CA1091864A - Nontacky shaped objects from polymer latices - Google Patents
Nontacky shaped objects from polymer laticesInfo
- Publication number
- CA1091864A CA1091864A CA281,448A CA281448A CA1091864A CA 1091864 A CA1091864 A CA 1091864A CA 281448 A CA281448 A CA 281448A CA 1091864 A CA1091864 A CA 1091864A
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- Prior art keywords
- bath
- weight
- latex
- shaped object
- inorganic oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
ABSTRACT
Montacky, elastomeric shaped objects (e.g., pellets or filaments) comprising a normally tacky, uncured elastomer having an integral, porous coating of silicic or aluminic acid polymer can be prepared by bringing shaped bodies of a normally tacky, uncured elastomer latex into contact with an aqueous bath containing a soluble coagulating salt for the latex, and a silicic or aluminic acid polymer, and washing and drying the resulting coated shaped objects. The shaped objects are highly porous before washing and drying, and some porosity remains even after washing and drying.
Montacky, elastomeric shaped objects (e.g., pellets or filaments) comprising a normally tacky, uncured elastomer having an integral, porous coating of silicic or aluminic acid polymer can be prepared by bringing shaped bodies of a normally tacky, uncured elastomer latex into contact with an aqueous bath containing a soluble coagulating salt for the latex, and a silicic or aluminic acid polymer, and washing and drying the resulting coated shaped objects. The shaped objects are highly porous before washing and drying, and some porosity remains even after washing and drying.
Description
~(J91864 BACKGROUND OF THE INVENTION
(1) Field of the Invention This invention is concerned with nontacky shaped objects of normally tacky elastomers, and a process for preparing them.
(1) Field of the Invention This invention is concerned with nontacky shaped objects of normally tacky elastomers, and a process for preparing them.
(2) Description of the Prior Art ;~-It is a well known process to emulsify polymerizable monomers in water and then convert them to polymers in dis-persed form. The resulting dispersions are called latices.
Natural rubber also occurs as a latex. Some latices are highly useful as formed, for example, basic formulations for latex paints. For other uses, it is necessary to coagulate the polymer and separate it from the latex. The most important commercial form for these polymers is as washed and dried, non-tacky shaped objects. These shaped objects should be washed ' until they contain less than about 3~ by weight of water ` soluble material, and dried until they contain less than about 1% by weight of volatile material.
! If the coagulated polymer is inherently nontacky, the polymer is readily isolated from the aqueous phase, washed and dried to form a free-flowing powder which is readily handled :
in further processing. If, however, the polymer is inherently tacky, coagulating of the latex yields the polymer in an agglo-merated mass which is difficult to wash free of impurities and also difficult to dissolve, to blend with other materials, and ;:
to feed in compounding, curing and molding operations.
;' :~
i~ In the field of natural and synthetic rubber, much attention has been given to the problem of agglomeration of normally tacky polymers before curing. Some operable solutions ... .
, . . . .
~0~1864 have been found.
In U.S. 2,879,173, Yacoe shows a process for coagulating a polychloroprene latex by suspending drops in a volatile, water-immiscible, organic liquid in which the poly- `-chloroprene latex is insoluble while maintaining the liquid below about -20C until the drops are completely frozen and coagulated. The resulting frozen pellets are separated and coated, while still frozen, with from 5~ to 20~ by weight of an inert powder, such as talc, so that they will not stick together when thawed and dried. However, the use of this process has been limited by the cost of organic liquid recovery, the energy cost of the refrigeration, and the un-desirable high loading of inert material. The need for a more practical and economical method of preparing nontacky, washed and dried shaped objects of normally tacky elastomers remains.
In U.S. 3,053,824, Heinz shows coagulation of a phosphate or borate buffered elastomer latex by running it into an aqueous aluminum or titanium salt solution containing ,:
-~ 20 also an alkali metal or alkaline earth metal salt. The patent ;
states that the resulting coagulated particles do not stick together before being washed to remove the coagulating salts.
There is no statement as to the tack of the particles after .-washing.
In U.S. 3,846,365, Berg et al. show a powdery,filled polymer prepared by emulsifying together a dilute :
solution of an elastomer in a volatile organic solvent and a solid, finely-divided filler for the eIastomer, passing the emulsion into an aqueous alkali silicate solution at a pH preferably of 7 to 12, and evaporating the organic solvent.
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A finely-divided, tack-free coprecipitate of the latex and ;~
silicic acid residue is formed. It is stated that condensation - of the silicate anions should be avoided.
, SUMMARY OF THE INVENTION
This invention is based on the discovery that nontacky, uncured, washed and dried, elastomeric shaped ob-jects can be produced from a normally tacky elastomer latex by a simple and inexpensive process. This invention provides nontacky, elastomeric shaped objects which comprise a normally tacky, uncured elastomer containing, baséd on the total weight of the shaped object, less than about 3% by weight of water soluble material, and less than about 1% by weight of volatile material, and having about 0.05 to about 3% by weight of an integral, porous coating of a water insoluble, hydrous inor-ganic oxide selected from the group consisting of silicic and aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, said shaped objects having a minimum dimension of about 0.01 to about 10 millimeters. By "integral"
., is meant a coating which has unity, rather than being composed ~0 of discrete particles such as in the case of a powder coating.
By "minimum dimension" is meant the diameter of the smallest round hole through which the shaped object will pass lengthwise.
A unique feature of this invention is that, prior to ; removing the water soluble and volatile materials, the nontacky ., shaped objects are highly porous. This porosity is evidenced . .
by the objects being opaque in appearance when dispersed in ....
~ water, and by their cross section having a vesicular structure . .
in micrographs. Because of this porosity, water soluble and ` volatile materials are easily removed by washing and drying ": .
:~ - 3 -,' ' , :' ~-. . . : . -109~864 techniques. Some of the porosity is retained even after washing and drying.
The nontacky, elastomeric shaped objects of this invention are prepared by a process which comprises bringing shaped bodies of a normally tacky, uncured elastomer latex having a solids content of 20% to 65% by weight into contact with an aqueous bath containing, based on the total weight of the bath, a) about 0.5% to about 25% by weight of a soluble coagulating salt for the latex, and b) about 0.01% to about 5% by weight of a ;~ soluble or colloidally dispersed, hydrous inorganic oxide selected from the group consisting of silicic and aluminic acid - polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, , said bath having a pH of about 2 to about 7 such that, when a drop of 1.0N NaOH is added to the . ~
;~` 20 bath, the drop is immediately surrounded by a ,, ~ cloudy coating of gelled, hydrous inorganic oxide, :, -:
thereby coagulating the lateX and forming highly porous shaped objects of the coagulated elastomer coated with water insoluble, . .
hydrous, inorganic oxide. These shaped objects can then be washed with water until the water soluble material content is less than about 3% by weight, and dried until the volatile material content is less than a~out 1% by weight, thereby providing free-flowing, nontacky, elastomeric shaped objects.
This invention is particularly suitable for producing nontacky , .
pellets of uncured neoprene.
The term "shaped body" is used herein to designate 86~
tho letex berore lt contacts the aqueous bath. m e tor~
~8haped obJoct~ 18 used hereln to deslgnato the latex and ~ub~oquent elastomer arter the shaped body enter~ the bath.
BRIEF DESCRIPTION OF THE DRANING~
Flgure 1 illustrate~ a vle~ in central vortical ~ection and partlally ln slde elevation of a preferred apparatus ~or carrylng out one embodiment Or the procoss o~
- thls lnventlon. m i8 apparatus and the method of u8ing lt 18 clalmed ln U.S. Patent 4,110,491 Or R. ~. Secor, whlch : 10 lssu d 1978 August 29.
Figure 2 lllustrates a top vle~ o~ the same apparatNs a~ Flgure 1 taken through cut 2-2.
Figure 3 i~ a photoEicrograph Or a cross ~oction Or a porous ~haped obJect ln accordance ulth thla in~entlon.
` DE~CRIPTION OP THE PREF~RRED EMBODIMENTS
In accordance ulth thls lnvention, an lnorganlc ~- oxido polymer coatlng 18 ¢hemically depo~lted on a shaped ob~ect Or normally tacky ola~tomer from solutlon or disper-sion ln an aquoous bath. The ¢oatlng, as formed, 18 there-fore a porou~, nonp-rtlculate, unitary pelllcle entirely ; surroundlng each shaped ob~ect. Eecause of the integral .
~- nature o~ the coating, no~tacky ob~octs can be obtalned with very 8mall loadings o~ coating material. Thls 1~
;
~ particularly lmportant ~or elastomers that are subsequently .~
~;~ di~solved be~ore curing, and is ln sharp contra~t to the requisite heavy lo~dlngs of p~rtieulate materials, sueh as ; tale, uhieh have previ~usly been u~ed to render uncured el~stomeric ob~ects nont~eky.
Tho produets Or th~s ln~ontlon are nontacky shaped ob~ect~ of normally taeky, uneured elastomers. m e term " ~
' .. . .
"elastomer" is well known to those skilled in the art and has been defined in publications such as "ASTM Glossary of Terms Relating to Rubber and Rubber Like Materials", page 38. By "normally tacky elastomer" is meant an elastomer, two pieces of which, when uncured and in the most decrystallized condition, will stick together at room temperature.
Suitable elastomers for use in accordance with this invention include homopolymers and copolymers of conjugated dienes such as neoprene and natural rubber; copolymers of conjugated dienes with other polymerizable, organic monomers, for example butadiene-acrylonitrile and butadiene-styrene copolymers; elastomeric fluoropolymers (fluorine-containing polymers), preferably copolymers of vinylidene fluoride and at least one other fluorine-containing monomer, for exam~ple copolymers of vinylidene fluoride and hexafluoropropene (U.S. 3,051,677), and terpolymers of tetrafluoroethylene, vinylidene fluoride and hexafluoropropene (U.S. 2,968,649);
adhesive-type elastomers such as polyvinyl acetate and ethylene-vinyl acetate copolymers; acrylate rubbers such as .~:
the lower alkyl acrylate ester polymers; hydrocarbon elastomers such as polyisobutylene, the terpolymers of ethylene, propylene and non-conjugated dienes; and similar materials.
The preferred elastomer is neoprene. By "neoprene"
., is meant an elastomer comprising at least about 50~ chloroprene . .
(2-chloro-1,3-butadiene?. Representative comonomers that can be used with chloroprene include vinyl aromatic compounds, " ~
such as styrene, the vinyl toluenes, and vinyl-naphthalenes;
. .
aliphatic conjugated diolefin compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 2,3-dichloro-1,3-butadiene; vinyl ethers, esters, and ketones, such as methyl , ~091864 vinyl ether, vinyl acetate, and methyl vinyl ketone; esters,amines, and nitriles of acrylic and methacryIic acids, such a~i ethyl acrylate, methyl methacrylate, methacrylamide, and acrylonitrile; and the like.
Neoprene latices for use in this invention may be prepared by the known aqueous emulsion polymerization of chloroprene, using a sodium rosinate dispersant and a free-radical type polymerization catalyst such as potassium persulfate. The sodium resinate dispersant may be prepared in situ from rosin acids and sodium hydroxide.
Additives such as fillers, antioxidants and the like ; may be present during the polymerization. The polymerization is allowed to proceed to a predetermined degree of completion, after which a catalyst ~hortstop can be added, and residual chloroprene monomer is stripped off. Minor variations in the procedure yield latices of polymers varying in molecular weight, viscosity, crystallinity, and other properties. In order to form pellets in the process of this invention, the latex should have a solids content of at least about 20% by ~- 20 weight. Suitable latices can have solids contents up to about :~.
65%. Latices generally coagulate when the solids content goes above about 65%. Preferably the latex has a solids content from about 35% to about 50~i. -This invention involves the process of adding drops, a controlled stream, or some other dispensed form of a latex of the normally tacky elastomer to an aqueous coagulating and coating bath thereby forming a coated shaped object. The latex emulsion should be stable enough to survive through the .
addition step until the shaped object is fully penetrated by '^.
; 30 the coagulating salt and any neutralizing agent present.
i .i `~ - 7 ., _ ' :
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Neoprene latices are normally stabilized against premature coalescence by sodium rosinate; natural rubber by ammonia.
The aqueous coagulating and coating bath contains a coagulating salt for the latex, that is, a salt which will coagulate the elastomer latex. Suitable coagulating salts are well known to those skilled in the art; for example, see "Neoprene Latex", by J. C. Carl, pages 19-21, published by E. I. du Pont de Nemours and Company (Inc.), Wilmington, Delaware. Operable salts which may be employed include the water soluble sulfates, chlorides, bromides, nitrates, -citrates, acetates, formates and phosphates of ammonium, sodium, potassium, calcium, magnesium, strontium, barium, lithium, beryllium, aluminum, manganese, zinc, yttrium, iron and cadmium. Mixtures of such salts may also be used.
Desirable, but nonlimiting, characteristics of the coagulating salt include low cost, colorless solutions, cations ,, and anions which are not readily oxidizable or reducible, noncoprecipitating with the alkali metal salt accumulating in the bath, nontoxic, and nonpolluting. Preferably, the salt t". 20 should be chemically inert to the elastomer and insoluble therein. The preferred salts are soluble chlorides, sulfates, acetates, nitrates and phosphates of sodium, potassium, ammonium, calcium, magnesium and aluminum. The most preferred salts are the soluble chlorides and sulfates of the above cations. The coagulating salt may constitute from about 0.5%
to about 25% by weight of the bath. The operable amount of coagulating salt within this range in any given case will depend upon the particular latex, the pH of the bath, and the `/ particular inorganic oxide present. Generally, the optimum and preferred amount of salt is in the range of about 1% to 1~91864 about 10%.
he bath also contains a soluble or colloidally ; dispersed, hydrous inorganic oxide selected from the group consisting of silicic and aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. These oxides àre those commonly considered as existing in polymeric , ~ form, the structure of which may be linear chains, ribbons, ~
., or when highly cross-linked) even globules, in which atoms . ~.
of the inorganic element alternate with oxygen atoms. In .i, .
such polymers, some of the peripheral groups are -OH groups.
The inorganic oxide may be used in water soluble form, as in the case of polysilicic acid and polyaluminic -, . .
acid, or in more highly polymerized, particulate form as in the case of colloidally dispersible silica sols as described ~
.. ...
in U.S. 2,574,902 and alumina sols as described in U.S.
2,590,833. In practice, most a~ueous systems containing such compounds have at least part of the polymeric oxide in the form of dispersed particles. The terms, "silicic acid polymers" and "aluminic acid polymers" are intended to in-clude these polymers in both the soluble and the colloidally dispersible form. The inorganic oxides may be in crystalline or amorphous form, and a mixture of two or more such oxides may be used. The most preferred inorganic oxides are poly-silicic acid, polyaluminic acid and silicic acid-aluminic acid copolymers.
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~ If the coagulating salt employed is an aluminum ,:;., salt and the inorganic oxide is polysilicic acid, some of the aluminic hydroxyls generated at the alkaline surface of the latex may copolymerize by condensation with silanol ~; 30 groups to form an aluminic acid-silicic acid copolymer. If :"
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the coagulating salt employed is not an aluminum salt, particularly if the bath is utilizing polysilicic acid as t~e coating material, it is desirable, though not essential, to add to the bath about 0.002~ to about 2% by weight of an ionizable aluminum salt. Although copolymerization of the aluminum has not been established, it is believed that this accounts for the inorganic oxide being rendered more effective as a coating, possibly by reducing any subsequent solubility of the coating in the wash water. For this pur-pose, it has been found that yttrium salts are equivalent to aluminum salts and may be substituted in whole or in part therefor. Accordingly, the term "silicic acid-aluminic acid copolymer" should be construed in the claims to cover this substitution of equivalents.
It is generally recognized that, in freshly prepared silicic acid solutions, the silicic acid is not .~ ,. , monomeric, but has a molecular weight of the order of about 1000. As the silicic acid solution ages, the molecular weight continues to rise until finally the solution gels (see 20 Bechtold, J. Phys. Chem., 59, 532-541 (1955)). The silicic acid solution used in accordance with this invention should not have aged for more than about 90% of its gel time prior .~, ~ to being added to the bath. Preferably, the silicic acid , .~.
solution has aged for about 5% to about 70% of its gel time prior to being added to the bath. When operating in a continuous manner, silicic acid is continuously added to and removed from the bath, whereby the average age of the -; polysilicic acid réaches a constant value which is less than .:
its gel time.
..~
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~ - 10-,~, The hydrous inorganic oxide may constitute from about 0.01% to about 5% by weight of the coagulating bath.
The presence of more than about 5% inorganic oxide does not lead to any further improvement in the nontacky proper-ties of the product. Preferably the inorganic oxide is present in the amount of about 0.03~ to about 2%. The oxide ; may be polymerized or crystallized during the coating opera-tion. One criterion for determining when a bath is no longer suitable for the present process is coagulation of the bath ; 10 due to changed conditions such as pH or to exhaustion of ;~
essential ingredients.
Optionally, the bath may also contain a minor amount of surfactant to reduce the air-liquid interfacial -tension and assist penetration of the shaped latex body into the bath. Suitable surfactants are characterized by ., , ; being effective at low concentrations and being compatible, " . .
that is, not causing polymerization or cross-linking of the ~: .
~ç, hydrous oxide component, and being inert to the coagulating ~,. , salt. A wide variety of nonionic, anionic, cationic and ~ 20amphoteric surfactants may be used. Examples of suitable i surfactants include lower alkyl alcohols such as ethanol, the trimethylnonanol ether of ethylene oxide, sodium ; heptadecyl sulfate, sodium lauryl sulfate, the condensation , products of tertiary amines with ethylene oxide, fluori-nated amphoteric surfactants, and the like. The surfactant ~, ;~ preferably is added in an amount sufficient to reduce the .--.
`'t"air-liquid interfacial tension to less than about 50 dynes/cm -: -and particularly less than about 35 dynes/cm.
The bath is operable in a pH range of about 2 to ... .
~ 30 about 7. If the pH is below about 2, the inorganic oxide . "
;
, ::,,- , :
- 1a91864 is difficult to gel on the surface of the shaped object.
If the pH is above about 7, the inorganic oxide may be converted to a soluble salt. The operable pH within this range for any given system will depend on the particular latex, coagulating salt and inorganic oxide present.
Within this range, pH values from about 2.5 to about 5.5 are particularly preferred for optimum balance of bath stability with coating effectiveness. If the pH of the bath is maintained in the desired range by proportional addition of a neutralizing agent as the alkaline latex bodies enter the bath, the life of the bath can be substan-tially prolonged. Organic and inorganic acids such as acetic acid and aqueous hydrochloric acid, and hydrolyzable acidic salts such as AlC13 are particularly suitable neutralizing agents .
Operability of the bath to provide a coating on the shaped object is a function of the amount and type of hydrous inorganic oxide present and the pH of the bath. It has been found that not all combinations of the above vari-.... .
ables lead to operable baths. Although the requîrements for a functional bath are not fully understood, a simple . .
- test has been found for determining whether the bath is ~; functional. In this test, a drop of 1.0N sodium hydroxide .. .
is added to the bath. If the drop is immediately surrounded s by a cloudy coating of gelled hydrous oxide, the bath is -- functional.
Although the pH of various latices vary over wide limits, it is preferable that the pH of the latex be equal to or greater than the pH of the bath. When the latex is : 30 neoprene containing sodium rosinate as the stabilizer, the ' 64 :~
p~ of the latex will be greater than about 7 unless it has been acidified.
When the latex is added as drops, the precipitated shaped objects obtained may be lumps, beads, pellets ~with or without a "tail"), discs or rings depending on the sur-face tension and density of the precipitating bath and the speed and direction of the latex as it enters the bath.
When the latex is added as a controlled stream, the stream may be filamentous, yielding a precipitated fiber or bead- `~
ing, or the stream may be spread out in flat or curved form .: . . -:
yielding a precipitated ribbon, sheet or tube. Drops and ~' controlled streams may be added either above or below the ~ surface of the bath. Preferably the latex is added as drops ~ above the surface of the bath Entry of the latex into the bath and movement of the precipitated, coated object through the bath impart to the bath a degree of agitation. Additional agitation in the . ,.~ .
, form of stirring or shaking may be supplied, if desired, to r' assist in maintaining the uniformity of the bath. Agitation ~ 20 is particularly desirable when the pH of the bath is being :~:
-~ maintained by addition of acid as noted above.
~ The present process may be operated at temperatures :." ~ , r in the range from about 0C to about 100C. Temperatures in the range from about 5C to about 70C are preferred, with the range from about 10C to about 40 QC being particularly ''.~r preferred because of the improved stability of the bath in . .~, . .
this range.
Pressure is not a critical variable in the present process and pressures both above and below atmospheric pressure are operable. Atmospheric pressure is preferred for :, . . .
:.
~ - 13 -..", :,'' 1~91864 convenience.
The time from entry of a particular elastomeric latex body into the bath until removal of the nontacky elastomeric shaped object therefrom may be varied widely, depending somewhat on the minimum dimension of the object being coated. The time may vary from about 0.5 second up to about 6 hours or more. On contact with the bath, the latex starts to coagulate and a nontacky coating is formed immediately on the surface of the coagulated shaped object, e.g., within about 0.5 to about 5 seconds. Longer retention of the coated object in the bath is employed when it is desired to complete coagulation and neutralization of the latex in the center of the coated object before it is removed from the bath. In preferred baths, this requires less than about 6 minutes. Complete coagulation in the bath is not essential since coagulant which has penetrated the shaped object can continue to migrate toward the center of the ; object after removal of the object from the bath. It is preferable, however, to leave the object in the bath until , 20 sufficient coagulant has penetrated the object to complete the coagulation.
~- Referring now to the drawings, Figure 1 shows a preferred embodiment of suitable apparatus for carrying out ~- the process of this invention. This apparatus comprises a cylindrical tank 11 (27.94 cm i.d.) and a cylindrical draft ;~. , ~ tube 12 (12.7 cm i.d.) which is concentric with tank 11.
:, The tube and tank may be constructed of any rigid material such as glass, metal, or plastic. Draft tube 12 is extended on its upper end by a wire mesh screen 13 having a mesh size smaller than the size of the shaped objects being produced.
., :
: - :
Bath 14 containing the inorganic oxide polymer and the : coagulating salt is maintained at a liquid level such that the bath surface 15 is slightly below the upper edge of screen 13. Drops or discrete masses of polymer latex are introduced - into the bath within the zone circumscribed by screen 13. In this embodiment, stainless steel capillary tubes 16 (l.9 cm long, 0.86 mm i.d. and 1.3 mm o.d.) are used for forming the ;
latex drops. These tubes are mounted through polytetrafluoro-.' ethylene plugs in a stainless steel plate bolted to the lower end of pipe 17 (lO.l cm i.d.). The center-to-center distance between the tubes mounted in the plate is 1.11 cm. Sixty-one ' tubes are arranged in a hexagonal array with five tubes on a side. The frequency of drop addition to the bath is adjusted by varying the level of latex in pipe 17.
,,A;" An agitator 18 is provided in the bottom of tank 11 ~ to promote circulation of the bath in such a manner that flow , .~;
; of the bath solution is generally down through the draft tube, :, up through the space between the draft tube and the tank wall, ~ and through the screen to the confined bath surface. For this - 20 purpose, a 3-lobed (15.24 cm diameter) marine propeller is , . ., ,.,~
used.
:. ;~., s The screen at the top of the draft tube provides a .~ means of passing a solution which is free of shaped objects to the top of the draft tube. It also keeps out foam produced .: .
. by the agitation and helps keep the surface free of disturb-.;
l~; ances which might affect the uniformity of the shaped objects :,;
dropped through the surface. To increase agitation and thereby aid suspension of the coated latex particles in the annular space outside the draft tube, baffles 19 (3.81 cm wide) are .,.
placed vertically along the walls of tank 11 at 90 intervals.
. .
.
~ 15 --:
These baffles are not always necessary depending on the type of agitation used.
Through the action of the draft tube, screen, agitator and baffles, the shaped bodies contact a fresh solution, free of coated particles and foam. The shaped objects remain discrete as they pass down through the draft tube. By the time they emerge from the draft tube they are ~-coated so that the tendency to agglomerate with previously coated shaped objects is eliminated. The coated shaped ~;
objects are then held in suspension outside of the draft tube until they are removed from the bath.
A typical batch run can be made using this apparatus :~ .
; as follows: First, bath 14 comprising an aqueous solution of an inorganic salt, a small amount of surfactant, and the coating material is prepared, The salt serves to coagulate the latex during coating and after it is coated. The surfac-tant facilitates passage of latex drops through the surface of the bath.
Latex is added to standpipe 17 to produce a given head pressure and then continuously added to maintain this ' head pressure on the capillary tubes. Since no solution is withdrawn from the bath during the run, the bath level rises . , .
due to the addition of latex. Both standpipe 17 and draft ~ tube 12 are mounted so that they can be moved vertically.
; They are moved during the course of each run to maintain the capillary exits about 2.54 cm above bath surface 15, and the ;, upper edge of screen 13 about 0.835 cm above bath surface 15.
Although the apparatus illustrated in the drawings allows only batch removal of coated shaped objects at the con-clusion of each run, the process can be operated continuously :`
:' .
~' , by providing an overflow tube in tank 11 for continuous removal of coagulated, coated shaped ~bjects from the bath, filtering the suspension of shaped objects passing through ,. , the overflow tube, recycling the filtrate to the bath, and . r~placement o~ the bath components as they become exhausted.
A major advantage of the invention is that, when large numbers of uncured shaped objects are stored in contact ~- with each other under ordinary conditions, they do not . :
- agglomerate, but remain readily separable and free flowing. ' ~,...
The shaped objects have a minimum dimension of about Q.01 to ."", ~ .
about 10 millimeters. The minimum dimension should be at least about 0.01 mm to avoid dusting. Shaped objects wit~ a ` minimum dimension above about 10 mm require excessive power .,. :
' to mix with other ingredients in use applications. Prefer-,.......................................................................... .
,.,,i.i ably the shaped objects have minimum dimensions of about 0.1 i,, - mm to about 5 mm, Since the shaped bodies added to the bath are composed of latex, the water soluble coagulating salt quickly penetrates into the aqueous phase of the shaped objects, , 20 thereby coagulating the latex with a minimum of internal coalescence. As a result, the coagulated elastomer within ,~, .
the nontacky coating remains sufficiently porous for a suf-~ . .
~, ficient period of time to permit the washing out of water soluble components, including the coagulating salt. In the case of relatively crystalline elastomers, this porosity is retained indefinitely. In the case of relatively noncrystal-line elastomers such as neoprene, the porosity decreases on ,~..1 ",;
;~ long standing, but it does not completely disappear.
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After the precipitated shaped objects have been ` 30 coagulated and coated they can be separated from the bath . .
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by any suitable means. It is desirable to remove water soluble and volatile materials from the shaped objects after they have been separated from the bath. This may be accom-plished by washing with water or a polar organic solvent, followed by squeezing, centrifuging or drying, using conven-tional techniques. The shaped objects should be washed until ; they contain less than about 3% by weight of water soluble material, and preferably less than about 1%.
After the water soluble material has been removed . 10 to the desired extent, the shaped objects are dried to remove volatile material. Drying may be carried out at air temper-atures of about 25C to about 25QC. Preferably the drying is carried out at air temperatures of about 100C to about .
135C~ During this drying operation the temperature of the shaped objects is kept below the known thermal decomposition temperature of the polymer. Drying is continued until the shaped objects contain less than about 1% by weight of volatile material, and preferably less than about 0.5%. `~
,;~ . :.
~l During these finishing steps, polymers that are . ,,;~ .
relatively stiff (because of crystallinity, for example) remain opaque and porous, while normally tacky polymers ..:, ;~ coalesce further to translucence. Nevertheless, even these : ,i retain vestiges of their formerly highly porous structure, and the nontacky nature of the hydrous oxide coating deposited on - their exterior surface is retained. This nontacky coating may be supplemented by minor additions of talc, for example, '`b~' in the latter stages of high temperature drying, if desired.
The nontacky coating on the normally tacky elastomer ` is initially also porous so that moisture, solvents, soluble reaction ingredients and by-products can be readily removed :.
--- 11)91~;4 from within the coated object. The coating may represent from about 0.05 to about 3% by weight of the coated shaped object. Less than about 0.05~ generally does not provide adequate nontacky properties, while more than about 3% usually gives no added advantage to offset increased cost. Preferably the coating is about 0.5 to about 2% by weight of the coated object. Washing operations, such as noted above, point up the necessity for both the nontacky coating and the coagulated elastomer being porous for a period of time after formation - 10 of the shaped objects.
:; , Figure 3 is a photomicrograph of a cross section of a typical, porous shaped object in accordance with this invention. In this photograph, the porosity of the shaped object is apparent; voids appear as dark areas as observed at 20 The nontacky coating appears as light areas as is readily observed at 21.
The nontacky coated objects of this invention can also contain fillers, pigments, colorants, softeners, ; extenders, antioxidants, stabilizers, curing agents, and the like. Such materials may be incorporated by adding them to ,. . .
the starting polymer latex or to the coagulating and coating ~- bath.
.,~, ?'.- The following examples illustrate the preparation of nontacky, elastomeric shaped objects of this invention.
Each of the washed and dried, nontacky, elastomeric :, shaped objects prepared in these examples had a water soluble ~! material content of less than about 3~ by weight and a volatile material content of less than about 1%. In each case the inorganic oxide polymer coating was about 0.05 to about 3% by weight of the shaped objects and the minimum ,:
:: -- 19 --. .
,; .
10918~4 dimension of the shaped objects was about 0.01 to about 10 millimeters. All parts and percentages are by weight throughout the examples.
; The neoprene latices used in these examples were prepared as follows.
Neoprene Latex #l ;~ This latex was prepared from an aqueous, alkaline emulsion containing 100 parts of chloroprene and 0.23 part ~-~'~ of dodecyl mercaptan as modifier and stabilized by 2.9 parts of the sodium salt of disproportionated wood rosin. Chloro-prene was polymerized by adjusting the emulsion temperature ~., ' to 40C and add~ng continuously, at a rate allowing control of the temperature at 4QC by external cooling, an aqueous solution containing 0.3% K2S2O8 and 0.015% Na salt of ' anthraquinone-~-sulfonic acid. The polymerization was ter- ~ '~
minated at about 67% conversion of the chloroprene monomer by , '~'!'~ theaddition of an aqueous emulsion of a toluene solution - ::
:~.
~: containing 0.015 part of phenothiazine and 0.015 part of ~ 4-tert.-butylcatechol.
`;' 20 After removal of residual monomer by distillation, ' the latex contained about 37~ solids. The polymer had an -'~ inherent vi$cosity of 1.20 (0.1 g/100 ml benzene at 30C~.
....
~ The pH of the latex was about 12.
: '.'.`
Neoprene Latex #2 , .- .
~' An aqueous, alkaline emulsion was prepared containing 100 parts of chloroprene, 0.15 part of dodecyl mercaptan and
Natural rubber also occurs as a latex. Some latices are highly useful as formed, for example, basic formulations for latex paints. For other uses, it is necessary to coagulate the polymer and separate it from the latex. The most important commercial form for these polymers is as washed and dried, non-tacky shaped objects. These shaped objects should be washed ' until they contain less than about 3~ by weight of water ` soluble material, and dried until they contain less than about 1% by weight of volatile material.
! If the coagulated polymer is inherently nontacky, the polymer is readily isolated from the aqueous phase, washed and dried to form a free-flowing powder which is readily handled :
in further processing. If, however, the polymer is inherently tacky, coagulating of the latex yields the polymer in an agglo-merated mass which is difficult to wash free of impurities and also difficult to dissolve, to blend with other materials, and ;:
to feed in compounding, curing and molding operations.
;' :~
i~ In the field of natural and synthetic rubber, much attention has been given to the problem of agglomeration of normally tacky polymers before curing. Some operable solutions ... .
, . . . .
~0~1864 have been found.
In U.S. 2,879,173, Yacoe shows a process for coagulating a polychloroprene latex by suspending drops in a volatile, water-immiscible, organic liquid in which the poly- `-chloroprene latex is insoluble while maintaining the liquid below about -20C until the drops are completely frozen and coagulated. The resulting frozen pellets are separated and coated, while still frozen, with from 5~ to 20~ by weight of an inert powder, such as talc, so that they will not stick together when thawed and dried. However, the use of this process has been limited by the cost of organic liquid recovery, the energy cost of the refrigeration, and the un-desirable high loading of inert material. The need for a more practical and economical method of preparing nontacky, washed and dried shaped objects of normally tacky elastomers remains.
In U.S. 3,053,824, Heinz shows coagulation of a phosphate or borate buffered elastomer latex by running it into an aqueous aluminum or titanium salt solution containing ,:
-~ 20 also an alkali metal or alkaline earth metal salt. The patent ;
states that the resulting coagulated particles do not stick together before being washed to remove the coagulating salts.
There is no statement as to the tack of the particles after .-washing.
In U.S. 3,846,365, Berg et al. show a powdery,filled polymer prepared by emulsifying together a dilute :
solution of an elastomer in a volatile organic solvent and a solid, finely-divided filler for the eIastomer, passing the emulsion into an aqueous alkali silicate solution at a pH preferably of 7 to 12, and evaporating the organic solvent.
. .
.; - 2 -"
,-'.,:
. . .
- , .
. ~ .
A finely-divided, tack-free coprecipitate of the latex and ;~
silicic acid residue is formed. It is stated that condensation - of the silicate anions should be avoided.
, SUMMARY OF THE INVENTION
This invention is based on the discovery that nontacky, uncured, washed and dried, elastomeric shaped ob-jects can be produced from a normally tacky elastomer latex by a simple and inexpensive process. This invention provides nontacky, elastomeric shaped objects which comprise a normally tacky, uncured elastomer containing, baséd on the total weight of the shaped object, less than about 3% by weight of water soluble material, and less than about 1% by weight of volatile material, and having about 0.05 to about 3% by weight of an integral, porous coating of a water insoluble, hydrous inor-ganic oxide selected from the group consisting of silicic and aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, said shaped objects having a minimum dimension of about 0.01 to about 10 millimeters. By "integral"
., is meant a coating which has unity, rather than being composed ~0 of discrete particles such as in the case of a powder coating.
By "minimum dimension" is meant the diameter of the smallest round hole through which the shaped object will pass lengthwise.
A unique feature of this invention is that, prior to ; removing the water soluble and volatile materials, the nontacky ., shaped objects are highly porous. This porosity is evidenced . .
by the objects being opaque in appearance when dispersed in ....
~ water, and by their cross section having a vesicular structure . .
in micrographs. Because of this porosity, water soluble and ` volatile materials are easily removed by washing and drying ": .
:~ - 3 -,' ' , :' ~-. . . : . -109~864 techniques. Some of the porosity is retained even after washing and drying.
The nontacky, elastomeric shaped objects of this invention are prepared by a process which comprises bringing shaped bodies of a normally tacky, uncured elastomer latex having a solids content of 20% to 65% by weight into contact with an aqueous bath containing, based on the total weight of the bath, a) about 0.5% to about 25% by weight of a soluble coagulating salt for the latex, and b) about 0.01% to about 5% by weight of a ;~ soluble or colloidally dispersed, hydrous inorganic oxide selected from the group consisting of silicic and aluminic acid - polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, , said bath having a pH of about 2 to about 7 such that, when a drop of 1.0N NaOH is added to the . ~
;~` 20 bath, the drop is immediately surrounded by a ,, ~ cloudy coating of gelled, hydrous inorganic oxide, :, -:
thereby coagulating the lateX and forming highly porous shaped objects of the coagulated elastomer coated with water insoluble, . .
hydrous, inorganic oxide. These shaped objects can then be washed with water until the water soluble material content is less than about 3% by weight, and dried until the volatile material content is less than a~out 1% by weight, thereby providing free-flowing, nontacky, elastomeric shaped objects.
This invention is particularly suitable for producing nontacky , .
pellets of uncured neoprene.
The term "shaped body" is used herein to designate 86~
tho letex berore lt contacts the aqueous bath. m e tor~
~8haped obJoct~ 18 used hereln to deslgnato the latex and ~ub~oquent elastomer arter the shaped body enter~ the bath.
BRIEF DESCRIPTION OF THE DRANING~
Flgure 1 illustrate~ a vle~ in central vortical ~ection and partlally ln slde elevation of a preferred apparatus ~or carrylng out one embodiment Or the procoss o~
- thls lnventlon. m i8 apparatus and the method of u8ing lt 18 clalmed ln U.S. Patent 4,110,491 Or R. ~. Secor, whlch : 10 lssu d 1978 August 29.
Figure 2 lllustrates a top vle~ o~ the same apparatNs a~ Flgure 1 taken through cut 2-2.
Figure 3 i~ a photoEicrograph Or a cross ~oction Or a porous ~haped obJect ln accordance ulth thla in~entlon.
` DE~CRIPTION OP THE PREF~RRED EMBODIMENTS
In accordance ulth thls lnvention, an lnorganlc ~- oxido polymer coatlng 18 ¢hemically depo~lted on a shaped ob~ect Or normally tacky ola~tomer from solutlon or disper-sion ln an aquoous bath. The ¢oatlng, as formed, 18 there-fore a porou~, nonp-rtlculate, unitary pelllcle entirely ; surroundlng each shaped ob~ect. Eecause of the integral .
~- nature o~ the coating, no~tacky ob~octs can be obtalned with very 8mall loadings o~ coating material. Thls 1~
;
~ particularly lmportant ~or elastomers that are subsequently .~
~;~ di~solved be~ore curing, and is ln sharp contra~t to the requisite heavy lo~dlngs of p~rtieulate materials, sueh as ; tale, uhieh have previ~usly been u~ed to render uncured el~stomeric ob~ects nont~eky.
Tho produets Or th~s ln~ontlon are nontacky shaped ob~ect~ of normally taeky, uneured elastomers. m e term " ~
' .. . .
"elastomer" is well known to those skilled in the art and has been defined in publications such as "ASTM Glossary of Terms Relating to Rubber and Rubber Like Materials", page 38. By "normally tacky elastomer" is meant an elastomer, two pieces of which, when uncured and in the most decrystallized condition, will stick together at room temperature.
Suitable elastomers for use in accordance with this invention include homopolymers and copolymers of conjugated dienes such as neoprene and natural rubber; copolymers of conjugated dienes with other polymerizable, organic monomers, for example butadiene-acrylonitrile and butadiene-styrene copolymers; elastomeric fluoropolymers (fluorine-containing polymers), preferably copolymers of vinylidene fluoride and at least one other fluorine-containing monomer, for exam~ple copolymers of vinylidene fluoride and hexafluoropropene (U.S. 3,051,677), and terpolymers of tetrafluoroethylene, vinylidene fluoride and hexafluoropropene (U.S. 2,968,649);
adhesive-type elastomers such as polyvinyl acetate and ethylene-vinyl acetate copolymers; acrylate rubbers such as .~:
the lower alkyl acrylate ester polymers; hydrocarbon elastomers such as polyisobutylene, the terpolymers of ethylene, propylene and non-conjugated dienes; and similar materials.
The preferred elastomer is neoprene. By "neoprene"
., is meant an elastomer comprising at least about 50~ chloroprene . .
(2-chloro-1,3-butadiene?. Representative comonomers that can be used with chloroprene include vinyl aromatic compounds, " ~
such as styrene, the vinyl toluenes, and vinyl-naphthalenes;
. .
aliphatic conjugated diolefin compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 2,3-dichloro-1,3-butadiene; vinyl ethers, esters, and ketones, such as methyl , ~091864 vinyl ether, vinyl acetate, and methyl vinyl ketone; esters,amines, and nitriles of acrylic and methacryIic acids, such a~i ethyl acrylate, methyl methacrylate, methacrylamide, and acrylonitrile; and the like.
Neoprene latices for use in this invention may be prepared by the known aqueous emulsion polymerization of chloroprene, using a sodium rosinate dispersant and a free-radical type polymerization catalyst such as potassium persulfate. The sodium resinate dispersant may be prepared in situ from rosin acids and sodium hydroxide.
Additives such as fillers, antioxidants and the like ; may be present during the polymerization. The polymerization is allowed to proceed to a predetermined degree of completion, after which a catalyst ~hortstop can be added, and residual chloroprene monomer is stripped off. Minor variations in the procedure yield latices of polymers varying in molecular weight, viscosity, crystallinity, and other properties. In order to form pellets in the process of this invention, the latex should have a solids content of at least about 20% by ~- 20 weight. Suitable latices can have solids contents up to about :~.
65%. Latices generally coagulate when the solids content goes above about 65%. Preferably the latex has a solids content from about 35% to about 50~i. -This invention involves the process of adding drops, a controlled stream, or some other dispensed form of a latex of the normally tacky elastomer to an aqueous coagulating and coating bath thereby forming a coated shaped object. The latex emulsion should be stable enough to survive through the .
addition step until the shaped object is fully penetrated by '^.
; 30 the coagulating salt and any neutralizing agent present.
i .i `~ - 7 ., _ ' :
''-, 109~86~
Neoprene latices are normally stabilized against premature coalescence by sodium rosinate; natural rubber by ammonia.
The aqueous coagulating and coating bath contains a coagulating salt for the latex, that is, a salt which will coagulate the elastomer latex. Suitable coagulating salts are well known to those skilled in the art; for example, see "Neoprene Latex", by J. C. Carl, pages 19-21, published by E. I. du Pont de Nemours and Company (Inc.), Wilmington, Delaware. Operable salts which may be employed include the water soluble sulfates, chlorides, bromides, nitrates, -citrates, acetates, formates and phosphates of ammonium, sodium, potassium, calcium, magnesium, strontium, barium, lithium, beryllium, aluminum, manganese, zinc, yttrium, iron and cadmium. Mixtures of such salts may also be used.
Desirable, but nonlimiting, characteristics of the coagulating salt include low cost, colorless solutions, cations ,, and anions which are not readily oxidizable or reducible, noncoprecipitating with the alkali metal salt accumulating in the bath, nontoxic, and nonpolluting. Preferably, the salt t". 20 should be chemically inert to the elastomer and insoluble therein. The preferred salts are soluble chlorides, sulfates, acetates, nitrates and phosphates of sodium, potassium, ammonium, calcium, magnesium and aluminum. The most preferred salts are the soluble chlorides and sulfates of the above cations. The coagulating salt may constitute from about 0.5%
to about 25% by weight of the bath. The operable amount of coagulating salt within this range in any given case will depend upon the particular latex, the pH of the bath, and the `/ particular inorganic oxide present. Generally, the optimum and preferred amount of salt is in the range of about 1% to 1~91864 about 10%.
he bath also contains a soluble or colloidally ; dispersed, hydrous inorganic oxide selected from the group consisting of silicic and aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. These oxides àre those commonly considered as existing in polymeric , ~ form, the structure of which may be linear chains, ribbons, ~
., or when highly cross-linked) even globules, in which atoms . ~.
of the inorganic element alternate with oxygen atoms. In .i, .
such polymers, some of the peripheral groups are -OH groups.
The inorganic oxide may be used in water soluble form, as in the case of polysilicic acid and polyaluminic -, . .
acid, or in more highly polymerized, particulate form as in the case of colloidally dispersible silica sols as described ~
.. ...
in U.S. 2,574,902 and alumina sols as described in U.S.
2,590,833. In practice, most a~ueous systems containing such compounds have at least part of the polymeric oxide in the form of dispersed particles. The terms, "silicic acid polymers" and "aluminic acid polymers" are intended to in-clude these polymers in both the soluble and the colloidally dispersible form. The inorganic oxides may be in crystalline or amorphous form, and a mixture of two or more such oxides may be used. The most preferred inorganic oxides are poly-silicic acid, polyaluminic acid and silicic acid-aluminic acid copolymers.
....
:~
~ If the coagulating salt employed is an aluminum ,:;., salt and the inorganic oxide is polysilicic acid, some of the aluminic hydroxyls generated at the alkaline surface of the latex may copolymerize by condensation with silanol ~; 30 groups to form an aluminic acid-silicic acid copolymer. If :"
:.
:. _ 9 _ ,.~
. . ~ ,.
, : . .
' .
. ~ , ~ . . . .
109~
the coagulating salt employed is not an aluminum salt, particularly if the bath is utilizing polysilicic acid as t~e coating material, it is desirable, though not essential, to add to the bath about 0.002~ to about 2% by weight of an ionizable aluminum salt. Although copolymerization of the aluminum has not been established, it is believed that this accounts for the inorganic oxide being rendered more effective as a coating, possibly by reducing any subsequent solubility of the coating in the wash water. For this pur-pose, it has been found that yttrium salts are equivalent to aluminum salts and may be substituted in whole or in part therefor. Accordingly, the term "silicic acid-aluminic acid copolymer" should be construed in the claims to cover this substitution of equivalents.
It is generally recognized that, in freshly prepared silicic acid solutions, the silicic acid is not .~ ,. , monomeric, but has a molecular weight of the order of about 1000. As the silicic acid solution ages, the molecular weight continues to rise until finally the solution gels (see 20 Bechtold, J. Phys. Chem., 59, 532-541 (1955)). The silicic acid solution used in accordance with this invention should not have aged for more than about 90% of its gel time prior .~, ~ to being added to the bath. Preferably, the silicic acid , .~.
solution has aged for about 5% to about 70% of its gel time prior to being added to the bath. When operating in a continuous manner, silicic acid is continuously added to and removed from the bath, whereby the average age of the -; polysilicic acid réaches a constant value which is less than .:
its gel time.
..~
,.:
~ - 10-,~, The hydrous inorganic oxide may constitute from about 0.01% to about 5% by weight of the coagulating bath.
The presence of more than about 5% inorganic oxide does not lead to any further improvement in the nontacky proper-ties of the product. Preferably the inorganic oxide is present in the amount of about 0.03~ to about 2%. The oxide ; may be polymerized or crystallized during the coating opera-tion. One criterion for determining when a bath is no longer suitable for the present process is coagulation of the bath ; 10 due to changed conditions such as pH or to exhaustion of ;~
essential ingredients.
Optionally, the bath may also contain a minor amount of surfactant to reduce the air-liquid interfacial -tension and assist penetration of the shaped latex body into the bath. Suitable surfactants are characterized by ., , ; being effective at low concentrations and being compatible, " . .
that is, not causing polymerization or cross-linking of the ~: .
~ç, hydrous oxide component, and being inert to the coagulating ~,. , salt. A wide variety of nonionic, anionic, cationic and ~ 20amphoteric surfactants may be used. Examples of suitable i surfactants include lower alkyl alcohols such as ethanol, the trimethylnonanol ether of ethylene oxide, sodium ; heptadecyl sulfate, sodium lauryl sulfate, the condensation , products of tertiary amines with ethylene oxide, fluori-nated amphoteric surfactants, and the like. The surfactant ~, ;~ preferably is added in an amount sufficient to reduce the .--.
`'t"air-liquid interfacial tension to less than about 50 dynes/cm -: -and particularly less than about 35 dynes/cm.
The bath is operable in a pH range of about 2 to ... .
~ 30 about 7. If the pH is below about 2, the inorganic oxide . "
;
, ::,,- , :
- 1a91864 is difficult to gel on the surface of the shaped object.
If the pH is above about 7, the inorganic oxide may be converted to a soluble salt. The operable pH within this range for any given system will depend on the particular latex, coagulating salt and inorganic oxide present.
Within this range, pH values from about 2.5 to about 5.5 are particularly preferred for optimum balance of bath stability with coating effectiveness. If the pH of the bath is maintained in the desired range by proportional addition of a neutralizing agent as the alkaline latex bodies enter the bath, the life of the bath can be substan-tially prolonged. Organic and inorganic acids such as acetic acid and aqueous hydrochloric acid, and hydrolyzable acidic salts such as AlC13 are particularly suitable neutralizing agents .
Operability of the bath to provide a coating on the shaped object is a function of the amount and type of hydrous inorganic oxide present and the pH of the bath. It has been found that not all combinations of the above vari-.... .
ables lead to operable baths. Although the requîrements for a functional bath are not fully understood, a simple . .
- test has been found for determining whether the bath is ~; functional. In this test, a drop of 1.0N sodium hydroxide .. .
is added to the bath. If the drop is immediately surrounded s by a cloudy coating of gelled hydrous oxide, the bath is -- functional.
Although the pH of various latices vary over wide limits, it is preferable that the pH of the latex be equal to or greater than the pH of the bath. When the latex is : 30 neoprene containing sodium rosinate as the stabilizer, the ' 64 :~
p~ of the latex will be greater than about 7 unless it has been acidified.
When the latex is added as drops, the precipitated shaped objects obtained may be lumps, beads, pellets ~with or without a "tail"), discs or rings depending on the sur-face tension and density of the precipitating bath and the speed and direction of the latex as it enters the bath.
When the latex is added as a controlled stream, the stream may be filamentous, yielding a precipitated fiber or bead- `~
ing, or the stream may be spread out in flat or curved form .: . . -:
yielding a precipitated ribbon, sheet or tube. Drops and ~' controlled streams may be added either above or below the ~ surface of the bath. Preferably the latex is added as drops ~ above the surface of the bath Entry of the latex into the bath and movement of the precipitated, coated object through the bath impart to the bath a degree of agitation. Additional agitation in the . ,.~ .
, form of stirring or shaking may be supplied, if desired, to r' assist in maintaining the uniformity of the bath. Agitation ~ 20 is particularly desirable when the pH of the bath is being :~:
-~ maintained by addition of acid as noted above.
~ The present process may be operated at temperatures :." ~ , r in the range from about 0C to about 100C. Temperatures in the range from about 5C to about 70C are preferred, with the range from about 10C to about 40 QC being particularly ''.~r preferred because of the improved stability of the bath in . .~, . .
this range.
Pressure is not a critical variable in the present process and pressures both above and below atmospheric pressure are operable. Atmospheric pressure is preferred for :, . . .
:.
~ - 13 -..", :,'' 1~91864 convenience.
The time from entry of a particular elastomeric latex body into the bath until removal of the nontacky elastomeric shaped object therefrom may be varied widely, depending somewhat on the minimum dimension of the object being coated. The time may vary from about 0.5 second up to about 6 hours or more. On contact with the bath, the latex starts to coagulate and a nontacky coating is formed immediately on the surface of the coagulated shaped object, e.g., within about 0.5 to about 5 seconds. Longer retention of the coated object in the bath is employed when it is desired to complete coagulation and neutralization of the latex in the center of the coated object before it is removed from the bath. In preferred baths, this requires less than about 6 minutes. Complete coagulation in the bath is not essential since coagulant which has penetrated the shaped object can continue to migrate toward the center of the ; object after removal of the object from the bath. It is preferable, however, to leave the object in the bath until , 20 sufficient coagulant has penetrated the object to complete the coagulation.
~- Referring now to the drawings, Figure 1 shows a preferred embodiment of suitable apparatus for carrying out ~- the process of this invention. This apparatus comprises a cylindrical tank 11 (27.94 cm i.d.) and a cylindrical draft ;~. , ~ tube 12 (12.7 cm i.d.) which is concentric with tank 11.
:, The tube and tank may be constructed of any rigid material such as glass, metal, or plastic. Draft tube 12 is extended on its upper end by a wire mesh screen 13 having a mesh size smaller than the size of the shaped objects being produced.
., :
: - :
Bath 14 containing the inorganic oxide polymer and the : coagulating salt is maintained at a liquid level such that the bath surface 15 is slightly below the upper edge of screen 13. Drops or discrete masses of polymer latex are introduced - into the bath within the zone circumscribed by screen 13. In this embodiment, stainless steel capillary tubes 16 (l.9 cm long, 0.86 mm i.d. and 1.3 mm o.d.) are used for forming the ;
latex drops. These tubes are mounted through polytetrafluoro-.' ethylene plugs in a stainless steel plate bolted to the lower end of pipe 17 (lO.l cm i.d.). The center-to-center distance between the tubes mounted in the plate is 1.11 cm. Sixty-one ' tubes are arranged in a hexagonal array with five tubes on a side. The frequency of drop addition to the bath is adjusted by varying the level of latex in pipe 17.
,,A;" An agitator 18 is provided in the bottom of tank 11 ~ to promote circulation of the bath in such a manner that flow , .~;
; of the bath solution is generally down through the draft tube, :, up through the space between the draft tube and the tank wall, ~ and through the screen to the confined bath surface. For this - 20 purpose, a 3-lobed (15.24 cm diameter) marine propeller is , . ., ,.,~
used.
:. ;~., s The screen at the top of the draft tube provides a .~ means of passing a solution which is free of shaped objects to the top of the draft tube. It also keeps out foam produced .: .
. by the agitation and helps keep the surface free of disturb-.;
l~; ances which might affect the uniformity of the shaped objects :,;
dropped through the surface. To increase agitation and thereby aid suspension of the coated latex particles in the annular space outside the draft tube, baffles 19 (3.81 cm wide) are .,.
placed vertically along the walls of tank 11 at 90 intervals.
. .
.
~ 15 --:
These baffles are not always necessary depending on the type of agitation used.
Through the action of the draft tube, screen, agitator and baffles, the shaped bodies contact a fresh solution, free of coated particles and foam. The shaped objects remain discrete as they pass down through the draft tube. By the time they emerge from the draft tube they are ~-coated so that the tendency to agglomerate with previously coated shaped objects is eliminated. The coated shaped ~;
objects are then held in suspension outside of the draft tube until they are removed from the bath.
A typical batch run can be made using this apparatus :~ .
; as follows: First, bath 14 comprising an aqueous solution of an inorganic salt, a small amount of surfactant, and the coating material is prepared, The salt serves to coagulate the latex during coating and after it is coated. The surfac-tant facilitates passage of latex drops through the surface of the bath.
Latex is added to standpipe 17 to produce a given head pressure and then continuously added to maintain this ' head pressure on the capillary tubes. Since no solution is withdrawn from the bath during the run, the bath level rises . , .
due to the addition of latex. Both standpipe 17 and draft ~ tube 12 are mounted so that they can be moved vertically.
; They are moved during the course of each run to maintain the capillary exits about 2.54 cm above bath surface 15, and the ;, upper edge of screen 13 about 0.835 cm above bath surface 15.
Although the apparatus illustrated in the drawings allows only batch removal of coated shaped objects at the con-clusion of each run, the process can be operated continuously :`
:' .
~' , by providing an overflow tube in tank 11 for continuous removal of coagulated, coated shaped ~bjects from the bath, filtering the suspension of shaped objects passing through ,. , the overflow tube, recycling the filtrate to the bath, and . r~placement o~ the bath components as they become exhausted.
A major advantage of the invention is that, when large numbers of uncured shaped objects are stored in contact ~- with each other under ordinary conditions, they do not . :
- agglomerate, but remain readily separable and free flowing. ' ~,...
The shaped objects have a minimum dimension of about Q.01 to ."", ~ .
about 10 millimeters. The minimum dimension should be at least about 0.01 mm to avoid dusting. Shaped objects wit~ a ` minimum dimension above about 10 mm require excessive power .,. :
' to mix with other ingredients in use applications. Prefer-,.......................................................................... .
,.,,i.i ably the shaped objects have minimum dimensions of about 0.1 i,, - mm to about 5 mm, Since the shaped bodies added to the bath are composed of latex, the water soluble coagulating salt quickly penetrates into the aqueous phase of the shaped objects, , 20 thereby coagulating the latex with a minimum of internal coalescence. As a result, the coagulated elastomer within ,~, .
the nontacky coating remains sufficiently porous for a suf-~ . .
~, ficient period of time to permit the washing out of water soluble components, including the coagulating salt. In the case of relatively crystalline elastomers, this porosity is retained indefinitely. In the case of relatively noncrystal-line elastomers such as neoprene, the porosity decreases on ,~..1 ",;
;~ long standing, but it does not completely disappear.
-',:
After the precipitated shaped objects have been ` 30 coagulated and coated they can be separated from the bath . .
.
`:
:~
.
~ . :
by any suitable means. It is desirable to remove water soluble and volatile materials from the shaped objects after they have been separated from the bath. This may be accom-plished by washing with water or a polar organic solvent, followed by squeezing, centrifuging or drying, using conven-tional techniques. The shaped objects should be washed until ; they contain less than about 3% by weight of water soluble material, and preferably less than about 1%.
After the water soluble material has been removed . 10 to the desired extent, the shaped objects are dried to remove volatile material. Drying may be carried out at air temper-atures of about 25C to about 25QC. Preferably the drying is carried out at air temperatures of about 100C to about .
135C~ During this drying operation the temperature of the shaped objects is kept below the known thermal decomposition temperature of the polymer. Drying is continued until the shaped objects contain less than about 1% by weight of volatile material, and preferably less than about 0.5%. `~
,;~ . :.
~l During these finishing steps, polymers that are . ,,;~ .
relatively stiff (because of crystallinity, for example) remain opaque and porous, while normally tacky polymers ..:, ;~ coalesce further to translucence. Nevertheless, even these : ,i retain vestiges of their formerly highly porous structure, and the nontacky nature of the hydrous oxide coating deposited on - their exterior surface is retained. This nontacky coating may be supplemented by minor additions of talc, for example, '`b~' in the latter stages of high temperature drying, if desired.
The nontacky coating on the normally tacky elastomer ` is initially also porous so that moisture, solvents, soluble reaction ingredients and by-products can be readily removed :.
--- 11)91~;4 from within the coated object. The coating may represent from about 0.05 to about 3% by weight of the coated shaped object. Less than about 0.05~ generally does not provide adequate nontacky properties, while more than about 3% usually gives no added advantage to offset increased cost. Preferably the coating is about 0.5 to about 2% by weight of the coated object. Washing operations, such as noted above, point up the necessity for both the nontacky coating and the coagulated elastomer being porous for a period of time after formation - 10 of the shaped objects.
:; , Figure 3 is a photomicrograph of a cross section of a typical, porous shaped object in accordance with this invention. In this photograph, the porosity of the shaped object is apparent; voids appear as dark areas as observed at 20 The nontacky coating appears as light areas as is readily observed at 21.
The nontacky coated objects of this invention can also contain fillers, pigments, colorants, softeners, ; extenders, antioxidants, stabilizers, curing agents, and the like. Such materials may be incorporated by adding them to ,. . .
the starting polymer latex or to the coagulating and coating ~- bath.
.,~, ?'.- The following examples illustrate the preparation of nontacky, elastomeric shaped objects of this invention.
Each of the washed and dried, nontacky, elastomeric :, shaped objects prepared in these examples had a water soluble ~! material content of less than about 3~ by weight and a volatile material content of less than about 1%. In each case the inorganic oxide polymer coating was about 0.05 to about 3% by weight of the shaped objects and the minimum ,:
:: -- 19 --. .
,; .
10918~4 dimension of the shaped objects was about 0.01 to about 10 millimeters. All parts and percentages are by weight throughout the examples.
; The neoprene latices used in these examples were prepared as follows.
Neoprene Latex #l ;~ This latex was prepared from an aqueous, alkaline emulsion containing 100 parts of chloroprene and 0.23 part ~-~'~ of dodecyl mercaptan as modifier and stabilized by 2.9 parts of the sodium salt of disproportionated wood rosin. Chloro-prene was polymerized by adjusting the emulsion temperature ~., ' to 40C and add~ng continuously, at a rate allowing control of the temperature at 4QC by external cooling, an aqueous solution containing 0.3% K2S2O8 and 0.015% Na salt of ' anthraquinone-~-sulfonic acid. The polymerization was ter- ~ '~
minated at about 67% conversion of the chloroprene monomer by , '~'!'~ theaddition of an aqueous emulsion of a toluene solution - ::
:~.
~: containing 0.015 part of phenothiazine and 0.015 part of ~ 4-tert.-butylcatechol.
`;' 20 After removal of residual monomer by distillation, ' the latex contained about 37~ solids. The polymer had an -'~ inherent vi$cosity of 1.20 (0.1 g/100 ml benzene at 30C~.
....
~ The pH of the latex was about 12.
: '.'.`
Neoprene Latex #2 , .- .
~' An aqueous, alkaline emulsion was prepared containing 100 parts of chloroprene, 0.15 part of dodecyl mercaptan and
3.5 parts of the sodium salt of disproportionated wood rosin.
:
Chloroprene was polymerized by adjusting the emulsion temper-' ature to 10C and adding continuously an aqueous dispersion ''""
:' " . .
.~
:, `'' "
109~864 containing 1.0~ K2S2O8, 0.05% sodium salt of anthraquinone-~~sulfonic acid, and 0.14% cumene hydroperoxide at a rate allowing control of the temperature between 10 and 20C.
The polymerization was terminated at about 85% conversion of the chloroprene monomer by addition in the form of an aqueous emulsion of a toluene solution of 0.03 part of phenothiazine and 0.03 part of 4-tert.-butylcatechol.
After removal of residual monomer the emulsion contained 37% solids and had a pH of 12.5.
Neoprene Latex #3 The preparation of neoprene latex #l was repeated except that the 100 parts of chloroprene was replaced by a -mixture of 92 parts of chloroprene and 8 parts of 2,3-dichloro-1,3-butadiene. The polymerization was stopped at 65% conversion, and the latex, after stripping, contained about 33% solids and had a pH of 12.
",, .
Neoprene LateX #4 The procedure described for neoprene latex #2 was repeated except that the amount of dodecyl mercaptan in the monomer emulsion was 0.12 part instead of 0.15 part~ The resulting latex had a solids content of 37% and a pH of 12.5.
Example l :.
A bath containing approximately 0.7% sio2 and 3.9%
Ca(NO3)2 was made by combining 90 ml of 0.25M aqueous silicic ` acid (produced by the ion exchange of H+ for Na+ in 0.25M
sodium metasilicate solution), 10 ml of a 50% aqueous Ca(NO3)2 solution, and lO0 ml of absolute ethanol. About 20 ml of neoprene latex #l (37% solids, pH 12) was added dropwise ''~
','`
"~
.:
1C)9~864 to this bath from an orifice about 2 cm above it. The surface of the drops coagulated on contact to yield globules which within a few minutes were coagulated throughout and c~vered with a nontacky coating. The resulting opaque pellets were lifted from the bath and dried in a 60C oven.
At room temperature they remained dry to the touch and free-flowing.
For comparison, the following experiment, not within the scope of the invention, was carried out. The above example was repeated using 9Q ml of water in place of the silicic acid solution. The drops of emulsion coagulated ; rapidly, but remained very tacky and were difficult to :
separate after drying at 60C.
Example 2 A bath containing approximately 3.6% SiO2 and 2.6% CaC12 was made by mixing 1000 ml of lM silicic acid, 60 ml of 50~ CaC12 solution, 700 ml of absolute ethanol, and 240 ml of distilled water. About 200 ml of neoprene , latex #1 (37~ solids, pH 12) was introduced into the bath dropwise. The resulting pellets were allowed to remain in the bath for 30 minutes. They were removed, washed with 70%
ethanol, and dried for 48 hours in a vacuum drying pistol heated by refluxing acetone. The resulting pellets had the following analysis: Ca, 0.25; Na, 0.38; Si, 0.51; % ash, 2.8. Pellets prepared in this way retained a small amount , ,:
of alkali. Such amounts of residual alkali stabilize neo-prene against HCl degradation. A 5% suspension of these pellets in water had a pH of 9Ø The pellets were more than 90% soluble in toluene, indicating little or no crosslinking ':
.
1~)91864 of the neoprene had occurred.
Example 3 An alcohol-free bath containing approximately 1.5 SiO2 and 2.1~ CaC12 was made, utilizing a dilute aqueous nonionic surfactant solution to reduce interfacial tension at the air-liquid interface. A mixture of 10 ml of freshly prepared 0.5M silicic acid, 9.4 ml of 0.2% aqueous tri-methylnonanol ether of ethylene oxide (Tergitol~ TMN-6, Union Carbide), and 0.6 ml of 50% CaC12 completed the bath. About 2 ml of neoprene latex #1 (37% solids, pH 12) introduced drop-wise into the bath formed opaque nonsticking pellets. These were isolated, washed with water, and air dried to produce free-flowing, nonsticking pellets 3-4 mm in diameter. The moisture content of the pellets was 0.38%; the ash residue was 3.05~; other analyses were: Ca, 0.44~; Na, 0.26~;Si, ~, 1. 11~.
Example 4 A bath containing approximately 1.5% SiO2 and 2.1 CaC12 was prepared from lQ00 ml of 0.5M silicic acid (pH
3.3), 940 ml of 0.2% aqueous trimethylnonanol ether of ethyl-' ene oxide (Tergitol~ TMN-6), and 60 ml of 50% aqueous CaC12 solution. The initial pH of the bath was 4.45. One hundred ~ milliliters of neoprene latex #1 (37% solids, pH 12) was added ,~
` dropwise over a period of 10 minutes during which the bath , ~ was stirred and the pH was maintained at 4.Q by continuous , . . .
addition of 1.0N hydrochloric acid. The bath showed no evi-dence of gelation. The neoprene pellets which formed were ....
filtered from the bath on a lQ0 mesh stainless steel screen, washed with cold water and dried. They were non-tacky and free-flowing.
: .
:.' ":
.
~091864 Example 5 A silicic acid solution was prepared from a sodium silicate solution having an SiO2/Na20 ratio of 1.95. The -sodium silicate solution utilized was Grade 6 (Du Pont Co.) which had a viscosity of 60,000 centipoises (68C), a specific gravity of 1.708, % Na20 = 18.4, and ~ SiO2 = 36Ø This solution (166.5 ml) was diluted to 2 liters with distilled water. The resulting solution was passed through a cation exchange column in acid form containing 1300 gms of cation exchange resin (Rexyn 101, H+). The first 500 ml of effluent, equivalent to the retention volume of the column, was discarded and the remainder collected.
A 1000 ml portion of this 0.85M silicic acid ~, ~olution was employed in the procedure of Example 4 to give a bath containing approximately 2.5% SiO2. At the start of the addition of neoprene latex the bath was a pH 3.1 and at the conclusion the pH was 4.1. The resulting pellets were washed with distilled water and dried. They showed little tendency to aggregate.
Example 6 A bath containing approximately 1.4% SiO2 and 7.6%
; NaCl was prepared from 15 ml of 10% aqueous NaCl and 5 ml of l.OM aqueous silicic acid. About 2 ml of a 55% solids latex ' of a copolymer derived about 18% from vinyl acetate and about 82% from ethylene was added dropwise to the bath. The drops : -coagulated into pellets which were filtered from the bath, dried under vacuum at 80C, washed with water to remove all traces of NaCl and again dried. They were nontacky and free-flowing.
For comparison, the following experiments, not within ''' , ,:
1091~964 the scope of the invention, were carried out. The above example was repeated twice, first with replacement of the NaCl soluti~n by water, and second by replacement of the ciliclc acld solutlon by water. In both lnstances, the treated drops were too fragile to be removed whole from the bath.
Example 7 A solution containing approximately 1.4% SiO2 and 6.1% NaCl was prepared by adding 262 ml of lN HCl, 14.7 gm ;-~ 10 Or NaCl, and 38 ml of H20 to 100 ml of rapidly stirred lM
Na2SiO 9H200 To this solution at about 0C were added 20 drops of the vinyl acetate/ethylene copolymer latex described in Example 60 After 10 minutes, the resulting pellets were removed from the bath and dried in a vacuum oven at 80C
for 2 hoursO The pellets were coated with a nontàcky coating and were ~ree-flowing.
Exam~le 8 ~ About 200 ml of a 62% solids natural rubber latex - (LATEX TSC*, General Latex CoO) was added dropwise to a bath ~ 20 containing approximately 0.9% SiO2 and 2.5% CaC12 which was ;-i prepared from 250 ml of lM 9ilicic acid, 1750 ml of absolute EtOH, and 60 ml of ~0% aqueous CaC12. m e latex rapidly coagulated and a nontacky coating formed on the surface of , ; the particlesO When isolated and dried, the pellets were nontacky and free-flowing.
, l~xamPle 9 Into neoprene latex #1 (37~ solids, pH 12) was mixed enough carbon black (STERLING R*, Cabot) to y~eld a uniform emulsion containing 4% of carbon black based on the neopreneO About 20 ml of this modified latex was added * denotes trade mark ~ - 25 -,~
dropwise to a bath containing 1.5% SiO2 and 201~ CaC12 prepared from 100 ml of 0.5M aqueous silicic acid, 94 ml of 0.2% aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 6 ml of 50% aqueouq CaC12. The drop~
were delivered from a Pa~teur pipette near the surface of the bath and the bath was stirred by a imagnetic bar. After 30 minutes ln the bath the pellets which formed were removed by decantation, wa~hed three tlmes with 500 ml portions of water and air dried. The carbon-conta~ning pellets were nontacky and free-flowing.
Example 10 The procedure of Example 9 was repeated with the exception that the 4% of carbon black in the latex was -~ replaced by 10% of atomized aluminum powder. Nontacky, - ~ree-flowing aluminum~containlng pellets were obtained.
Example 11 The procedure of Example 9 was repeated with the ~;i exception that the 4% of carbon black in the latex was re-placed by 10% of alumina trihydrate (powder, baked at 135-195C). Nontacky, free-flowing alumina-containing pellets w0re obtained.
Example 12 . ., ;~ The procedure of Example 9 was repeated with the ,- exception that the 4% of carbon black ln the latex was re-: placed by 10% of magnetic iron oxide (Fe304, Mo-4232*, Pfizer ~i Minerals). Nontacky, free-f lowing iron oxlde-containing . . .
pellets were obtained whlch were readily manipulated with .;
0~ magnets.
I Exam~le 13 , . .
About 100 ml of a 65% solids latex of fluoro-` * denotes trade mark :;
elastomer terpolymer derived from 45% vinylidene fluoride, 30% hexafluoropropylene and 25% tetrafluoroethylene was added dropwise to a bath prepared from 500 ml of 0.5M aqueous silicic acid saturated with BaC12, 500 ml of water saturated with BaC12, and 2 ml of 2~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6). The drops flattened on contact with the bath, but coagulated throughout and were coated with a nontacky coating. The particles were decanted from the bath, washed repeatedly with water and air dried to give white, free-flowing flakes about 5 mm in diameter.
Example 14 A mixture was prepared from equal volumes of , neoprene latex ~1 (37% solids, pH 12) and the aqueous fluoro-elastomer latex described in Example 13. This mixture (20 ml) was introduce~ dropwise into a bath containing approximately 1.5% SiO2 and 2.1~ CaC12 prepared from 100 ml of 0.5M aqueous silicic acid, 94 ml of 0.2% aqueous trimethylnonanol ether of i ethylene oxide (Tergitol~ TMN-6), and 6 ml of 50% aqueous ., .
- CaC12. The pellets which formed were washed with water and then dried, first in air and then over P2O5 under vacuum at room temperature. The resulting mixed elastomer pellets were nontacky and free-flowing.
. .
~ Example 15 ,~ ~
A portion (422 ml) of sodium silicate solution (Grade F, Du Pont Co., SiO2/Na2O ratio = 3.25, Na2O = 8.7%, sio2 = 28.4%, viscosity (68C) = 160 cp, specific gravity =
., ~ 1.386) was diluted to 4 liters with distilled water. This , . . .
solution was put through the cation exchange column in acid form described in Example 5. A bath containing approximately 0.5~ SiO2 and 7.6~ NH4Cl was prepared using 250 ml of the ,~
, ., 1~91864 resulting approximately 0.69M silicic acid solution, lQQ0 ml of 15~ NH4Cl, 250 ml of distilled water, and 500 ml of 0.05 aqueous trimethylnonanol ether of ethylene oxide (Tergitol~
TMN-6). Two hundred ml of neoprene latex #2 (37% solids, pH 12.5) was added dropwise to the bath. The pellets which formed were allowed to remain in the bath for 30 minutes.
The bath was decanted and the pellets were washed three times with 2-liter portions of water. The pellets were air dried : at room temperature and atmospheric pressure. The resulting pellets were nontacky and free-flowing.
Example 16 A bath was prepared with a buffer to resist the pH elevation associated with the addition of alkaline neoprene ¢
- latex. The buffer was prepared by diluting a mixture of 1.75 ml of 2M HCl, 0.1 g of trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 12.60 ml of 2M glycine solution ; to 50 ml with distilled water. The bufer was then added to ' 100 ml of 0.69M silicic acid (prepared according to Example , lS), and 50 ml of 30% aqueous NH4Cl. Twenty ml of neoprene ~ 20 latex #2 (37% solids, pH 12.5) was added to the bath dropwise.
',~4. The pH of the bath changed from 3.35 to 3.55 as compared to a pH change to approximately 6.0 for a similar unbuffered bath. Approximately 80 ml of the latex could be added to . . .
the buffered bath before the pH rose above 6.0, at which pH
gelation of the bath occurred rapidly.
Example 17 - A bath containing approximately 2.Q% sio2 and 7.9%
I~ NH4Cl was prepared from lOQQ ml of 0.69M silicic acid, (pre-......
^j pared according to Example 15) 5Q0 ml of 30~ NH4Cl, and 500 ml of 0.2% aqueous trimethylnonanol ether of ethylene oxide .,.~ .
. .
.
, . ., ~ .
.
- 1~91864 (Tergitol~ TMN-6). A 200-ml sample of neoprene latex #3 (33% solids, pH 12) was adjusted from pH 12.0 to pH 12.5 by addition of lN NaOH. This latex was added dropwise to the bath. The pellets which formed were washed with water and then freeze-dried at about -178C under high vacuum. At room temperature the dried pellets were nontacky and free-flowing.
Example 18 ; A bath was prepared using an alumina-modified silica sol (Ludox~ 130M, Du Pont Co.). This product is a 30~ solids, acidic, aqueous dispersion of positiveIy-charged colloidal particles consisting of a dense silica core coated 'f with positively-charged polymeric alumina. The approximate chemical composition is SiO2 = 26~, A12O3 = 4.0~, Cl = 1.4~, MgO z 0.2~, viscosity (25C) = 5-15 cp, pH (25C) = 4.3-4.5, approximate particle diameter = 16 m~, and specific gravity (25C) = 1.23.
The bath containing approximately 0.7% SiO2/A12O3 and 6.1% NH4Cl was composed of 116 ml of 0.2% aqueous sodium `
heptadecyl sulfate anionic surfactant (Tergitol~ Anionic 7, Union Carbide), 80 ml of 15% aqueous NH4Cl, and 4 ml of the . ,-. .
' alumina-modified silica sol described above. To this bath was added dropwise 20 ml of neoprene latex #2 (37% solids, - pH 12.5). The drops coagulated and the resulting coated }
`~ pellets were washed and dried. Nontacky, free-flowing pellets were obtained.
Example 19 A bath containing approximately 1.0% SiO2 and 8.0 ; AlC13 was prepared from 5 ml of 0.69M aqueous silicic acid :;
^` 30 (prepared according to Example 15), 9 ml of 30~ aqueous ,~:
~., ;-AlC13-6H20, 5 ml of 0.2~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 1 ml of distilled water.
To this bath was added dropwise 2 ml of neoprene latex #2 (~7% solids, pH 12.5). The drops coagulated and were removed Prom the bath, washed and dried. Nontacky, free-flowing pellets were obtained.
Examples 20-23 Four baths were prepared, each from 2.5 ml of 0.69M ~
^ aqueous silicic acid (prepared according to Example 15), 5 ml -~ 10 of 0.5~ aqueous trimethylnonanol ether of ethylene oxide ; (Tergitol~ TMN-6), and 12.5 ml of a 30~ aqueous solution of the indicated salts:
~, .
Example 20 NH4Br i~ Example 21 (NH4)2HC6HsO7(citrate) ~"
Example 22 (NH4)2cr2o7 Example 23 NH4SCN
'~
~ To each bath was then added dropw~se 2 ml of neoprene latex ', #2 (37% solids, pH 12.5~. The elastomer pellets which formed : were separately washed with water and dried. All yielded :, nontacky, free-flowing pellets.
~v, ~s Example 24 -~ Ten ml of naphthenic extender oil (Sundex~ 790, Sun Oil Co.) was added to 90 ml of neoprene latex #2 (37% solids, ; pH 12.5) and the mixture vigorously shaken to give an emul-sion. A bath containing approximately 1.0% SiO2 and 7.6%
NH4Cl was prepared from 50 ml of 0.69M aqueous silicic acid - (prepared according to Example 15), lQO ml of 15~ aqueous NH4Cl, and 50 ml of Q.05~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6). The oil extended polymer latex was added dropwise to the bath. The pellets which :~
' .,: : - . .
109~864 formed were separated from the bath, washed with water and dried to yield nontacky, free-flowing pellets of oil-extended elastomer.
Example 25 ~ A bath con'caining approximately 0.9% SiO2 and 10.0%
`~ NaCl was prepared by dissolving 100 g of NaCl in 900 g of i 0.35M aqueous silicic acid, dissolving 100 g of NaCl in 900 g of 0.05% aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and combining the two solutions. The bath was maintained at pH 4-4. 5 by additions of lN HCl during the -~
dropwise addition of 200 ml of neoprene latex #2 (37% solids, pH 12.5). The pellets which formed were allowed to stand in the bath for 16 hours, then washed with water and dried to yield nontacky, free-flowing pellets of uncured elastomer.
Example 2 6 ~.
A bath containing approximately 1.3% SiO2, 3.9% -~ NH4Cl and 11.1% NaCl was made by combining 25 ml of 0. 69M
.'4'~ silicic acid (prepared in accordance with Example 15), 10 , ........................................................................ .
ml of 30~ NH4C1 in 0.2% aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), 40 ml of 20% NaCl in 0.2%
, .~.
~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~
`~ TMN-6), and 125 ml of distilled water. The bath was adjusted to pH 5.0 with lN NaOH. Twenty milliliters of neoprene latex .,, -~ #2 (37% solids, pH 12.5) was added to the bath dropwise while the pH was maintained at 5.0 by dropwise addition of lN HC1.
":
~- The resulting pellets were removed from the bath after one hour, washed three times with 500-ml portions of distilled water, and air dried to yield nontacky, free-flowing pellets.
Example 27 A bath containing approximately 0.5% chlorhydrol :
'f (aluminum chlorohydroxide polymeric complex containing 47.0~
A12O3 and 16.3~ chloride, Reheis Chemical Co.) and 2.3% CaC12 was prepared by combining 10 ml of 10~ aqueous chlorhydrol, 175 ml of 0.05~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 15 ml of 25% aqueous CaC12. The solution was brought to pH 5.0 with lN NaOH. As 20 ml of neoprene latex #2 (37% solids, pH 12.5) was added dropwise, -~
the bath was gently stirred and maintained at pH 5.0 by drop-wise addition of lN HCl. The pellets were allowed to remain in the bath for 1 hour, after which they were washed with three 250-ml charges of distilled water. The pellets were then air dried to form free-flowing nontacky elastomer particles.
Example 28 A surfactant-free bath containing 1.0% SiO2 and 7.6% NH4Cl was prepared from 100 ml of 0.69M agueous silicic . , acid (prepared according to Example 15), 200 ml of 15~ aqueous , NH4Cl, and 100 ml of distilled water. A 100 ml graduated cylinder was filled with this bath. From a 10 ml syringe fitted with a 20 gauge needle, neoprene latex #2 (37~ solids, ~ pH 12.5) was extruded as a continuous stream onto the surface ."~
-~ of the bath at one side of the graduated cylinder, forming c a small puddle. By grasping the edge of the puddle with . . .
tweezers at the other side of the graduated cylinder a continuous fiber of coagulated, hydrous silica-coated poly-chloroprene was drawn off. After being washed and air dried, the fiber was nontacky.
~, Example 29 The procedure of Example 28 was repeated except that more force was used on the syringe, thus causing the :
~` - 32 -. ~ .
- 1~)91864 stream of latex to go through the surface of the bath. The weight of the coagulating stream pulled it to the bottom of the bath where a nontacky continuous fiber of the elastomer about 1-2 mm in diameter collected.
Example 30 The procedure of Example 29 was repeated except that, after the interface at the surface of the bath had been penetrated by the latex stream, the force on the syringe was reduced and adjusted so that free drops fell , 10 from the needle into the bath. The pellets which formed were nontacky and free-flowing when washed and dried.
Example 31 Part A
,., ~, .
To 200 ml of a 30% solids aqueous colloidal sol of alumina-modified silica of pH 8.6-9.3 (Ludox~ AM, Du Pont ;~ Co.) under agitation in a blender was added 2.0 ml of concentrated HC1 (38%). The resulting colloidal solution , containing approximately 29% solids had a pH of 3Ø
Part B
~"
A modified neoprene latex was prepared by adding , 10 ml of a 1% aqueous solution of hydroxyethyl cellulose "
(Cellosize~ QP 30,000, Union Carbide Corp.) to 90 ml of neoprene latex ~2 (37% solids, pH 12.5). The emulsion was . kept agitated to avoid creaming.
~;. Part C
^ A bath containing approximately 4.3% SiO2/A12O3 and 7.5% NH4Cl was prepared by mixing 2.5 ml of the colloidal `~- silica solution prepared in Part A above, 10.0 ml of 15%
aqueous NH4Cl, 1 ml of a 0.2~ aqueous solution of an ampho-teric fluorinated surfactant (Zonyl~ FSB, Du Pont Co.), and , . .:
:~"
:
: -: .
:; -6~5 ml of water. To this bath was added dropwise about 5 ;~
ml of the modified neoprene latex prepared in Part B above. `
The pellets which formed were separated from the bath, washed ~, with water, and dried to obtain nontacky, free-flowing, ~ `
sll~stantially spherical pellets of modified neoprene.
~' Example 32 :'r' ;i~ A bath containing approximately 0.5% SiO2, 7.6%
,: -NH4Cl and 0.01% AlCl3 was prepared by mixing 250 ml of 0.69M
aqueous silicic acid (prepared according to Example 15 and aged for two days), 1000 ml of 15% aqueous NH4Cl, 200 ml of water, 500 ml of 0.05% aqueous trimethylnonanol ether of ~.". :::
. ethylene oxide (Tergitol~ TMN-6), and 50 ml of 1% aqueous , ......................................................... .
AlC13-6H2O which had been adjusted to pH 5.0 by addition of lN NaOH. This bath was kept at pH 4.5-5.0 by addition of lN HCl during the dropwise addition of 200 ml of neoprene latex ~2 (37% solids, pH 12.5) which took eight minutes, and for one hour thereafter. The drops, which coagulated, were separated from the bath, washed three times with water, soaked for three hours in water, and then air dried. The .", ; 20 resulting pellets were nontacky and free-flowing.
Example 33 A silica sol containing approximately 4.6% solids ~; with a pH of 5.0 was prepared by adding 265 ml of a 15%
-~ solids aqueous silica sol (Nyacol~ 215, Nyacol, Inc., .;
pH 10.5) dropwise with vigorous stirring to a solution of ~; 70 ml of lN HCl in 595 ml of water. A bath containing approximately 0.6% SiO2, 7.6% NH4Cl and 0.013% AlC13 was ~,~ prepared by mixing 250 ml of the above sol, 1000 ml of 15%
~ aqueous NH4Cl, 700 ml of a 0.03% aqueous solution of an - 30 amphoteric fluorinated surfactant (Zonyl~ FSB, Du Pont Co.), ,;.
.....
,.,~
.... .
~"
and 50 ml of 1% aqueous AlC13 6H2O which had been adjusted to pH 5.0 with lN NaOH. The resulting bath had a pH of 4.3.
Th.is bath was stirred and kept at pH 4.5-5.0 by addition of HCl during the dropwise addition of 200 ml of neoprene latex #2 (37~ solids, pH 12.5). The pellets which formed were stirred in the bath for one hour, separated, washed three times with water and soaked in 2 liters of water. After drying the pellets were nontacky and showed little tendency -to agglomerate.
Example 34 :;.
In the manner of Example 33, 42 ml of a 49% solids aqueous colloidal silica sol (Ludox~ TM, Du Pont Co., pH 8.9, particles 220-250A in diameter) was blended with 3.9 ml of lN HCl and 454 ml of water to give an aqueous sol containing ~ 5,6% SiO2. A bath containing approximately 0.7~ SiO2, 7.6%
; NH4Cl and 0.013% AlC13 was prepared by substituting 250 ml of the above sol for the sol employed in Example 33 and maintained at a pH of 5.0 by addition of lN HCl. The ~, ' remaining procedure of Example 33 was then repeated to yield nontacky, free-flowing elastomer pellets.
.":
Example 35 In the manner of Example 33, 125 ml of a 30%
; solids aqueous colloidal silica sol (Ludox~ SM, p~l 9.9, Du Pont Co.) in 125 ml of distilled water, was blended with 28 ml of lN HCl and 637 ml of water. A bath was prepared ~; by substituting 250 ml of the above sol for the sol employed ~- in Example 33 and the remaining procedure of Example 33 was repeated. Nontacky, free-flowing pellets were obtained.
Example 36 To 400 ml of a 30~ solids aqueous colloidal sol .~
; - 35 -- 109~864 of alumina-modified silica of pH about 8.9 (Ludox~ AM, Du Pont Co.) was added 4.0 ml of concentrated (38%) hydro-chloric acid with vigorous agitation. The resulting sol had a pH of 3.0 and a solids content of about 29.7%. A bath containing approximately 4.3% SiO2 and 7.5% NH4Cl was pre-pared from 250 ml of this sol, 1000 ml of 15% aqueous NH4Cl, 650 ml of water, and 100 ml of a 0.2% aqueous amphoteric fluorosurfactant solution (Zonyl~ FSB, Du Pont Co.). The bath had a pH of 3.7 and was kept below pH 4. 5 by adding , O.lN HCl during the dropwise addition of 200 ml of neoprene latex #2 (39% solids, pH 12.5). The drops coagulated and were stirred in the bath for 30 minutes, separated, washed three times with water and dried at 60C to obtain nontacky pellets.
Example 37 A bath containing approximately 1.5% SiO2 and 7.6%
NH4Cl was prepared by mixing 100 ml of 0.69M aqueous silicic acid (prepared according to Example 15), 94 ml of 0.2%
trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6) in ethanol, and 6 ml of a 50~ aqueous solution of CaC12 2H2O.
. . .
- To this bath was added dropwise about 20 ml of a 40% solids butadiene/acrylonitrile copolymer latex (Chemigum~ Nitrile Latex 550, Goodyear) having a pH of 8Ø The coagulated ; drops were stirred in the bath for one hour, separated, and .::.
dried under vacuum at 60C to obtain perfectly spherical pellets which were nontacky and free-flowing.
, Example 38 .:
A mixed latex was prepared from 100 ml of neoprene latex #2 (37~ solids, pH 12.5) and 60 ml of natural rubber latex TSC (62~ solids, General Latex Co.). The resulting .~
~ - 36 --' mixture was brought to pH 12.2 by adding lN NaOH. A bath was prepared like the one in Example 37, except on a 10-fold larger scale. During dropwise addition of the mixed latex to the bath, the bath was maintained at pH 5.0 by the addi-ti.on of lN HCl. The coagulated drops remained in the bath for one hour. They were then separated, washed three times with water, and dried, first for five hours in air and then for three days under vacuum over P2O5 at room temperature. -The coated pellets of neoprene/rubber were nontacky and free-flowing.
Example 39 . ,~ .
A bath containing approximately 0.7% SiO2/A12O3 and 7.6% NH4Cl was prepared by mixing 40 ml of a positi~e alumina-modified silica sol tLudox~ 130 M, Example 18), 1000 ml of 15~ a~ueous NH4Cl, and 960 ml of 0.05% aqueous sodium lauryl sulfate (Duponol~ WAQE, Du Pont Co.). The bath had a pH of 4.9 and was maintained at pH 5.0 by addition of lN HCl during dropwise addition of 200 ml of neoprene latex . ., #2 (37% solids, pH 12.5). The coagulated drops were stirred in the bath for one hour, washed with water, and air dried to yield nontacky, free-flowing pellets.
Example 40 A bath containing approximately 0.1% chlorhydrol .~. i ~ and 7.6% NH4Cl was prepared by mixing 1000 ml of 15~ aqueous :
~; NH4Cl, 980 ml of 0.1% aqueous sodium lauryl sulfate (Duponol~
- WAQE), and 20 ml of 10% aqueous chlorhydrol (A12O3 47.0%, ., .
~` chloride 16.3%, Reheis Chemical Co.). To the bath was added ` dropwise 200 ml of neoprene latex #4 while maintaining the ~- bath at pH 5.5 by adding lN HCl. After the addition, the pellets were stirred in the bath for one hour, washed with ''','~;' , ., i()918~;4 water, and air dried. The uncured elastomer pellets were nontacky and free-flowing.
Example 41 Using the apparatus illustrated in Figures 1 and 2, the following aqueous solutions were mixed in tank 1.
10,000 ml of 15% aqueous ammonium chloride ""
`~; 9,500 ml of 0.03% aqueous sodium lauryl sulfate ' surfactant ~Duponol~ WAQE) ~-~,, .
500 ml of 30~ solids colloidal alumina-modified .3"
silica sol (Ludox~ 130M, Example 18) `
The bath thus prepared had a pH of 5.4 and contained approxi- `
.", mately 0.9% SiO2 and 7.6% NH4Cl. While providing agitation, 3480 g of a 40% solids neoprene latex prepared in the manner . ., ~
of neoprene latex #2 was added through the capillary tubes over a period of 13 minutes. Simultaneously, the pH of the i, >- bath was maintained at 5.4 by gradual addition of 51 ml of lN hydrochloric acid. Immediately following the 13-minute ~j:
~ latex addition period, agitation was continued for 17 minutes :
with no further addition of acid, during which time the pH of the bath rose to 6.6. The particles were kept in suspension by agitation during the 17-minute holding period. The ~ agitator was then turned off, the particles were allowed to .i,; .
settle, and the supernatant liquid was separated from the particles by decantation.
The particles were washed by addition of 8000 ml ;~ of distilled water folIowed by a 5-minute agitation period.
~ A
The agitator was then turned off and the supernatant liquid ~ was separated from the particles by decantation. This washing ;~ procedure was repeated twice. The particles were allowed to :.
dry in the air to a constant weight of 1315 g. They were .
`;
,, '`"~
., - : .- , ,, ~ ~ . - . .
, .-. .
1~)9~864 free-flowing and nontacky.
Example 42 Using the apparatus illustrated in Figures 1 and 2, a bath was prepared by mixing the following aqueous solutions in tank 1.
; 10,000 ml of 15% aqueous ammonium chlorlde 9,950 ml of 0.03% aqueous sodium lauryl sulfate surfactant (Duponol~ WAQE) 50 ml of a polyaluminic acid-modified aqueous ~- 10 colloidal silica sol The modified silica sol was prepared by slowly adding 500 g of 35% aqueous boric acid-stabilized basic aluminum acetate solution (Niaproof~, Union Carbide Corp.) to 400 g of aqueous colloidal silica sol [Ludox~ SM, Du Pont Co., 30~ SiO2, average particle size 7 m~, weight ratio SiO2/Na2O 50, pH
~25C) 9.9, freezing point 0C] in a blender and filtering the mixture through coarse filter paper to remove the small amount of gel. The bath thus prepared had a pH of 5.3 and contained approximately 0.1% colloidal silica sol coated :
. .
with polyaluminic acid and 7.6~ NH4Cl.
While providing agitation, 3590 g of 40% solids ` neoprene latex prepared like neoprene latex #l was added to the bath through the capillary tubes over a period of 9 t~ minutes, during which time the pH of the bath rose to 6.7.
, Agitation was continued, keeping the particles in suspension ~; for an additional 51 minutes, with no appreciable change in pH of the bath. The agitator was turned off, the particles . .
- were allowed to settle and the supernatant liquid was separated from the particles by decantation.
....
` 30 The particles were washed by addition of 8000 ml :~.
.
''.':~
of distilled water followed by a 10-minute agitation period.
The agitator was then turned off and the supernatant liquid was separated from the particles by decantation. This washing procedure was repeated three times. The particles were allowed to dry in the air to a constant weight of 1446 g.
They were free-flowing and nontacky.
Example 43 Using the apparatus illustrated in Figures 1 and 2, the following aqueous solutions were mixed in tank 1.
10,000 ml of 15% aqueous ammonium chloride .~
9,950 ml of 0.03% aqueous sodium lauryl sulfate surfactant (Duponol~ WAQE) 50 ml of the polyaluminic acid-modified aqueous ; colloidal silica sol described in Example The bath thus prepared had a pH o 5.2. rflhile providing agitation, 4578 g of 40~ solids neoprene latex prepared like neoprene latex #2 was added through the capillary tubes over a period of 18 minutes, during which time the pH rose to 6.7.
Agitation was continued, keeping the particles in suspension for an additional 42 minutes, with no appreciable change in pH of the bath. The agitator was turned off, the particles were allowed to settle and the supernatant liquid was separated from the particles by decantation.
The particles were washed by addition of 20,000 ml of distilled water followed by a 10-minute agitation period.
The agitator was then turned off and the supernatant liquid was separated from the particles by decantation. This washing procedure was repeated once. The particles were allowed to dry in air to a constant weight of 1767 g. They were free-flowing and nontacky.
i ~,... .
:.
-^ 1091864 Example 44 A bath containing approximately 0.6% SiO2, 0.9~
CaC12, 0.3% AlC13 and 0.6% NaCl was prepared by mixing 1694 g of H2O, 10.0 g of AlC13 6~2O, 24.2 g of CaC12 2H2O, 12-Q g of NaCl, 1.2 g of an amphoteric fluorinated surfactant (Zonyl~
FSB, Du Pont Co.), and 250 ml of a colloidal sil~ca sol having - a pH of 2.0 and containing 4.8% SiO2. This colloidal sol was prepared by adding a mixture of 125 ml of a 30% solids aqueous silica sol (Ludox~ SM, Du Pont Co.) and 125 ml of H2O to a running blender containing 637 ml of H2O and 40 ml of lN HCl.
To this bath was added dropwise 198 ml of 40% solids neoprene latex prepared like neoprene latex #1. After 30 minutes, the bath was decanted fxom the pellets which had formed. The pellets were soaked in 2 liters of H2O for 3Q
, minutes and then filtered from the wash water and spun for 2 minutes in a basket centrifuge. The pellets were then shaken with 1.5~ of their weight of talcum powder and spread in a tray to air dry overnight. They were further dried over P2O5 `~ under vacuum at room temperature. The resulting nontacky free-flowing pellets contained 1.56 milliequivalents of residual alkalinity per 100 g of isolated polymer, as sho~n by nonaqueous titration to a bromophenol end point.
Example 45 ~,. .
; A bath containing approximately 0.5% SiO2, 0.9%
CaC12 and 0.3~ AlC13 was prepared by mixing 1714.6 ml of H2O, lO.Q g of AlC13-6H2O, 24.4 g of CaC12-2H2O, 1.2 g of the trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6) and 250 ml of 0.69M silicic acid which had aged for five days.
- To this bath was added dropwise 200 ml of 40% solids neoprene . .
latex prepared like neoprene latex #1. The pellets which , . .
. .~
;~
.
,, .
, .
109~864 formed were isolated, washed and dried as in the procedure of Example 44. The resulting free-flowing, nontacky pellets had a residual alkalinity of 2.43 meq/100 g.
Example 46 A latex mixture was prepared from 2 ml of the sodium silicate solution described in Example 15, 15 ml of lN NaOH, and 198 ml of 40% solids neoprene latex prepared like neoprene latex #2. This mixture was added dropwise to a bath containing approximately 1.8% CaC12, 1.7~ NaCl, 0.6 AlC13 and 0.6~ modified sol prepared from 898.6 ml of H2O, 1000 ml of 2~ AlC13-6H2O (adjusted to pH 3.5 with lN NaOH), 36.4 g of anhydrous CaC12, 34 g of NaCl, 1.0 g of 30% sodium lauryl sulfate (Duponol~ WAQE), and 30 ml of the modified aqueous colloidal silica sol described in Example 42. The pellets which formed were removed from the bath after 15 minutes, washed with water, centrifuged, treated with talc and dried as described in Example 44. The resulting pellets were nontacky and free-flowing.
,~ .
:"
;
: . .
. . .
~ .
;';
;, ~ - 42 -~
'`;
:.
:
Chloroprene was polymerized by adjusting the emulsion temper-' ature to 10C and adding continuously an aqueous dispersion ''""
:' " . .
.~
:, `'' "
109~864 containing 1.0~ K2S2O8, 0.05% sodium salt of anthraquinone-~~sulfonic acid, and 0.14% cumene hydroperoxide at a rate allowing control of the temperature between 10 and 20C.
The polymerization was terminated at about 85% conversion of the chloroprene monomer by addition in the form of an aqueous emulsion of a toluene solution of 0.03 part of phenothiazine and 0.03 part of 4-tert.-butylcatechol.
After removal of residual monomer the emulsion contained 37% solids and had a pH of 12.5.
Neoprene Latex #3 The preparation of neoprene latex #l was repeated except that the 100 parts of chloroprene was replaced by a -mixture of 92 parts of chloroprene and 8 parts of 2,3-dichloro-1,3-butadiene. The polymerization was stopped at 65% conversion, and the latex, after stripping, contained about 33% solids and had a pH of 12.
",, .
Neoprene LateX #4 The procedure described for neoprene latex #2 was repeated except that the amount of dodecyl mercaptan in the monomer emulsion was 0.12 part instead of 0.15 part~ The resulting latex had a solids content of 37% and a pH of 12.5.
Example l :.
A bath containing approximately 0.7% sio2 and 3.9%
Ca(NO3)2 was made by combining 90 ml of 0.25M aqueous silicic ` acid (produced by the ion exchange of H+ for Na+ in 0.25M
sodium metasilicate solution), 10 ml of a 50% aqueous Ca(NO3)2 solution, and lO0 ml of absolute ethanol. About 20 ml of neoprene latex #l (37% solids, pH 12) was added dropwise ''~
','`
"~
.:
1C)9~864 to this bath from an orifice about 2 cm above it. The surface of the drops coagulated on contact to yield globules which within a few minutes were coagulated throughout and c~vered with a nontacky coating. The resulting opaque pellets were lifted from the bath and dried in a 60C oven.
At room temperature they remained dry to the touch and free-flowing.
For comparison, the following experiment, not within the scope of the invention, was carried out. The above example was repeated using 9Q ml of water in place of the silicic acid solution. The drops of emulsion coagulated ; rapidly, but remained very tacky and were difficult to :
separate after drying at 60C.
Example 2 A bath containing approximately 3.6% SiO2 and 2.6% CaC12 was made by mixing 1000 ml of lM silicic acid, 60 ml of 50~ CaC12 solution, 700 ml of absolute ethanol, and 240 ml of distilled water. About 200 ml of neoprene , latex #1 (37~ solids, pH 12) was introduced into the bath dropwise. The resulting pellets were allowed to remain in the bath for 30 minutes. They were removed, washed with 70%
ethanol, and dried for 48 hours in a vacuum drying pistol heated by refluxing acetone. The resulting pellets had the following analysis: Ca, 0.25; Na, 0.38; Si, 0.51; % ash, 2.8. Pellets prepared in this way retained a small amount , ,:
of alkali. Such amounts of residual alkali stabilize neo-prene against HCl degradation. A 5% suspension of these pellets in water had a pH of 9Ø The pellets were more than 90% soluble in toluene, indicating little or no crosslinking ':
.
1~)91864 of the neoprene had occurred.
Example 3 An alcohol-free bath containing approximately 1.5 SiO2 and 2.1~ CaC12 was made, utilizing a dilute aqueous nonionic surfactant solution to reduce interfacial tension at the air-liquid interface. A mixture of 10 ml of freshly prepared 0.5M silicic acid, 9.4 ml of 0.2% aqueous tri-methylnonanol ether of ethylene oxide (Tergitol~ TMN-6, Union Carbide), and 0.6 ml of 50% CaC12 completed the bath. About 2 ml of neoprene latex #1 (37% solids, pH 12) introduced drop-wise into the bath formed opaque nonsticking pellets. These were isolated, washed with water, and air dried to produce free-flowing, nonsticking pellets 3-4 mm in diameter. The moisture content of the pellets was 0.38%; the ash residue was 3.05~; other analyses were: Ca, 0.44~; Na, 0.26~;Si, ~, 1. 11~.
Example 4 A bath containing approximately 1.5% SiO2 and 2.1 CaC12 was prepared from lQ00 ml of 0.5M silicic acid (pH
3.3), 940 ml of 0.2% aqueous trimethylnonanol ether of ethyl-' ene oxide (Tergitol~ TMN-6), and 60 ml of 50% aqueous CaC12 solution. The initial pH of the bath was 4.45. One hundred ~ milliliters of neoprene latex #1 (37% solids, pH 12) was added ,~
` dropwise over a period of 10 minutes during which the bath , ~ was stirred and the pH was maintained at 4.Q by continuous , . . .
addition of 1.0N hydrochloric acid. The bath showed no evi-dence of gelation. The neoprene pellets which formed were ....
filtered from the bath on a lQ0 mesh stainless steel screen, washed with cold water and dried. They were non-tacky and free-flowing.
: .
:.' ":
.
~091864 Example 5 A silicic acid solution was prepared from a sodium silicate solution having an SiO2/Na20 ratio of 1.95. The -sodium silicate solution utilized was Grade 6 (Du Pont Co.) which had a viscosity of 60,000 centipoises (68C), a specific gravity of 1.708, % Na20 = 18.4, and ~ SiO2 = 36Ø This solution (166.5 ml) was diluted to 2 liters with distilled water. The resulting solution was passed through a cation exchange column in acid form containing 1300 gms of cation exchange resin (Rexyn 101, H+). The first 500 ml of effluent, equivalent to the retention volume of the column, was discarded and the remainder collected.
A 1000 ml portion of this 0.85M silicic acid ~, ~olution was employed in the procedure of Example 4 to give a bath containing approximately 2.5% SiO2. At the start of the addition of neoprene latex the bath was a pH 3.1 and at the conclusion the pH was 4.1. The resulting pellets were washed with distilled water and dried. They showed little tendency to aggregate.
Example 6 A bath containing approximately 1.4% SiO2 and 7.6%
; NaCl was prepared from 15 ml of 10% aqueous NaCl and 5 ml of l.OM aqueous silicic acid. About 2 ml of a 55% solids latex ' of a copolymer derived about 18% from vinyl acetate and about 82% from ethylene was added dropwise to the bath. The drops : -coagulated into pellets which were filtered from the bath, dried under vacuum at 80C, washed with water to remove all traces of NaCl and again dried. They were nontacky and free-flowing.
For comparison, the following experiments, not within ''' , ,:
1091~964 the scope of the invention, were carried out. The above example was repeated twice, first with replacement of the NaCl soluti~n by water, and second by replacement of the ciliclc acld solutlon by water. In both lnstances, the treated drops were too fragile to be removed whole from the bath.
Example 7 A solution containing approximately 1.4% SiO2 and 6.1% NaCl was prepared by adding 262 ml of lN HCl, 14.7 gm ;-~ 10 Or NaCl, and 38 ml of H20 to 100 ml of rapidly stirred lM
Na2SiO 9H200 To this solution at about 0C were added 20 drops of the vinyl acetate/ethylene copolymer latex described in Example 60 After 10 minutes, the resulting pellets were removed from the bath and dried in a vacuum oven at 80C
for 2 hoursO The pellets were coated with a nontàcky coating and were ~ree-flowing.
Exam~le 8 ~ About 200 ml of a 62% solids natural rubber latex - (LATEX TSC*, General Latex CoO) was added dropwise to a bath ~ 20 containing approximately 0.9% SiO2 and 2.5% CaC12 which was ;-i prepared from 250 ml of lM 9ilicic acid, 1750 ml of absolute EtOH, and 60 ml of ~0% aqueous CaC12. m e latex rapidly coagulated and a nontacky coating formed on the surface of , ; the particlesO When isolated and dried, the pellets were nontacky and free-flowing.
, l~xamPle 9 Into neoprene latex #1 (37~ solids, pH 12) was mixed enough carbon black (STERLING R*, Cabot) to y~eld a uniform emulsion containing 4% of carbon black based on the neopreneO About 20 ml of this modified latex was added * denotes trade mark ~ - 25 -,~
dropwise to a bath containing 1.5% SiO2 and 201~ CaC12 prepared from 100 ml of 0.5M aqueous silicic acid, 94 ml of 0.2% aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 6 ml of 50% aqueouq CaC12. The drop~
were delivered from a Pa~teur pipette near the surface of the bath and the bath was stirred by a imagnetic bar. After 30 minutes ln the bath the pellets which formed were removed by decantation, wa~hed three tlmes with 500 ml portions of water and air dried. The carbon-conta~ning pellets were nontacky and free-flowing.
Example 10 The procedure of Example 9 was repeated with the exception that the 4% of carbon black in the latex was -~ replaced by 10% of atomized aluminum powder. Nontacky, - ~ree-flowing aluminum~containlng pellets were obtained.
Example 11 The procedure of Example 9 was repeated with the ~;i exception that the 4% of carbon black in the latex was re-placed by 10% of alumina trihydrate (powder, baked at 135-195C). Nontacky, free-flowing alumina-containing pellets w0re obtained.
Example 12 . ., ;~ The procedure of Example 9 was repeated with the ,- exception that the 4% of carbon black ln the latex was re-: placed by 10% of magnetic iron oxide (Fe304, Mo-4232*, Pfizer ~i Minerals). Nontacky, free-f lowing iron oxlde-containing . . .
pellets were obtained whlch were readily manipulated with .;
0~ magnets.
I Exam~le 13 , . .
About 100 ml of a 65% solids latex of fluoro-` * denotes trade mark :;
elastomer terpolymer derived from 45% vinylidene fluoride, 30% hexafluoropropylene and 25% tetrafluoroethylene was added dropwise to a bath prepared from 500 ml of 0.5M aqueous silicic acid saturated with BaC12, 500 ml of water saturated with BaC12, and 2 ml of 2~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6). The drops flattened on contact with the bath, but coagulated throughout and were coated with a nontacky coating. The particles were decanted from the bath, washed repeatedly with water and air dried to give white, free-flowing flakes about 5 mm in diameter.
Example 14 A mixture was prepared from equal volumes of , neoprene latex ~1 (37% solids, pH 12) and the aqueous fluoro-elastomer latex described in Example 13. This mixture (20 ml) was introduce~ dropwise into a bath containing approximately 1.5% SiO2 and 2.1~ CaC12 prepared from 100 ml of 0.5M aqueous silicic acid, 94 ml of 0.2% aqueous trimethylnonanol ether of i ethylene oxide (Tergitol~ TMN-6), and 6 ml of 50% aqueous ., .
- CaC12. The pellets which formed were washed with water and then dried, first in air and then over P2O5 under vacuum at room temperature. The resulting mixed elastomer pellets were nontacky and free-flowing.
. .
~ Example 15 ,~ ~
A portion (422 ml) of sodium silicate solution (Grade F, Du Pont Co., SiO2/Na2O ratio = 3.25, Na2O = 8.7%, sio2 = 28.4%, viscosity (68C) = 160 cp, specific gravity =
., ~ 1.386) was diluted to 4 liters with distilled water. This , . . .
solution was put through the cation exchange column in acid form described in Example 5. A bath containing approximately 0.5~ SiO2 and 7.6~ NH4Cl was prepared using 250 ml of the ,~
, ., 1~91864 resulting approximately 0.69M silicic acid solution, lQQ0 ml of 15~ NH4Cl, 250 ml of distilled water, and 500 ml of 0.05 aqueous trimethylnonanol ether of ethylene oxide (Tergitol~
TMN-6). Two hundred ml of neoprene latex #2 (37% solids, pH 12.5) was added dropwise to the bath. The pellets which formed were allowed to remain in the bath for 30 minutes.
The bath was decanted and the pellets were washed three times with 2-liter portions of water. The pellets were air dried : at room temperature and atmospheric pressure. The resulting pellets were nontacky and free-flowing.
Example 16 A bath was prepared with a buffer to resist the pH elevation associated with the addition of alkaline neoprene ¢
- latex. The buffer was prepared by diluting a mixture of 1.75 ml of 2M HCl, 0.1 g of trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 12.60 ml of 2M glycine solution ; to 50 ml with distilled water. The bufer was then added to ' 100 ml of 0.69M silicic acid (prepared according to Example , lS), and 50 ml of 30% aqueous NH4Cl. Twenty ml of neoprene ~ 20 latex #2 (37% solids, pH 12.5) was added to the bath dropwise.
',~4. The pH of the bath changed from 3.35 to 3.55 as compared to a pH change to approximately 6.0 for a similar unbuffered bath. Approximately 80 ml of the latex could be added to . . .
the buffered bath before the pH rose above 6.0, at which pH
gelation of the bath occurred rapidly.
Example 17 - A bath containing approximately 2.Q% sio2 and 7.9%
I~ NH4Cl was prepared from lOQQ ml of 0.69M silicic acid, (pre-......
^j pared according to Example 15) 5Q0 ml of 30~ NH4Cl, and 500 ml of 0.2% aqueous trimethylnonanol ether of ethylene oxide .,.~ .
. .
.
, . ., ~ .
.
- 1~91864 (Tergitol~ TMN-6). A 200-ml sample of neoprene latex #3 (33% solids, pH 12) was adjusted from pH 12.0 to pH 12.5 by addition of lN NaOH. This latex was added dropwise to the bath. The pellets which formed were washed with water and then freeze-dried at about -178C under high vacuum. At room temperature the dried pellets were nontacky and free-flowing.
Example 18 ; A bath was prepared using an alumina-modified silica sol (Ludox~ 130M, Du Pont Co.). This product is a 30~ solids, acidic, aqueous dispersion of positiveIy-charged colloidal particles consisting of a dense silica core coated 'f with positively-charged polymeric alumina. The approximate chemical composition is SiO2 = 26~, A12O3 = 4.0~, Cl = 1.4~, MgO z 0.2~, viscosity (25C) = 5-15 cp, pH (25C) = 4.3-4.5, approximate particle diameter = 16 m~, and specific gravity (25C) = 1.23.
The bath containing approximately 0.7% SiO2/A12O3 and 6.1% NH4Cl was composed of 116 ml of 0.2% aqueous sodium `
heptadecyl sulfate anionic surfactant (Tergitol~ Anionic 7, Union Carbide), 80 ml of 15% aqueous NH4Cl, and 4 ml of the . ,-. .
' alumina-modified silica sol described above. To this bath was added dropwise 20 ml of neoprene latex #2 (37% solids, - pH 12.5). The drops coagulated and the resulting coated }
`~ pellets were washed and dried. Nontacky, free-flowing pellets were obtained.
Example 19 A bath containing approximately 1.0% SiO2 and 8.0 ; AlC13 was prepared from 5 ml of 0.69M aqueous silicic acid :;
^` 30 (prepared according to Example 15), 9 ml of 30~ aqueous ,~:
~., ;-AlC13-6H20, 5 ml of 0.2~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 1 ml of distilled water.
To this bath was added dropwise 2 ml of neoprene latex #2 (~7% solids, pH 12.5). The drops coagulated and were removed Prom the bath, washed and dried. Nontacky, free-flowing pellets were obtained.
Examples 20-23 Four baths were prepared, each from 2.5 ml of 0.69M ~
^ aqueous silicic acid (prepared according to Example 15), 5 ml -~ 10 of 0.5~ aqueous trimethylnonanol ether of ethylene oxide ; (Tergitol~ TMN-6), and 12.5 ml of a 30~ aqueous solution of the indicated salts:
~, .
Example 20 NH4Br i~ Example 21 (NH4)2HC6HsO7(citrate) ~"
Example 22 (NH4)2cr2o7 Example 23 NH4SCN
'~
~ To each bath was then added dropw~se 2 ml of neoprene latex ', #2 (37% solids, pH 12.5~. The elastomer pellets which formed : were separately washed with water and dried. All yielded :, nontacky, free-flowing pellets.
~v, ~s Example 24 -~ Ten ml of naphthenic extender oil (Sundex~ 790, Sun Oil Co.) was added to 90 ml of neoprene latex #2 (37% solids, ; pH 12.5) and the mixture vigorously shaken to give an emul-sion. A bath containing approximately 1.0% SiO2 and 7.6%
NH4Cl was prepared from 50 ml of 0.69M aqueous silicic acid - (prepared according to Example 15), lQO ml of 15~ aqueous NH4Cl, and 50 ml of Q.05~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6). The oil extended polymer latex was added dropwise to the bath. The pellets which :~
' .,: : - . .
109~864 formed were separated from the bath, washed with water and dried to yield nontacky, free-flowing pellets of oil-extended elastomer.
Example 25 ~ A bath con'caining approximately 0.9% SiO2 and 10.0%
`~ NaCl was prepared by dissolving 100 g of NaCl in 900 g of i 0.35M aqueous silicic acid, dissolving 100 g of NaCl in 900 g of 0.05% aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and combining the two solutions. The bath was maintained at pH 4-4. 5 by additions of lN HCl during the -~
dropwise addition of 200 ml of neoprene latex #2 (37% solids, pH 12.5). The pellets which formed were allowed to stand in the bath for 16 hours, then washed with water and dried to yield nontacky, free-flowing pellets of uncured elastomer.
Example 2 6 ~.
A bath containing approximately 1.3% SiO2, 3.9% -~ NH4Cl and 11.1% NaCl was made by combining 25 ml of 0. 69M
.'4'~ silicic acid (prepared in accordance with Example 15), 10 , ........................................................................ .
ml of 30~ NH4C1 in 0.2% aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), 40 ml of 20% NaCl in 0.2%
, .~.
~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~
`~ TMN-6), and 125 ml of distilled water. The bath was adjusted to pH 5.0 with lN NaOH. Twenty milliliters of neoprene latex .,, -~ #2 (37% solids, pH 12.5) was added to the bath dropwise while the pH was maintained at 5.0 by dropwise addition of lN HC1.
":
~- The resulting pellets were removed from the bath after one hour, washed three times with 500-ml portions of distilled water, and air dried to yield nontacky, free-flowing pellets.
Example 27 A bath containing approximately 0.5% chlorhydrol :
'f (aluminum chlorohydroxide polymeric complex containing 47.0~
A12O3 and 16.3~ chloride, Reheis Chemical Co.) and 2.3% CaC12 was prepared by combining 10 ml of 10~ aqueous chlorhydrol, 175 ml of 0.05~ aqueous trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6), and 15 ml of 25% aqueous CaC12. The solution was brought to pH 5.0 with lN NaOH. As 20 ml of neoprene latex #2 (37% solids, pH 12.5) was added dropwise, -~
the bath was gently stirred and maintained at pH 5.0 by drop-wise addition of lN HCl. The pellets were allowed to remain in the bath for 1 hour, after which they were washed with three 250-ml charges of distilled water. The pellets were then air dried to form free-flowing nontacky elastomer particles.
Example 28 A surfactant-free bath containing 1.0% SiO2 and 7.6% NH4Cl was prepared from 100 ml of 0.69M agueous silicic . , acid (prepared according to Example 15), 200 ml of 15~ aqueous , NH4Cl, and 100 ml of distilled water. A 100 ml graduated cylinder was filled with this bath. From a 10 ml syringe fitted with a 20 gauge needle, neoprene latex #2 (37~ solids, ~ pH 12.5) was extruded as a continuous stream onto the surface ."~
-~ of the bath at one side of the graduated cylinder, forming c a small puddle. By grasping the edge of the puddle with . . .
tweezers at the other side of the graduated cylinder a continuous fiber of coagulated, hydrous silica-coated poly-chloroprene was drawn off. After being washed and air dried, the fiber was nontacky.
~, Example 29 The procedure of Example 28 was repeated except that more force was used on the syringe, thus causing the :
~` - 32 -. ~ .
- 1~)91864 stream of latex to go through the surface of the bath. The weight of the coagulating stream pulled it to the bottom of the bath where a nontacky continuous fiber of the elastomer about 1-2 mm in diameter collected.
Example 30 The procedure of Example 29 was repeated except that, after the interface at the surface of the bath had been penetrated by the latex stream, the force on the syringe was reduced and adjusted so that free drops fell , 10 from the needle into the bath. The pellets which formed were nontacky and free-flowing when washed and dried.
Example 31 Part A
,., ~, .
To 200 ml of a 30% solids aqueous colloidal sol of alumina-modified silica of pH 8.6-9.3 (Ludox~ AM, Du Pont ;~ Co.) under agitation in a blender was added 2.0 ml of concentrated HC1 (38%). The resulting colloidal solution , containing approximately 29% solids had a pH of 3Ø
Part B
~"
A modified neoprene latex was prepared by adding , 10 ml of a 1% aqueous solution of hydroxyethyl cellulose "
(Cellosize~ QP 30,000, Union Carbide Corp.) to 90 ml of neoprene latex ~2 (37% solids, pH 12.5). The emulsion was . kept agitated to avoid creaming.
~;. Part C
^ A bath containing approximately 4.3% SiO2/A12O3 and 7.5% NH4Cl was prepared by mixing 2.5 ml of the colloidal `~- silica solution prepared in Part A above, 10.0 ml of 15%
aqueous NH4Cl, 1 ml of a 0.2~ aqueous solution of an ampho-teric fluorinated surfactant (Zonyl~ FSB, Du Pont Co.), and , . .:
:~"
:
: -: .
:; -6~5 ml of water. To this bath was added dropwise about 5 ;~
ml of the modified neoprene latex prepared in Part B above. `
The pellets which formed were separated from the bath, washed ~, with water, and dried to obtain nontacky, free-flowing, ~ `
sll~stantially spherical pellets of modified neoprene.
~' Example 32 :'r' ;i~ A bath containing approximately 0.5% SiO2, 7.6%
,: -NH4Cl and 0.01% AlCl3 was prepared by mixing 250 ml of 0.69M
aqueous silicic acid (prepared according to Example 15 and aged for two days), 1000 ml of 15% aqueous NH4Cl, 200 ml of water, 500 ml of 0.05% aqueous trimethylnonanol ether of ~.". :::
. ethylene oxide (Tergitol~ TMN-6), and 50 ml of 1% aqueous , ......................................................... .
AlC13-6H2O which had been adjusted to pH 5.0 by addition of lN NaOH. This bath was kept at pH 4.5-5.0 by addition of lN HCl during the dropwise addition of 200 ml of neoprene latex ~2 (37% solids, pH 12.5) which took eight minutes, and for one hour thereafter. The drops, which coagulated, were separated from the bath, washed three times with water, soaked for three hours in water, and then air dried. The .", ; 20 resulting pellets were nontacky and free-flowing.
Example 33 A silica sol containing approximately 4.6% solids ~; with a pH of 5.0 was prepared by adding 265 ml of a 15%
-~ solids aqueous silica sol (Nyacol~ 215, Nyacol, Inc., .;
pH 10.5) dropwise with vigorous stirring to a solution of ~; 70 ml of lN HCl in 595 ml of water. A bath containing approximately 0.6% SiO2, 7.6% NH4Cl and 0.013% AlC13 was ~,~ prepared by mixing 250 ml of the above sol, 1000 ml of 15%
~ aqueous NH4Cl, 700 ml of a 0.03% aqueous solution of an - 30 amphoteric fluorinated surfactant (Zonyl~ FSB, Du Pont Co.), ,;.
.....
,.,~
.... .
~"
and 50 ml of 1% aqueous AlC13 6H2O which had been adjusted to pH 5.0 with lN NaOH. The resulting bath had a pH of 4.3.
Th.is bath was stirred and kept at pH 4.5-5.0 by addition of HCl during the dropwise addition of 200 ml of neoprene latex #2 (37~ solids, pH 12.5). The pellets which formed were stirred in the bath for one hour, separated, washed three times with water and soaked in 2 liters of water. After drying the pellets were nontacky and showed little tendency -to agglomerate.
Example 34 :;.
In the manner of Example 33, 42 ml of a 49% solids aqueous colloidal silica sol (Ludox~ TM, Du Pont Co., pH 8.9, particles 220-250A in diameter) was blended with 3.9 ml of lN HCl and 454 ml of water to give an aqueous sol containing ~ 5,6% SiO2. A bath containing approximately 0.7~ SiO2, 7.6%
; NH4Cl and 0.013% AlC13 was prepared by substituting 250 ml of the above sol for the sol employed in Example 33 and maintained at a pH of 5.0 by addition of lN HCl. The ~, ' remaining procedure of Example 33 was then repeated to yield nontacky, free-flowing elastomer pellets.
.":
Example 35 In the manner of Example 33, 125 ml of a 30%
; solids aqueous colloidal silica sol (Ludox~ SM, p~l 9.9, Du Pont Co.) in 125 ml of distilled water, was blended with 28 ml of lN HCl and 637 ml of water. A bath was prepared ~; by substituting 250 ml of the above sol for the sol employed ~- in Example 33 and the remaining procedure of Example 33 was repeated. Nontacky, free-flowing pellets were obtained.
Example 36 To 400 ml of a 30~ solids aqueous colloidal sol .~
; - 35 -- 109~864 of alumina-modified silica of pH about 8.9 (Ludox~ AM, Du Pont Co.) was added 4.0 ml of concentrated (38%) hydro-chloric acid with vigorous agitation. The resulting sol had a pH of 3.0 and a solids content of about 29.7%. A bath containing approximately 4.3% SiO2 and 7.5% NH4Cl was pre-pared from 250 ml of this sol, 1000 ml of 15% aqueous NH4Cl, 650 ml of water, and 100 ml of a 0.2% aqueous amphoteric fluorosurfactant solution (Zonyl~ FSB, Du Pont Co.). The bath had a pH of 3.7 and was kept below pH 4. 5 by adding , O.lN HCl during the dropwise addition of 200 ml of neoprene latex #2 (39% solids, pH 12.5). The drops coagulated and were stirred in the bath for 30 minutes, separated, washed three times with water and dried at 60C to obtain nontacky pellets.
Example 37 A bath containing approximately 1.5% SiO2 and 7.6%
NH4Cl was prepared by mixing 100 ml of 0.69M aqueous silicic acid (prepared according to Example 15), 94 ml of 0.2%
trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6) in ethanol, and 6 ml of a 50~ aqueous solution of CaC12 2H2O.
. . .
- To this bath was added dropwise about 20 ml of a 40% solids butadiene/acrylonitrile copolymer latex (Chemigum~ Nitrile Latex 550, Goodyear) having a pH of 8Ø The coagulated ; drops were stirred in the bath for one hour, separated, and .::.
dried under vacuum at 60C to obtain perfectly spherical pellets which were nontacky and free-flowing.
, Example 38 .:
A mixed latex was prepared from 100 ml of neoprene latex #2 (37~ solids, pH 12.5) and 60 ml of natural rubber latex TSC (62~ solids, General Latex Co.). The resulting .~
~ - 36 --' mixture was brought to pH 12.2 by adding lN NaOH. A bath was prepared like the one in Example 37, except on a 10-fold larger scale. During dropwise addition of the mixed latex to the bath, the bath was maintained at pH 5.0 by the addi-ti.on of lN HCl. The coagulated drops remained in the bath for one hour. They were then separated, washed three times with water, and dried, first for five hours in air and then for three days under vacuum over P2O5 at room temperature. -The coated pellets of neoprene/rubber were nontacky and free-flowing.
Example 39 . ,~ .
A bath containing approximately 0.7% SiO2/A12O3 and 7.6% NH4Cl was prepared by mixing 40 ml of a positi~e alumina-modified silica sol tLudox~ 130 M, Example 18), 1000 ml of 15~ a~ueous NH4Cl, and 960 ml of 0.05% aqueous sodium lauryl sulfate (Duponol~ WAQE, Du Pont Co.). The bath had a pH of 4.9 and was maintained at pH 5.0 by addition of lN HCl during dropwise addition of 200 ml of neoprene latex . ., #2 (37% solids, pH 12.5). The coagulated drops were stirred in the bath for one hour, washed with water, and air dried to yield nontacky, free-flowing pellets.
Example 40 A bath containing approximately 0.1% chlorhydrol .~. i ~ and 7.6% NH4Cl was prepared by mixing 1000 ml of 15~ aqueous :
~; NH4Cl, 980 ml of 0.1% aqueous sodium lauryl sulfate (Duponol~
- WAQE), and 20 ml of 10% aqueous chlorhydrol (A12O3 47.0%, ., .
~` chloride 16.3%, Reheis Chemical Co.). To the bath was added ` dropwise 200 ml of neoprene latex #4 while maintaining the ~- bath at pH 5.5 by adding lN HCl. After the addition, the pellets were stirred in the bath for one hour, washed with ''','~;' , ., i()918~;4 water, and air dried. The uncured elastomer pellets were nontacky and free-flowing.
Example 41 Using the apparatus illustrated in Figures 1 and 2, the following aqueous solutions were mixed in tank 1.
10,000 ml of 15% aqueous ammonium chloride ""
`~; 9,500 ml of 0.03% aqueous sodium lauryl sulfate ' surfactant ~Duponol~ WAQE) ~-~,, .
500 ml of 30~ solids colloidal alumina-modified .3"
silica sol (Ludox~ 130M, Example 18) `
The bath thus prepared had a pH of 5.4 and contained approxi- `
.", mately 0.9% SiO2 and 7.6% NH4Cl. While providing agitation, 3480 g of a 40% solids neoprene latex prepared in the manner . ., ~
of neoprene latex #2 was added through the capillary tubes over a period of 13 minutes. Simultaneously, the pH of the i, >- bath was maintained at 5.4 by gradual addition of 51 ml of lN hydrochloric acid. Immediately following the 13-minute ~j:
~ latex addition period, agitation was continued for 17 minutes :
with no further addition of acid, during which time the pH of the bath rose to 6.6. The particles were kept in suspension by agitation during the 17-minute holding period. The ~ agitator was then turned off, the particles were allowed to .i,; .
settle, and the supernatant liquid was separated from the particles by decantation.
The particles were washed by addition of 8000 ml ;~ of distilled water folIowed by a 5-minute agitation period.
~ A
The agitator was then turned off and the supernatant liquid ~ was separated from the particles by decantation. This washing ;~ procedure was repeated twice. The particles were allowed to :.
dry in the air to a constant weight of 1315 g. They were .
`;
,, '`"~
., - : .- , ,, ~ ~ . - . .
, .-. .
1~)9~864 free-flowing and nontacky.
Example 42 Using the apparatus illustrated in Figures 1 and 2, a bath was prepared by mixing the following aqueous solutions in tank 1.
; 10,000 ml of 15% aqueous ammonium chlorlde 9,950 ml of 0.03% aqueous sodium lauryl sulfate surfactant (Duponol~ WAQE) 50 ml of a polyaluminic acid-modified aqueous ~- 10 colloidal silica sol The modified silica sol was prepared by slowly adding 500 g of 35% aqueous boric acid-stabilized basic aluminum acetate solution (Niaproof~, Union Carbide Corp.) to 400 g of aqueous colloidal silica sol [Ludox~ SM, Du Pont Co., 30~ SiO2, average particle size 7 m~, weight ratio SiO2/Na2O 50, pH
~25C) 9.9, freezing point 0C] in a blender and filtering the mixture through coarse filter paper to remove the small amount of gel. The bath thus prepared had a pH of 5.3 and contained approximately 0.1% colloidal silica sol coated :
. .
with polyaluminic acid and 7.6~ NH4Cl.
While providing agitation, 3590 g of 40% solids ` neoprene latex prepared like neoprene latex #l was added to the bath through the capillary tubes over a period of 9 t~ minutes, during which time the pH of the bath rose to 6.7.
, Agitation was continued, keeping the particles in suspension ~; for an additional 51 minutes, with no appreciable change in pH of the bath. The agitator was turned off, the particles . .
- were allowed to settle and the supernatant liquid was separated from the particles by decantation.
....
` 30 The particles were washed by addition of 8000 ml :~.
.
''.':~
of distilled water followed by a 10-minute agitation period.
The agitator was then turned off and the supernatant liquid was separated from the particles by decantation. This washing procedure was repeated three times. The particles were allowed to dry in the air to a constant weight of 1446 g.
They were free-flowing and nontacky.
Example 43 Using the apparatus illustrated in Figures 1 and 2, the following aqueous solutions were mixed in tank 1.
10,000 ml of 15% aqueous ammonium chloride .~
9,950 ml of 0.03% aqueous sodium lauryl sulfate surfactant (Duponol~ WAQE) 50 ml of the polyaluminic acid-modified aqueous ; colloidal silica sol described in Example The bath thus prepared had a pH o 5.2. rflhile providing agitation, 4578 g of 40~ solids neoprene latex prepared like neoprene latex #2 was added through the capillary tubes over a period of 18 minutes, during which time the pH rose to 6.7.
Agitation was continued, keeping the particles in suspension for an additional 42 minutes, with no appreciable change in pH of the bath. The agitator was turned off, the particles were allowed to settle and the supernatant liquid was separated from the particles by decantation.
The particles were washed by addition of 20,000 ml of distilled water followed by a 10-minute agitation period.
The agitator was then turned off and the supernatant liquid was separated from the particles by decantation. This washing procedure was repeated once. The particles were allowed to dry in air to a constant weight of 1767 g. They were free-flowing and nontacky.
i ~,... .
:.
-^ 1091864 Example 44 A bath containing approximately 0.6% SiO2, 0.9~
CaC12, 0.3% AlC13 and 0.6% NaCl was prepared by mixing 1694 g of H2O, 10.0 g of AlC13 6~2O, 24.2 g of CaC12 2H2O, 12-Q g of NaCl, 1.2 g of an amphoteric fluorinated surfactant (Zonyl~
FSB, Du Pont Co.), and 250 ml of a colloidal sil~ca sol having - a pH of 2.0 and containing 4.8% SiO2. This colloidal sol was prepared by adding a mixture of 125 ml of a 30% solids aqueous silica sol (Ludox~ SM, Du Pont Co.) and 125 ml of H2O to a running blender containing 637 ml of H2O and 40 ml of lN HCl.
To this bath was added dropwise 198 ml of 40% solids neoprene latex prepared like neoprene latex #1. After 30 minutes, the bath was decanted fxom the pellets which had formed. The pellets were soaked in 2 liters of H2O for 3Q
, minutes and then filtered from the wash water and spun for 2 minutes in a basket centrifuge. The pellets were then shaken with 1.5~ of their weight of talcum powder and spread in a tray to air dry overnight. They were further dried over P2O5 `~ under vacuum at room temperature. The resulting nontacky free-flowing pellets contained 1.56 milliequivalents of residual alkalinity per 100 g of isolated polymer, as sho~n by nonaqueous titration to a bromophenol end point.
Example 45 ~,. .
; A bath containing approximately 0.5% SiO2, 0.9%
CaC12 and 0.3~ AlC13 was prepared by mixing 1714.6 ml of H2O, lO.Q g of AlC13-6H2O, 24.4 g of CaC12-2H2O, 1.2 g of the trimethylnonanol ether of ethylene oxide (Tergitol~ TMN-6) and 250 ml of 0.69M silicic acid which had aged for five days.
- To this bath was added dropwise 200 ml of 40% solids neoprene . .
latex prepared like neoprene latex #1. The pellets which , . .
. .~
;~
.
,, .
, .
109~864 formed were isolated, washed and dried as in the procedure of Example 44. The resulting free-flowing, nontacky pellets had a residual alkalinity of 2.43 meq/100 g.
Example 46 A latex mixture was prepared from 2 ml of the sodium silicate solution described in Example 15, 15 ml of lN NaOH, and 198 ml of 40% solids neoprene latex prepared like neoprene latex #2. This mixture was added dropwise to a bath containing approximately 1.8% CaC12, 1.7~ NaCl, 0.6 AlC13 and 0.6~ modified sol prepared from 898.6 ml of H2O, 1000 ml of 2~ AlC13-6H2O (adjusted to pH 3.5 with lN NaOH), 36.4 g of anhydrous CaC12, 34 g of NaCl, 1.0 g of 30% sodium lauryl sulfate (Duponol~ WAQE), and 30 ml of the modified aqueous colloidal silica sol described in Example 42. The pellets which formed were removed from the bath after 15 minutes, washed with water, centrifuged, treated with talc and dried as described in Example 44. The resulting pellets were nontacky and free-flowing.
,~ .
:"
;
: . .
. . .
~ .
;';
;, ~ - 42 -~
'`;
:.
Claims (24)
1. A washed and dried, nontacky, elastomeric shaped object which comprises a normally tacky, uncured elastomer con-taining, based on the total weight of the shaped object, less than 3% by weight of water soluble material and less than 1%
by weight of volatile material, and having 0.05 to 3% by weight of an integral, porous coating of a water insoluble, hydrous, inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, substantially all of said inorganic oxide being present as a coating, and said shaped object having a minimum dimension of 0.01 to 10 millimeters.
by weight of volatile material, and having 0.05 to 3% by weight of an integral, porous coating of a water insoluble, hydrous, inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, substantially all of said inorganic oxide being present as a coating, and said shaped object having a minimum dimension of 0.01 to 10 millimeters.
2. The shaped object of Claim 1 in which the elastomer is neoprene.
3. The shaped object of Claim 2 in which the coating is 0.5 to 2% by weight of the shaped object, the shaped object contains less than 1% by weight of water soluble material and less than 0.5% by weight of volatile material, and the minimum dimension of the shaped object is 0.1 to 5 millimeters.
4. The shaped object of Claim 3 in which the inor-ganic oxide is a silicic acid polymer.
5. The shaped object of Claim 4 in the form of a neoprene fiber having a silicic acid polymer coating.
6. The shaped object of Claim 4 in which the inor-ganic oxide is an aluminic acid polymer.
7. The shaped object of Claim 1 in which the elastomer is a fluoropolymer and the inorganic oxide is a silicic acid polymer.
8. A highly porous, nontacky, elastomeric shaped object which comprises normally tacky, uncured elastomer having 0.05 to 3% by weight of an integral, porous coating of a water insoluble, hydrous, inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, substantially all of said inorganic oxide being present as a coating, and said shaped object having a minimum dimension of 0.01 to 10 millimeters, an opaque appearance when the object is dispersed in water and a vesicular structure when a cross section of the object is observed in a micrograph.
9. The shaped object of Claim 8 in which the elastomer 18 neoprene and the inorganic oxide is a silicic acid polymer.
10. The shaped object of Claim 9 which contains less than 3% by weight of water soluble material and less than 1%
by weight of volatile material.
by weight of volatile material.
11. The shaped object of Claim 10 in which the coating 18 0.5 to 2% by weight of the shaped object, the shaped object contains less than 1% by weight of water soluble material and less than 0.5% by weight of volatile material, and the minimum dimension of the shaped object is 0.1 to 5 millimeters.
12. A method of preparing nontacky, elastomeric shaped objects which comprises bringing shaped bodies of a normally tacky, uncured elastomer latex having a solids content of 20%
to 65% by weight into contact with an aqueous bath containing, based on the total weight of the bath, (a) 0.5 to 25% by weight of a soluble coagulating salt for the latex, and (b) 0.01 to 5% by weight of a soluble or colloidally dispersed, hydrous, inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, said bath having a pH of 2 to 7 such that, when a drop of 1.0N NaOH is added to the bath, the drop is imme-diately surrounded by a cloudy coating of gelled, hydrous, inorganic oxide, thereby coagulating the latex and forming highly porous shaped objects of the coagulated elastomer coated with water insoluble, hydrous, inorganic oxide.
to 65% by weight into contact with an aqueous bath containing, based on the total weight of the bath, (a) 0.5 to 25% by weight of a soluble coagulating salt for the latex, and (b) 0.01 to 5% by weight of a soluble or colloidally dispersed, hydrous, inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof, said bath having a pH of 2 to 7 such that, when a drop of 1.0N NaOH is added to the bath, the drop is imme-diately surrounded by a cloudy coating of gelled, hydrous, inorganic oxide, thereby coagulating the latex and forming highly porous shaped objects of the coagulated elastomer coated with water insoluble, hydrous, inorganic oxide.
13. The method of Claim 12 in which the elastomer is neoprene.
14. The method of Claim 13 in which the inorganic oxide is soluble.
15. The method of Claim 14 in which the inorganic oxide is polysilicic acid which has not aged for more than 90% of its gel time prior to being added to the bath.
16. The method of Claim 13 in which the latex has a solids content of 35 to 50%, the latex is added as drops above the surface of the bath, and the pH of the bath is 2.5 to 5.5.
17. The method of Claim 16 in which the bath contains 1 to 10% by weight of coagulating salt including 0.002 to 2% by weight of an ionizable salt of a metal selected from the group consisting of aluminum and yttrium, and 0.03 to 2% by weight of inorganic oxide.
18. The method of Claim 17 in which the inorganic oxide is soluble.
19. The method of Claim 18 in which the inorganic oxide is polysilicic acid which has aged for 5 to 70% of its gel time prior to being added to the bath.
20. The method of Claim 12 in which the highly porous shaped objects are washed with water until the water soluble material content is less than 3% by weight, and dried until the volatile material content is less than 1% by weight, thereby providing free-flowing, nontacky, elastomeric shaped objects.
21. The method of Claim 20 in which the elastomer is neoprene and the inorganic oxide is polysilicic acid which has not aged for more than 90% of its gel time prior to being added to the bath.
22. The method of Claim 21 in which the latex has a solids content of 35 to 50%, the latex is added as drops above the surface of the bath, and the pH of the bath is 2.5 to 5.5.
23. The method of Claim 22 in which the bath contains 1 to 10% by weight of coagulating salt including 0.002 to 2% by weight of an ionizable salt of a metal selected from the group consisting of aluminum and yttrium, and 0.03 to 2% by weight of polysilicic acid which has aged 5 to 70% of its gel time prior to being added to the bath.
24. The method of Claim 23 in which the washing step reduces the water soluble material content to less than 1% by weight, and the drying step reduces the volatile material content to less than 0.5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA350,820A CA1099057A (en) | 1976-06-29 | 1980-04-29 | Coagulating and coating bath for uncured elastomer objects |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70096576A | 1976-06-29 | 1976-06-29 | |
| US700,965 | 1976-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091864A true CA1091864A (en) | 1980-12-23 |
Family
ID=24815533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA281,448A Expired CA1091864A (en) | 1976-06-29 | 1977-06-27 | Nontacky shaped objects from polymer latices |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6031864B2 (en) |
| CA (1) | CA1091864A (en) |
| DE (1) | DE2728979C2 (en) |
| FR (1) | FR2356671A1 (en) |
| IT (1) | IT1076070B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187322A (en) * | 1981-05-15 | 1982-11-18 | Mitsubishi Rayon Co Ltd | Production of particulate product |
| JPS62171969U (en) * | 1986-04-21 | 1987-10-31 | ||
| JPH01158761U (en) * | 1988-04-22 | 1989-11-02 | ||
| JP2898715B2 (en) * | 1990-07-24 | 1999-06-02 | 株式会社日本触媒 | Method for producing colored fine particles and toner for electrophotography using the same |
| JP6706798B2 (en) * | 2014-08-29 | 2020-06-10 | 国立大学法人山形大学 | Elastomer particle and method for producing the same, elastomer composition, elastomer particle dispersion and molded article |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2298713A (en) * | 1938-05-27 | 1942-10-13 | Wingfoot Corp | Method of treating rubber |
| US2879173A (en) * | 1956-03-06 | 1959-03-24 | Du Pont | Process for preparing free-flowing pellets of polychloroprene and the resulting product |
| DE1243863B (en) * | 1958-11-14 | 1967-07-06 | Bayer Ag | Process for coagulating aqueous dispersions of polychloroprene |
| DE2135266C3 (en) * | 1971-07-15 | 1979-09-06 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of free-flowing, powdery, fuel-containing rubber mixtures from rubber solutions |
| DE2346653C3 (en) * | 1973-09-17 | 1980-12-11 | Degussa Ag, 6000 Frankfurt | Process for the production of powdery elastomer mixtures with silicas and silicates |
| JPS5247943B2 (en) * | 1974-10-15 | 1977-12-06 |
-
1977
- 1977-06-27 CA CA281,448A patent/CA1091864A/en not_active Expired
- 1977-06-28 FR FR7719756A patent/FR2356671A1/en active Granted
- 1977-06-28 IT IT2514377A patent/IT1076070B/en active
- 1977-06-28 JP JP7624577A patent/JPS6031864B2/en not_active Expired
- 1977-06-28 DE DE19772728979 patent/DE2728979C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6031864B2 (en) | 1985-07-24 |
| FR2356671A1 (en) | 1978-01-27 |
| DE2728979C2 (en) | 1985-04-11 |
| IT1076070B (en) | 1985-04-22 |
| DE2728979A1 (en) | 1978-01-05 |
| FR2356671B1 (en) | 1982-03-26 |
| JPS533440A (en) | 1978-01-13 |
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