of polymerization is not below the Tg of the
-` polymer, coagulation will result. For example, t~e Tg of poly- ~ -
., .
vinyl chloride is 85C. and therefore, the polymerization of
vinyl chloride must take place below about 85C. in order to
produce a satisfactory product. We have found that temperatures
. in the range of about 15C. to about 75C. are satisfactory for -
. . .; ,
. :, .
polymerizing the vinyl monomers in accordance with the instant ~ A .
< process. Preferably, a temperature in the range of about 40C.
to about 55C. is employed.
The plastimerlzation process described herein is con-
, ducted ln the presence of a compound capable of initiating the
- polymerization reaction. Free radical yielding initlators,
:.
.,~.
,
l~SZ71
normally used for polymerizlng ole~inically uns~turated monomers,
~,
are satisfactory for use in the present process. These inltia-
tors or catalysts include, for example, the various peroxygen
compounds, such as persulfates, benzoyl peroxide, t-butyl hydro-
peroxide, cumene hydroperoxide, t-butyl diperphthalate, pelar-
gonyl peroxlde, l-hydroxycyclohexyl hydroperoxide, and the like;
azo compounds, such as azodiisobutyronitrile, dimethylaZodiiso-
butyrate, and the like. Particularly useful initiators are the
. . ,
water-soluble peroxygen compounds, such as hydrogen peroxide,
lauryl peroxide, isopropyl peroxydicarbonate, and the like, and
the sodium, potassium and ammonium persulfates used by them-
; /, selves or in an activated redox system. Typical redox systems
.~ .
include alkali metal persulfates in combination with a reducing
substance, such as sodium sulfite or sodium bisulfite, a reduc-
ing sugar, dimethylamino propionitrile, a diazomercapto compound
~- and a water-soluble ferricyanide compound, or the like. Heavy
metal ions may also be used to activate the persul~ate catalyzed
polymerization. Particularly useful are alkali metal and am-
monium persulfate. The amount of initiator used will generally
be in the range between about 0.1% to about 3.0% by weight,
based on the weight of 100 parts of monomer or monomers being
.. '3 polymerized, and preferably between about 0.15~ and about 1.0%
by weight.
Generally, the initiator is charged completely at t~e
outset of the polymerization. However, it is often advantageous
' t the employ incremental addition or proportioning of the initi-
i ator tQroughout the polymerization reaction. When the initiator
is charged at the outset it is added to the monomer premix with
the other ingredients of the reaction mixture. This is particu-
larly true when said premix is homogenized prior to lntroduction
into the reactor. However, when adding the initiation to the
premix and then homogenlzing; it is necessary that the tempera-
,
...
.
.,
1~45Z71
ture durlng the premlxing and homogenlzatlon steps be ~ept below
; the mlnlmum temperature of reactlvity of the partlcular inltla-
tor or inltiators being employed. For example, when maklng a
premix oP vinyl chloride, water and suitable emulsifiers, and
':~
then adding isopropyl peroxydicarbonate thereto, the temperature
.;
is maintained at 20C during the mixing step and then during
the homogenization step. Upon introduction of the homogenized
mixture into the polymerization reactor, the temperature is
' then raised to that at which the reaction i5 to take place.
~ 10 One o~ the most important aspects of the process of
.tl the instant invention is the step o~ homogenization. T~e plas-
ticlzer must be thoroughly and intimately mixed with the mono- ~
mer or monomers when more than one is employed, prior to the ~-
~ commencement of the polymerization reaction. This mixture is~ 15 referred to as the monomer premlx and will also contain the water
or reaction medium. Further, any emulsifier being employed will
~;~ likewise be added to the premix, all of the ingredients being
`~ added with suitable agitation. If the catalyst or initiator is
to be added prior to the commencement o~ the polymerization
reaction, it is the last lngredient added to the premix. As has
been pointed out, when adding the catalyst the temperature of
1 the premix should be below the minimum temperature at which the
-' catalyst becomes reactive. Further, when a particular catalyst
being employed is not water-soluble, it should be added to the
premix in a suitable solvent therefor which will insure emulsi- - -
~ication in the premix and even distribution. Needless to say,
any such solvent should be inert to the reaction ingredients
and reaction conditions. For example, when employing isopropyl
peroxydicarbonate as a catalyst, it is added to the premix in
hexane. In the Examples, which follow hereinafter, wherever
' isopropyl peroxydlcarbonate was used it was added to the premix
or to the reactor in hexane.
.
1~4SZ';'l
The monomer premix, or reaction premix, is thereafter
subjected to ~omogenization prior to entering the polymerization
step or reactor. Any convenient means of homogenizing may be
employed, We have found that a one stage Manton-Gaulin homo-
genizer (Model 31M-3TBA) is a convenient apparatus for homogen-
izing the premixes contemplated by the instant invention. The
` premix leaves the homogenizer and goes directly into the reac-
~.:
tion vessel which preferably contains an inert atmosphere,
`~ such as nitro~en.
Homogenization is most important and necessarg with
increasing plasticizer content in the premix to be polymerized.
Irrespective of the content of plasticizer used the best re-
. . .~
;`~' sults, i.e., the most stable polymer latices, are obtained when
the monomer and plasticizer are premixed and then homogenized
`'5 15 prior to polymerization. Further, in addition to latex in-
, stability, polymer buildup on the reactor walls occurs to a
very detrimental extent when homogenization is not employed.
i Homogenization is necessary in order to assure the
' proper particle size. A particle size in the range of 0.5 to
15 microns is desirable, with most of the particles being less
than 2 microns. It is to be noted that the particle size in-
creases as the amount of plasticizer employed increases. How-
ever, it is necessary to stay within the range of particle size
,,. ~ .
given in order to form a stable emulsion.
We have found that before homogenization the particle
size of the monomer premix or emulsion will be in the range o~
2 to 40 microns with no plasticizer present and in the range
of 10 to 50 microns with 90 parts by weight of plasticizer pre-
sent. On the other ~and, after homogenization the particle
size of the same premix or emulsion decreases to 0.5 to 2 mi-
crons with no plasticizer present and to 0.5 to 15 microns
with 90 parts by weight of plasticizer present. In the latter
* Trademark 9
/
: ~045271
case most of the particles are less than 2 microns in size.
In the plastimerization process of the present inven- ~ -
tion, pH is not critical provided that the homogenization step
is applied. Good results have been obtained when using homo-
genization in the present process in a pH range of from about
3 to about 10. However, if one is polymerizing a monomer pre-
mix without homogenization then pH is critical and also, the
particular emulsifier system emp:Loyed is important. In such a
case, a highly alkaline reaction medium is required with a pH
, 10 of around 10. Also, the exact level of plasticizer that can be
; used without homogenization depends on the emulsifier system
i used and on the pH of the polymerization reaction. For example,
.,j :
high pH polymerizations using ammonium laurate emulsifier are
better suited for plastimerization compared to sodium lauryl
sulfate based polymerizations. However, when using homogeniza-
. .... :
tion, as described herein, then any pH or emulsifier system may
be employed and obtain stable plasticized vinyl resin latices.
-~ It should be noted that in addition to the choice of ,~ ;
the proper emulsifier system, the pH of the reaction system can
be adjusted as by the use of ammonium hydroxide,and the like.
In addition one may employ buffering agents in the reaction mix-
ture, such as trisodium phosphate, tetrasodium pyrophos~hate,
; and the like. In any event, the plasticized vinyl polymer la-
tex produced may subsequently be adjusted to any desired pH by
suitable means. ~-
, To further illustrate the present invention, the fol-
lowing specific examples are given, it being understood that
- this is merely intended in an illùstrative and not a limitative
-~ sense. In the examples all parts and percents are by weight
unless otherwise indicated.
EXAMPLE I
In this example, two runs, along with a control run
--10--
. ~ . - . . . .
: ~ . . . ,, : : : ,, .
- - .
:~. ~ .. . . . . ..
, . . .
1(145Z71
were made to show that the plasticizer must be thoroughly mixed
with the monomer prior to the start of the polymerization reac-
tion. The recipes employed in the polymerizations are given
in the following table in which all the figues are in parts by
weight based on the weight of the total composition.
Table I
~I Run No. 1 2 Control
Vinyl chloride 100 100 100
Dioctyl phthalate 15 15 15
- 10 Water (demineralized)200 200 200
Isopropyl peroxydi- o.o6 o.o6 o.o4
carbonate
Sodium lauryl sulfate 4 - 4
(emulsi~ier)
~ 15 Straight-chain dodecyl - 4
-j benzene sodium sul-
,'.! ~ate (emulsifier)
` In each of runs 1 and 2 a monomer premix tank or vessel
was charged with vinyl chloride and the plasticizer dioctyl
phthalate thoroughly mixed therein. ~hile agitating this mix-
ture, the water and emulsifier were added. Therea~ter, the mix-
ture was cooled to 20C. and the isopropyl peroxydicarbonate
- added thereto. The tank was evacuated and nitrogen introduced.
The entire mixture was then agitated for 15 minutes under a
nitrogen atmosphere. Thereafter the mixture (monomer premix) -
was passed through a homogeniæer into a polymerization reactor
containing a nitrogen atmosphere. The homogenizer was a one ~ -
stage Manton-Gaulin!homogenizer (Model 31M-3TBA) operated at ~
,' ,
750-1000 psi stage pressure. Therea~ter the contents of the
reactor were heated to the polymerization temperature and the ~;~
reaction allowed to proceed to the desired conversion.
In the case o~ the control, all ingredients, except
, the plasticizer dioctyl phthalate were charged to the reactor
and mixed. A~ter the polymerization reaction had proceeded to
50% conversion of monomer to polymer latex, the plasticizer was
metered into the reactor. The polymerization conditions and
results o~ all the runs are given in the ~ollowing table:
* Trademark
., :
,........ . .... . .. . . .
,
`. ' ' .:~ ' , , ~
",,
: 1045271
Table II
Run ~o. 1 2 Control
Reaction Temp. C. 51 51 51 s
;~ Reaction Time, hours 12 16 Coagu: .ated
Total solids, % 31.5 33
Conversion, % 84 88
Coagulum, % O O
i,, Plasticizer content. % 14.7 14.7
Slurry condition OK OK
pH 7.1 3.3
;, Thus it can be seen that the addition of plasticizer after the
start of polymerization does not work. It is believed the re~
sults are self-explanatory.
EXAMPLE II
The purpose of this example was to show the criticality ~ -
of homogenization to obtain good polymer latices containing the
appropriate amount of plasticizer and without having to ad~ust ~ -~
the pH. Xere again the recipes employed are given in the table
which follows in which all figures are in parts by weight based ~-
~', 20 on the weight of the total composition. Also, the runs made in
~ ' this example show the importance of homogenization wit~ increas-
`'`i~ ing amounts of plasticizer and it is absolutely necessary when
one employs more than about 60 parts of plasticizer to obtain
~; satis~actory results.
Following the procedure outlined in Example I, Runs
3 and 4 were prepared the same way except that the K2S20g was
placed in the polymerization reactor prior to the introduction
of the homogenized premix. In the case of the Controls 3 and
4, the same procedure was followed except that the premix was
not homogenized prior to introduction into the polymerization
..~
~3 reactor. The recipe, polymerization conditions and results,
. ,~
,~ in each case, are set out in the following table: ~-$~
:',~
:`, .
..1.
.. :
;'
. ~ ..
: 1~45271
~,
b
,,~ ~ s~
:. ~ o ,, ' ' ' ~ ' ~,, " 0 ~ - .
i~ ~ o ~ o
~' ~ I o ~o o , , , ~ , ,I~o o ,1 o ,1~ X
' o ~ O
,',i . .
~5 :
~, ' , ' .
~ .
~j H O a~
.~ ~ ,,1 o o o I H ~N I ~D --10 ~ 1~) I E
~d l ~ ~ ~ ~ c'~
~ X ~ ~n E~ , ..
j':~ ' - ',' :
`~ I `0001 ~ 0 ~ O l~ll~
cu o ~ o ~ . .
' a~ .
'`j ta
~5 C 1--
O ~ o ~
U r~ ,p .~ O ':
'O ~ a) h ~ u~ ~1 ~ ~ ^~
o ~ ~ ^~ h~
E,~ ~ ~ O ^ a) O
0 ~1 ~ S: ~ O rl ~; ~ c,~ :
P~H~ al ~00
-13-
.:,; - , , ~ . . . .
1~45Z71
It can readlly be 3een from the ~bove Table III that
without homogenlzatlon no satls~actory product i8 obtalnable
when employing high amounts of plasticizer (gO parts). Further,
ad~u~tlng the pH to the highly alkaline side, as in Control 3,
with NH40H did not help either. On the other hand, such a high
pH does not affect the resultant product when the premix is
homogenized, as witness Run 3. Without homogenization and with-
,
'3 out pH ad~ustment, it is impos~iblè to obtain a product, as
witness Control 4.
EXAMPLE III -
.
In this example a series of runs were made to show that
homogenization is essential to secure a good latex in both batch
polymerization and in a polymerization employing prem~x propor-
tloning. Further, these runs also show that the exact level of
plasticizer that can be used without homogenization depends on
the emulsifier system and on the polymerization pH. In Table
IV that follows the conditlons of reaction, recipe and results
are set out in each case. Making of the premlx and homogeniza-
tion was carried out as described in Example I. Adding all the
, 20 material to the reactor and then polymerizing is referred to as
-~ "batch polymerization" and adding the premix to the reactor
,;~ .
continuously or intermittently during the reaction is referred
, to as proportioning. In Table IV several processes are referred
.;~
; to whlch are identified as ~ollows:
(1) Batch polymerizatlon of homogenized premix.
(2) Batch polymer~zation of non-homogenized premix.
(3) Proportionlng of homogenized premix.
(4) Proportioning of non-homogenized premix.
, :
..,
, , ~
.1 .
--14_
.,, . , . . - .
j, . . . .
.... . . . .
,-,., : . . . ,. ; ~ . .
10452'.31
~1 ~ ~ ~o o ' ~ U~ pa~ln~o~
~ ~U o ~- ~
,~1o ~1 o o ~--H-~ p~3~ n~BO~
N ¦ O~D ~1
~I N~ Pa~ln9~0;~
: ,1 o~o o. . ~co .~ o o~
!
- Hc~l ~ ~ O ~ * *
:. ~1 ,. ~,
col o o~o ~I LI~H ~co ~1
~ ~ N * * O*
O ~NO ~ o ~ ~) ~)
,
u~ ~ O J~ N ~ 0 ~!0
,~, 2E
$ ~¦ V
N I ,~ o E~ E~ V
o~ c ~0 c o c ~ c * ** *
~: ~ 8 ~ ~ ~ o ~ ~ ~ ~ o ~
1~ ~ q H U~ ~
.~ :
~ :-
. ~ .
1~J45Z71
Looking at the Table above lt can be seen that homo-
genization of t~e premix give6 superior results as witness runs
6, 8, 10 and 14. This is so irrespective of the emulsifier
used and the pH of the system.
EXAMPLE IV
In this example a series of runs were made to illus- ~ -
trate that the present invention, when employing homogenization
of the monomer-plasticizer premix prior to the start of poly-
merization, is not limited to the use of any particular emulsi-
fier. Further, the inventive process is not limited to a parti-
cular polymerization pE nor to a particular initiator or cata-
lyst system. Again the general procedure outlined in Example I
was followed in each o~ the runs made. In each run the proce-
dure involved the batch polymerization of a homogenized premix.
. . .
--` 15 The following Table V contains all the data with respect to
` recipe, polymerization conditions and results.
..~
'~ ,
.' 1~
, .
.~
, .
.
:.~
,
:
-16-
.
C
, ;~. .~ , . ~, .
1~4SZ71 ~`
~`1 8 ~ ' 8 '~ o o ,~ ~C o
--I O N ~ N
,, .
ooQ oo I I I I l ,l~ o,_~
0, ~ l ~ 00 0
' ' .
O~ O I I O I I I ~1~0~0
~ I . ~IC~I ~ U~ 0
'`! ~l
: ,,
--~1 8 0 ,, 8 0. 1 1 1 1 1 ~N U~ o ~ ~ ~1
~, o 'l ~ ~
. .~
.. ~ .
,,,1, P.l
,`. ~1 ..
., ~
.,~, ~ .
. J
.'~ ,~ ,
O
''' ~: -
N `l!R
.'
`' O ~ S: '
~ ~ ~ ,1 o ~ o ~ ~ :
h O ~ ~ ~ ~ a3 ~
. " ~1 ~1 ~ ~ ~1 0 ^ P~ O ' ' " "
. 5~ O O u~
O O ~,
.. ~ ~ Oa O ~ ~ ~ o
~ rl a3 o ~d ~ O ~ ~a) o o o o ~
P~ H ~ ~ CQ ~ V V 1
.', .
~ -17- :
.,
~,...
,
1~45'*7~ :
It i8 slgniflcant to note that the pH ln the above
runs varled from 3.0 to 10.0 which did not affect the resultant
~; polymer latices when homogenization of the premix is employed.
EXAMPLE V
Two runs were made to demonstrate that the plastimeri-
zation process should be conducted at a temperature below the
glass transitlon temperature (Tg) o~ the polymer being produced.
In this example, in making a polyvinyl chloride latex, the temp- -
r erature of polymerization should be below 80C. The general
procedure of Example I was followed using a batch polymerization
technique of a homogenized premix. The tabulation of data and
results are in the following Table VI.
Table VI
, ,
Run No. 20 21
~ 15 Vinyl chloride 100 100
.j Dioctyl phthalate 90 90
Sodium lauryl sulfate 4.0 4.0
.3 Water (demineralized) 200 200
Isopropyl peroxydicarbonate 0.1 0.005
Reaction time, hours 9 22
.~ Reaction temp., C. 51 80
Total solids, % 34 36
Coagulum, ~ 0 0
, pH 3.8 -
The present invention offers many advantages such as
the ability to produce vinyl resin latices having greatly im-
proved colloidal stability. This property increases the shelf-
aging of the vinyl resin latex. Further, the process described
herein results in a more efficient incorporation of plasticizer
in the polymer latex and more importantly,results in a reduced
plasticizer extractability and migration.
The plastimerized vinyl resins produced by the pre-
sent process are particularly useful in blending with latices
o~ nitrile rubber, and the like, since it is possible to accom-
, 35 plish such blending on a roll mill without sticking. Further,
when non-flammable properties are desired in the preplasticized
vinyl resin, it is a simple matter to choose a suitable plasti-
-18-
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clzer which will result ln ~uch propertle~. Numerous other
advantages o~ the present inventlon will be readlly apparent
to those skilled in the art.
While the present invention has been described in
- 5 terms of its specific embodiments, certain modifications and
equivalents will be apparent to those skilled in the art and
are intended to be included within the scope of the present in-
vention, which is to be limlted only by the reasonable scope of
the appended claims.
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