EP0432214A1 - Extrudable vinylidene chloride polymeric composition - Google Patents
Extrudable vinylidene chloride polymeric compositionInfo
- Publication number
- EP0432214A1 EP0432214A1 EP89910284A EP89910284A EP0432214A1 EP 0432214 A1 EP0432214 A1 EP 0432214A1 EP 89910284 A EP89910284 A EP 89910284A EP 89910284 A EP89910284 A EP 89910284A EP 0432214 A1 EP0432214 A1 EP 0432214A1
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- EP
- European Patent Office
- Prior art keywords
- acid
- polymeric composition
- salt
- amount
- nonalkenic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
Definitions
- the present -invention relates to a thermally sensitive plastic possessing decreased thermal sensitivity, and its method of preparation.
- Vinylidene chloride interpolymers are well- known in the prior art. Such polymers are also well- known to be thermally sensitive, which means that upon exposure to desirable processing temperatures such polymers tend to thermally decompose, e.g., generate carbonaceous material contamination, discolor or evolve hydrogen chloride.
- pellets of polymeric compositions comprising vinylidene chloride interpolymers may be an advantageous form from which to fabricate articles, the pellets of such polymeric compositions are particularly difficult to extrude.
- Pellet formation requires an exposure of the thermoplastic composition to heat prior to the conventional extrusion step of the polymeric composition into articles. This additional heat history is believed to make the vinylidene chloride interpolymer in pellet form even more susceptible to thermal instability than a vinylidene chloride interpolymer in powder form. Consequently, additive packages which improve the thermal stability of polymeric compositions comprising vinylidene chloride interpolymer in powder form do not necessarily improve the thermal stability of such polymeric compositions in pellet form.
- the process of the present invention is a method for making a polymeric composition, the steps of the method including:
- step (C) characterized by the step, after the beginning of step (A) and prior to the completion of step (C), of adding to either the polymerizable mixture or the polymer slurry an amount of at least one salt of a nonalkenic weak acid with the pH of the aqueous phase of the polymer slurry being maintained at an effective value to provide a reaction product in the polymeric composition in an amount effective to improve the color stability of the polymeric composition and within the ' range of 0.01 to 5 percent by weight of the combined amount of monomers at the time of addition.
- the invention in a second aspect, is a polymeric composition including a vinylidene chloride interpolymer, in an amount of at least 80 weight percent based on the total weight of the composition, the interpolymer being formed from a monomer mixture comprising vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the weight of the monomer mixture; characterized in that the polymeric composition also comprises from 0.01 to 5 weight percent, based on the total weight of the composition, of a reaction product of a salt of a nonalkenic weak acid in an amount effective to provide improved thermal stability to the polymeric composition.
- the invention relates to the use of the aforementioned polymeric composition in making melt-extruded articles.
- the present invention concerns a polymeric composition having "improved extrudability" (defined below) .
- the polymeric or plastic composition comprises a vinylidene chloride interpolymer and a reaction product of a nonalkenic weak acid to form a polymeric or plastic composition.
- polymeric or plastic composition is meant to include the vinylidene chloride interpolymer and reaction product of a nonalkenic weak acid, as well as other additives.
- the amount of vinylidene chloride polymer is at least 80 percent by weight based on the weight of the total composition. It is preferably at least 90 percent by weight.
- the term "improved extrudability" means that if subjected to desirable elevated processing temperatures, the polymeric composition is less thermally sensitive and consequently, the extrudate possesses a reduced level of carbonaceous material contamination, reduced discoloration or less hydrogen chloride evolvement.
- extrudate any composition which becomes partially or totally melted when subjected to elevated temperatures during processing methods, e.g., casting, blowing, extrusion molding, injection molding, blow molding, coextrusion, laminating or calendering.
- vinylidene chloride interpolymer encompasses homopolymers, copolymers, terpolymers, etc. of vinylidene chloride.
- the polymeric compositions suitable for use in the present invention are those vinylidene chloride interpolymers prepared from a monomer mixture comprising a predetermined amount of vinylidene chloride monomer and also a predetermined amount of ethylenically unsaturated comonomer copolym- erizable therewith.
- Such phase comprises a mixture containing essentially all of the monomer to be polymerized.
- An effective amount of polymerized vinylidene chloride monomer is generally in the range of from 60 to 99 percent by weight of interpolymer, with the preferred ranges, as is known to the skilled artisan, dependent upon the ethylenically unsaturated comonomer copolymerized therewith.
- the amount of ethylenically unsaturated comonomer is maintained below an amount effective to destroy the semicrystalline character of the interpolymer.
- semicrystalline character it is meant that the interpolymer has between about 5 percent and about 95 percent crystallinity. Crystallinity values depend upon the measuring technique, and as used herein crystallinity is defined by the commonly used density method. See, for example, the discussion by R. A. Wessling, in Chapter 6 of Polyvinylidene Chloride, Vol. 5, Gordon and Breach Science Publishers, New York (1977).
- the amount of ethylenically unsaturated comonomer or comonomers c ⁇ polymerizable with the vinylidene chloride monomer that are present in the monomer mixture is in an amount of from 1 to 40 weight percent, said weight percents being based on total monomer mixture weight.
- Suitable ethylenically unsaturated comonomers copolymerizable with the vinylidene chloride monomer include vinyl chloride, alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile and methacrylonitrile.
- the alkyl acrylates and alkyl methacrylates are generally selected to have from 1 to 8 carbon atoms per alkyl group.
- alkyl acrylates and alkyl methacrylates are selected to have from 1 to 4 carbon atoms per alkyl group.
- the alkyl acrylates and alkyl methacrylates are most preferably selected from the group consisting of methyl acrylate, ethyl acrylate and methylmethacrylate.
- the vinyl chloride will preferably be present in an amount of from 30 to 5 percent by weight of interpolymer and vinylidene chloride will be present in an amount of from 70 to 95 percent by weight of interpolymer; and more preferably the vinyl chloride will be present in an amount of from about 25 to about 10 percent by weight of interpolymer and the vinylidene chloride will be present in an amount of from 75 to 90 percent by weight of interpolymer.
- the alkyl acrylate When the ethylenically unsaturated comonomer employed is an alkyl ac ylate, the alkyl acrylate will preferably be present in an amount of from 30 to 2 percent by weight of interpolymer and the vinylidene chloride will be present in an amount of from 98 to 70 percent by weight of interpolymer; and preferably the alkyl acrylate will be present in an amount ' of from 40 to 6 percent by weight of interpolymer and the vinylidene chloride will be present in an amount of from 94 to 60 percent by weight of interpolymer.
- the vinylidene chloride interpolymer is generally formed through an emulsion or suspension polymerization process. Exemplary of such processes are U.S. Patents 2,558,728; 3,007,903; 3,642,743; and 3,879,359; and the methods described by R. A. Wessling, in Polyvinylidene Chloride, Gordon and Breach Science Publishers, New York (1977), Chapter 3.
- a monomer phase is suitably emulsified or suspended in an aqueous phase through the use of emulsifying or suspending agents.
- An initiator and surface active agent capable of emulsifying or suspending the monomeric materials in the aqueous phase is then added to the solution and polymerization of the monomers allowed to proceed until achieving its desired degree of conversion.
- the polymerization of the monomeric materials is usually carried out with heating and agitation.
- a relatively small amount of a water-soluble suspending agent or emulsifying agent is used as hereinafter described, and the predominant proportion of monomer is uniformly admixed along with at least about 0.01 weight percent, preferably between about 0.1 and 1 weight percent, said weight percent being based on the weight of the monomer, of the water-soluble dispersing agent, and between 0.1 and 0.5 weight percent of a monomer-soluble polymerization initiator.
- Exemplary water-soluble suspending or emulsifying agents are the water-soluble alkyl or hydroxyalkyl cellulose ethers wherein the alkyl group contains 1 to 2 carbon atoms and the hydroxyalkyl groups contain from 2 to 4 carbon atoms.
- Any viscosity grade of the cellulose ethers may be used although it is preferred to use the lower viscosity grades such as 10 cps to 400 cps.
- the low viscosity grades of methyl cellulose and hydroxypropyl methyl cellulose are more easily dissolved in water than the higher viscosity grades.
- viscosity grade as herein used is meant the viscosity of a 2 percent aqueous solution of the cellulose ether measured at 20°C.
- the process of this invention prepares a polymer in granular or bead form which is readily isolatable from the polymerization system by simple means, such as filtration. Washing with water will remove most of the residual components of the dispersant and catalyst system.
- exemplary initiators contemplated for use in the present invention include the peroxides, such as hydrogen peroxide, isopropyl peroxypercarbonate, lauroyl peroxide or mixtures thereof.
- the order of addition of the various ingredients is not critical, it is preferred to prepare the complete aqueous phase including initiator, and emulsifier or suspending agent, and then to add the monomer phase.
- preparing the aqueous phase it has been found to be most convenient, although not critical, to solubilize the emulsifier or suspending agent, and then to add the initiator.
- the amount of water used has little effect on the process, it is preferred to operate the polymerization process in the range of from 2 to 4 parts per water per part of monomer. When less water is used, there may be insufficient heat transfer to carry away the heat of polymerization.
- polymerization conditions e.g., temperature and agitation
- polymerization conditions are those conventionally employed in the polymerization of vinylidene chloride.
- the mixture is heated with agitation, in the substantial absence of oxygen, to a temperature of between 25°C and 85°C and preferably between 45°C and 60°C, for a period sufficient to provide the desired conversion of monomer to polymer.
- the conversion of monomer to polymer is between 80 and 99 weight percent, and preferably between 88 and 95 weight percent.
- the resulting suspension or emulsion slurry of vinylidene chloride interpolymer is then vacuum stripped to form a monomer-free slurry. Thereafter, the slurry is cooled down, unloaded and dewatered, and vinylidene chloride interpolymer is collected and further dried. The resin may be subsequently hydrated to reform the polymer slurry.
- the process may also include using prefilter, an electrofilter and a final dryer such as a fluid energy dryer, and the like.
- the salt of a nonalkenic weak acid is a composition selected to be soluble or partially soluble, and which will not adversely affect the properties of the vinylidene chloride interpolymer.
- soluble or partially soluble is meant that the nonalkenic weak acid salt will have a solubility greater than about 0.1 percent by weight in the aqueous phase, preferably about 0.5 percent in the aqueous phase, and most preferably about 1 percent by weight in the aqueous phase. Solubility will be affected by temperature, pressure, pH and other species in the composition; chese factors are known to those skilled in the art and their effect upon this invention may be readily determined without undue experimentation.
- the nonalkenic weak acid is selected from the following acids, or derivatives thereof, boric acid, hexapolyphosphoric acid, hypophosphoric acid, orthophosphoric acid, pyrophosphoric acid, phosphorous acid, tetrapolyphosphoric acid, tripolyphosphoric acid, alkyl monocarboxylic acid, aryl monocarboxylic acid, alkyl polycarb ⁇ xylic acid, aryl polycarboxylic acid, hydroxyalkyl monocarboxylic acid, hydroxyalkyl polycarboxylic acid.
- the salt may be selected from alkali metals (Group IA of the Periodic Table as found on the inside cover of "Advanced Inorganic Chemistry” by F. Albert Cotton and G. Wilkinson, published by Interscience in 1962) and alkali earth metals (Group IIA of the Periodic Table).
- nonalkenic weak acid salts may be culled from the above list of candidates based upon whether any of the following properties are adversely affected by the addition of a nonalkenic weak acid salt to the vinylidene chloride interpolymer alone, the vinylidene chloride interpolymer in a formulated resin, or the vinylidene chloride interpolymer in an extruded product:
- Effects on oxygen and gas permeability may be indirectly measured by differential scanning calorimetry to determine if the glass transition temperature of the vinylidene chloride interpolymer is altered or may be directly measured, for example, by using an OX-TRAN ® 1050, commercially available from Modern Controls, Inc.
- taste and odor properties may be determined preliminarily by reviewing the composition of the nonalkenic weak acid salt.
- Certain structures can, under varying conditions, sometimes adversely affect the taste and odor properties of the vinylidene chloride interpolymer; likewise, certain structures can, under varying conditions, sometimes generate by-products which could adversely affect the taste and odor properties of - 12-
- VDC interpolymer extrudate e.g., esters can hydrolyze releasing the free alcohol.
- sulfur and nitrogen contain structures tend to be odoriferous and have similar by-products.
- ketone or aldehyde structures tend to be detectable at low levels by taste and odor.
- Color and carbonaceous material contamination may be measured by inspecting an extrudate after running comparative extrusion trials on a 3/4" Brabender tape extrusion at about 175°C between a vinylidene chloride resin containing the nonalkenic weak acid salt and the resin without the nonalkenic weak acid salt.
- Thermostability may be measured by differential scanning calorimetry or thermogravimetric analysis to determine if the nonalkenic weak acid salt accelerates decomposition of vinylidene chloride interpolymer.
- Exemplary salts of nonalkenic inorganic weak acids include phosphate salts and derivatives thereof such as sodium phosphates (e.g., tetrasodium pyrophosphate, sodium pyroph ⁇ sphate, sodium o thophosphate, sodium polyphosphate) , the potassium phosphates (e.g.
- potassium pyrophosphate potassium orthophosphate, potassium polyphosphate
- salts of weak nonalkenic organic acids such as methyl trisodium pyrophosphate, sodium alkyl or aryl phosphates, phosphites and sulfates
- salts of nonalkenic carboxylic acids e.g., sodium oxalate, sodium citrate, potassium acetate
- salts of nonalkenic dicarboxylic acids such as succinic acid (e.g., sodium succinate, potassium succinate, lithium succinate); mixtures thereof and the like.
- Salts of nonalkenic weak acids suitable for purposes of the present invention are prepared by processes well-known in the art. By way of illustration only, techniques for preparing tetrasodium pyrophosphate are set forth in The Merck Index, 10th Edition (1983).
- the salt of a nonalkenic weak acid may be added to the monomers before they are copolymerized into a vinylidene chloride interpolymer, i.e., advance addition, or the salt of nonalkenic weak acid may be added to a vinylidene chloride interpolymer dispersion, i.e., polymer slurry addition.
- advance addition may be applied in combination.
- advance addition is preferred because the salts of the nonalkenic weak acid are more evenly dispersed in and throughout the resultant polymerization product.
- the nonalkenic weak acid salt can be formed prior to aqueous dissolution or by in situ combination of a salt with the acid or acid derivative.
- At least one salt of a nonalkenic weak acid is loaded in a reactor with the monomer mixture or the resultant polymer slurry an amount to provide a reaction product in the polymeric composition in an amount effective to improve the color stability of the polymeric composition.
- at least one salt of a nonalkenic weak acid will be added in an amount of from 0.001 to 10 weight percent, based on the weight of the monomer mixture or polymer slurry.
- the reaction product of the salt of a nonalkenic weak acid will generally be present in the resulting dried polymeric composition in an amount of 0.01 to 5 weight percent, preferably 0.05 to 3 weight percent and most
- an alkenic carboxylic j _- acid or salt may be applied via polymer slurry addition. That is, the alkenic carboxylic acid or salt may be added consecutively with the salt of a nonalkenic weak acid to the polymer slurry.
- the alkenic carboxylic acid or salt will be added in an amount of from 0.001 to 10 weight percent, whereby the resultant polymeric composition contains a reaction product of the alkenic carboxylic acid or salt in an amount effective to provide an improved color 5 stability of the polymeric composition.
- the reaction product of the alkenic carboxylic acid or salt will generally be present in the resulting dried polymeric composition in an amount of 0.01 to 5 weight percent, preferably 0.05 to 3 weight percent and most preferably
- alkenic carboxylic acids or salts include acrylic acid, oleic acid, linoleic acid, linolenic acid, and dicarboxylic acids such as fumaric acid, and maleic acid and salts thereof.
- the mixture comprises a salt of a nonalkenic weak acid such as tetrasodium pyrophosphate and an alkenic carboxylic acid or salt such as maleic acid, or its salt.
- Salts of alkenic carboxylic acids suitable for purposes of the present invention are prepared by processes well-known in the art. By way of illustration only, techniques for preparing maleic acid are set forth in the Merck Index, 10th Edition (1983).
- reaction product means that the relevant materials added together cannot be removed in their original form.
- reaction product specifically refers to the phenomena of the salt of the nonalkenic weak acid and alkenic carboxylic acid or salt becoming hydrated, protonated or deprotonated, whereby its composition is changed. Because the salt of a nonalkenic weak acid will dissolve in water, it will hydrolyze to form a variety of species. Upon subsequent drying and reduction of the composition it may not revert to its initial structure or composition. Thus, this invention differs from dry blending the components of the polymeric composition, because a reaction product will not form.
- the exact amount of the salt of a nonalkenic weak acid which is initially added to be solubilized in the aqueous phase of the the monomer mixture or polymer slurry will depend on the pH of the aqueous phase of the monomer mixture or polymer slurry, respectively; the pH profile, i.e., the change in pH during the reaction; the phase ratio of the monomer mix, i.e., monomer to aqueous ratio; and the solubility of the nonalkenic weak acid salt in the aqueous phase. Once the above parameters are selectively determined, a skilled artisan will be able to determine the amount of salt which is necessary without undue experimentation.
- the salt of a nonalkenic weak acid acts as an HCL scavenger to provide an effective reduction in the amount of free HCL in the polymeric composition.
- Acid scavenging is related to the number of basic sites in the reaction product moiety. One skilled in the art will recognize that this is inversely related to the number of protons on that same moiety.
- the pH of the monomer mixture aqueous phase must be maintained in the range of from 3 to 12, for a period varying inversely with the amount of time during which the pH is outside of the prescribed range.
- the inventors have found, however, that for the practice of the present invention, the pH of the aqueous phase of the polymer slurry must also be maintained within a selected range. If, after addition of the salt of a nonalkenic weak acid, the pH of the aqueous phase in the polymer slurry is too high or too low, discoloration of the polymeric composition may occur.
- the pH of the slurry after polymerization is generally in the range of 2 to 5.
- the interpolymer may be maintained in the polymer slurry when it has an extreme pH above about 12 or below about 3 for a period varying inversely with the amount of time during which the pH is outside of the prescribed range.
- the selection of the specific pH of the aqueous phase of polymer slurry may be determined by one of ordinary skill in the art without undue experimentation.
- the pH of the slurry will be dependent upon a number of factors, and may be determined by one skilled in the art without undue experimentation.
- Exemplary factors include the salt of the nonalkenic weak acid and, optionally, the alkenic carboxylic acid or salt employed; the stage when the salt of the nonalkenic weak acid and, optionally, the alkenic carboxylic acid or salt are added to the monomer mixture; the polymerization initiator chosen; the extent of dehydrochlorination of the polymer and any water-soluble species added to facilitate polymerization.
- the polymeric composition will generally con ⁇ tain substantially all of the hydrolyzed salt species; the relative level of each salt species will be dependent upon the pH of either or both the monomer mixture and slurry.
- Tetrasodium pyrophosphate for example, will hydrolyze to form the pyrophosphate anion, monohydrogen pyrophosphate, dihydrogen pyrophosphate, trihydrogen pyrophosphate and tetrahydrogen pyrophosphate.
- this invention differs from the blending of a dry powder and a vinylidene chloride interpolymer to form a uniform mixture, because composition of the powder will not change.
- additives may be incorporated in the polymeric composition of the present invention. Additive type and amount thereof will depend upon several factors. One factor is the intended use of the polymeric composition. A second factor is tolerance of the polymeric composition for the additives. That is, how much additive can be added before the physical properties of the polymeric composition are adversely affected to an unacceptable level. Other factors are apparent to those skilled in the art of polymer formulation and compounding.
- Additives which may be incorporated into the polymeric composition of the present invention are selected from the group consisting of plasticizers, heat stabilizers, light stabilizers, pigments, processing aids, lubricants and the like. Each of these additives is known and several types of each are commercially available.
- Blending of the additives in forming the polymeric composition can be accomplished by using conventional melt processing, as well as dry blending techniques.
- the additives may be blended concurrently with the vinylidene chloride interpolymer, or may be consecutively blended with the vinylidene chloride interpolymer.
- Exemplary melt processing equipment includes ,,- heated two-roll compounding mills, Brabender mixers, Banbury mixers, single screw extruders, twin screw extruders, and the like, which are constructed for use. with thermally sensitive polymers. See, for example, the discussion by R. A. Wessling, in Chapter 11 of 0 Polyvinylidene Chloride, Vol. 5, Gordon and Breach
- pellet or “pellets” refer to particles having a minimum cross-sectional dimension of at least 1/32 inch, preferably of at least 1/16 inch and most preferably of at least 1/8 inch; said pellets suitably have a maximum cross-sectional dimension of at least 1/2 inch, preferably of at least 3/8 inch and most preferably of at least 1/4 inch.
- An exemplary method of forming the polymeric composition into pellets includes extruding the polymeric composition through a strand die to form an extruded strand, and then chopping the extruded strand into pellets.
- the polymeric composition in either powder or pellet form, may be fabricated into any suitable final product, e.g., a variety of films or other articles.
- films and articles are fabricated with conventional coextrusion, e.g., feedblock coextrusion, multimanifold die coextrusion or combinations of the two; injection molding; coinjection molding; extrusion molding and lamination techniques.
- Articles formed therefrom include blown and cast, mono- and multilayer, films; rigid and foam sheet; tubes; pipes; rods; fibers and various profiles. Lamination techniques are particularly suited to produce multi-ply sheets.
- specific laminating techniques include fusion, i.e., whereby self-sustaining lamina are bonded together by applications of heat and pressure; wet combining, i.e., whereby two or more plies are laminated using a tie coat adhesive, which is applied wet, the liquid driven off and combining by subsequent pressure laminating in one continuous process; or by heat reactivation, i.e., combining a precoated film with another film by heating and reactivating the precoat adhesive so that it becomes receptive to bonding after subsequent pressure laminating.
- Exemplary articles include rigid containers used for the preservation of food, drink, medicine and other perishables. Such containers should have good mechanical properties, as well as low gas permeabilities too, for example, oxygen, carbon dioxide, water vapor, odor bodies or flavor bodies, hydrocarbons or agricultural chemicals. Consequently, multilayer sheet
- a polymeric composition is formed from a monomer mixture through a suspension polymerization process.
- Into a ten-gallon stirred polymerization 0 reactor is loaded 9000 grams of a mixture comprising about 94 weight percent of vinylidene chloride monomer and about 6 weight percent of methyl acrylate.
- To the mixture in the reactor is added 16,500 grams of demineralized water, 0.4 gram of di-tert-butylmethylphenol; 42 grams of t-butyl peroctoate, 8.5 grams of tetrasodium pyrophosphate as a trace metal scavenger and 19 grams of hydroxypropyl methylcellulose ether as a suspending agent.
- the pH of the monomer mixture should be between about 4-10, and adjusted as necessary.
- the reactor is sealed, purged with nitrogen and elevated to a temperature of about 25°C. After polymerization has begun, the temperature is raised to 80°C and polymerization is allowed to continue for about 16 hours.
- the polymer slurry of polymeric material has a pH of about 2-4.
- the pH of the polymer slurry is adjusted to be within a range of between about 3 and 12; the pH values of specific examples are set forth in Table 1.
- the pH is adjusted acidic by the addition of HC.l and basic by the addition of NaOH, and then maintained at various pH values, as set forth in Table I.
- the polymeric composition is then recovered from the polymer slurry and dried.
- tetrasodium pyrophosphate When tetrasodium pyrophosphate is dissolved in water, it hydrolyzes to form the pyrophosphate anion, monohydrogen pyrophosphate, dihydrogen pyrophosphate, trihydrogen pyrophosphate and tetrahydrogen pyrophosphate.
- the reaction product of tetrasodium pyrophosphate is calculated, in parts per hundred of vinylidene chloride interpolymer, as tetrasodium pyrophosphate.
- the polymeric composition is extruded through a 3/4" extruder having a length to diameter ratio of 25/1.
- the blends are passed to a 3/4" extruder die and extruded into a tape.
- the polymeric composition is extruded into an extrudate tape in a continuous process for a period of about 20 minutes.
- the resin decomposes it discolors, i.e., becomes brownish.
- the decomposition of the extruded resin is determined by visually inspecting the extrudate tape to determine its color. Color is qualitatively rated on a scale of 1 to 10 over a continuous range of discoloration, wherein 1 represents a creamy white color and 10 a rather dark brown.
- the polymeric compositions can be extruded into extrudate tapes which possess excellent color, and optimum color is obtained when the pH of the aqueous phase is greater than about 6.
- Example 5 The procedures of Example 5 are repeated with the following exception: the polymeric composition is extruded for a second time through a single strand die passed through a water bath and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated.
- the pellets are extruded into an extrudate tape in a continuous process for a period of about 20 minutes.
- the extrudate tapes of the extruded pellets exhibited good color.
- ® PS polymer slurry of a monomer mixture, in one hundred parts of polymer, which is polymerized from an initial monomer loading of 94 weight percent vinylidene chloride monomer and 6 weight percent of methyl acrylate monomer.
- ® TSPP tetrasodium pyrophosphate in parts per hundred parts of the polymer in the polymer slurry as added.
- the tetrasodium pyrophosphate is commercially available from the Monsanto Chemical Company.
- ® pH pH of the aqueous phase of the polymer slurry after being charged with tetrasodium pyrophosphate and being adjusted.
- Example 12 The procedures of Examples 5 and 9 are repeated with the following exception: the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride. The extrudate tapes of the polymeric composition exhibited good color.
- Example 12 The procedures of Examples 5 and 9 are repeated with the following exception: the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride. The extrudate tapes of the polymeric composition exhibited good color. Example 12
- Example 5 The procedures of Example 5 are repeated with the following exceptions: instead of addition of the 45 grams of tetrasodium pyrophosphate to the polymer slurry, 45 grams of tetrasodium pyrophosphate are added to the monomer mixture. The pH of the aqueous phase of the monomer mixture is adjusted to about 6.5. After polymerization, the pH of the polymer slurry is adjusted to values shown for Example 6. Thereafter, the polymer slurry is cooled down, unloaded and dewatered. The extrudate tapes from the extruded polymeric composition exhibited good color.
- Example 12 The procedures of Example 12 are repeated with the following exceptions: the polymeric composition is extruded a second time through a single strand die, passed through a water bath, and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated.
- the extrudate tapes of the extruded pellets exhibited good color.
- Example 12-13 The procedures of Examples 12-13 are repeated with the following exception: the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride.
- the extrudate tapes of the polymeric compositions exhibited good color.
- Example 5 The procedures of Example 5 are repeated with the following exceptions. Instead of adding 45 grams of tetrasodium pyrophosphate to the polymer slurry, 27 grams of orthophosphoric acid are added to the polymer slurry.
- the orthophosphoric acid is commercially available from the Fisher Scientific Company.
- orthophosphoric acid When orthophosphoric acid is dissolved in water, it hydrolyzes to form dihydrogen phosphate, mononydrogen phosphate and the orthophosphate anion.
- the reaction product of orthophosphoric acid is calculated, in parts per hundred of vinylidene chloride interpolymer, as trisodium orthophosphate.
- ® PS polymer slurry of a monomer mixture, in one hundred parts of polymer, which is polymer ⁇ ized from an initial monomer loading of 94 weight percent vinylidene chloride monomer and 6 weight percent of methyl acrylate monomer.
- ® OPA orthophosphoric acid, calculated as tri- sodium phosphate in parts per hundred parts of the polymer in the polymer slurry.
- the ortho ⁇ phosphoric acid and sodium hydroxide are com ⁇ dismissally available from the Fisher Scientific Company.
- ® pH pH of the aqueous phase of the polymer slurry after being charged with orthophosphoric acid and adjusted basic with NaOH.
- the polymeric compositions can be extruded into extrudate tapes which possess excellent color, and optimum color is obtained in the pH range from about 7 to about 12.
- Example 18 The procedures of Example 18 are repeated with the following exceptions: the polymeric composition is extruded a second time through a single strand die, passed through a water bath and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletlzing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated.
- the pellets are extruded into an extrudate tape in a continuous process for a period of about 20 minutes.
- the extrudate tapes of the extruded pellets exhibited good color.
- the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride.
- the extrudate tapes of the polymeric compositions exhibited good color.
- the pH of the polymer slurry is adjusted to the values as shown for Example 19. Thereafter, the polymer slurry is cooled down, unloaded and dewatered. The extrudate tapes from the extruded polymeric composition exhibited good color.
- Example 23 The procedures of Example 23 are repeated with the following exceptions: the polymeric composition is extruded a second time through a single strand die, passed through a water bath, and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from
- the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride.
- the extrudate tapes of the polymeric compositions exhibited good color.
- Example 5 The procedures of Example 5 are repeated with the exception that instead of adding 45 grams of tetrasodium pyrophosphate to the polymer slurry, 60 grams of oxalic acid are added to the polymer slurry.
- the oxalic acid is commercially available from the J. T. Baker Company.
- the pH of the polymer slurry is adjusted to values as shown in Table III.
- the pH of the aqueous phase of the polymer slurries is adjusted with NaOH and maintained at various pH's, as set forth in Table III.
- oxalic acid When oxalic acid is dissolved in water, it hydrolyzes to form monohydrogen oxalate and the oxalate anion.
- the reaction product of oxalic anion is calculated, in parts per hundred of vinylidene chloride interpolymer, as disodium oxalate.
- ® PS polymer slurry of a monomer mixture, in one hundred parts of polymer, which is polymerized from an initial monomer loading of 94 weight percent vinylidene chloride monomer and 6 weight percent of methyl acrylate monomer.
- ⁇ SO disodium oxalate, in parts per hundred parts of the polymer in the polymer slurry.
- ® pH pH of the aqueous phase of the polymer slurry after being charged with oxalic acid and adjusted basic with NaOH.
- the polymeric compositions can be extruded into extrudate tapes which possess excellent color, and optimum color Is obtained at pH values of about 4 and greater.
- Example 33
- Example 30 The procedures of Example 30 are repeated with the following exceptions: the polymeric composition is extruded a second time through a single strand die, passed through a water bath and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated.
- the pellets are extruded into an extrudate tape in a continuous process for a period of about 20 minutes.
- the extrudate tapes of the extruded pellets exhibited good color.
- the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride.
- the extrudate tapes of the polymeric composition exhibited good color.
- Example 30 The procedures of Example 30 are repeated with the following exceptions: instead of addition of the 8.5 grams of oxalic acid to the polymer slurry, 8.5 grams of sodium oxalate are added to the monomer mixture. The pH of the aqueous phase of the monomer mixture is adjusted to about 6.5.
- the pH of the polymer slurry is adjusted to values as shown for Example 30. Thereafter, the polymer slurry is cooled down, unloaded and dewatered. The extrudate tapes from the extruded polymeric composition exhibited good color.
- Example 38 The procedures of Example 38 are repeated with the following exceptions: the polymeric composition is extruded a second time through a single strand die, passed through a water bath and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated.
- the extrudate tapes of the extruded pellets exhibited good color.
- the monomer mixture comprises 80 ' weight percent of vinylidene chloride and 20 weight percent of vinyl chloride.
- the extrudate tapes of the polymeric composition exhibited good color.
- Example 5 The procedures of Example 5 are repeated with the following exceptions: in addition to the 90 grams of tetrasodium pyrophosphate added to the polymer slur ⁇ ry, about 20 grams of maleic acid are added to the polymer slurry as well.
- the maleic acid is commercially available from the Fisher Scientific Company. The results are set forth in Table IV.
- ® PS polymer slurry of a monomer mixture, in one hundred parts of polymer, which is polymerized 10 from an initial monomer loading of 94 weight per ⁇ cent vinylidene chloride monomer and 6 weight percent of methyl acrylate monomer.
- ® TSPP tetrasodium pyrophosphate in parts per hundred parts of the polymer in the polymer slurry as added.
- ® MA maleic acid in parts per hundred parts of the polymer in the polymer slurry as added.
- ® pH pH of the aqueous phase of the polymer slurry after being charged with tetrasodium pyro ⁇ phosphate and maleic acid and being adjusted.
- the polymeric compositions can be extruded into extrudate tapes which possess excellent color.
- Example 40 The procedures of Example 40 are repeated with the following exception: the polymeric composition is ⁇ Q extruded a second time through a single strand die, passed through a water bath and then pelletized.
- the strand die had an internal diameter of 0.32 centimeter.
- Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated.
- the pellets are extruded into an extrudate tape in a continuous process for a period of about 20 minutes.
- the extrudate tape of the extruded pellets exhibited good color.
- the monomer mixture comprises 80 weight percent of vinylidene chloride and 20 weight percent of vinyl chloride.
- the extrudate tapes of the polymeric composition exhibited good color.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Cette invention concerne une composition polymère comprenant du chlorure de vinylidène et présentant une stabilité thermique améliorée. Le procédé consiste soit en l'addition préalable soit en l'addition d'une pâte polymère d'un sel d'un acide faible non alcénoïque pendant la polymérisation du chlorure de vinylidène. La composition polymère comprend un produit de réaction d'un sel d'un acide faible non alcénoïque dans une quantité efficace lui conférant une stabilité thermique améliorée. Dans un mode de réalisation préféré, cette invention consiste en outre à ajouter un sel d'un acide carboxylique à ladite pâte polymère.This invention relates to a polymer composition comprising vinylidene chloride and having improved thermal stability. The process consists either of the prior addition or of the addition of a polymer clay of a salt of a non-alkenoic weak acid during the polymerization of vinylidene chloride. The polymer composition comprises a reaction product of a salt of a weak non-alkenoic acid in an effective amount giving it improved thermal stability. In a preferred embodiment, this invention further includes adding a salt of a carboxylic acid to said polymer clay.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US24001988A | 1988-09-02 | 1988-09-02 | |
US240019 | 1988-09-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0432214A1 true EP0432214A1 (en) | 1991-06-19 |
EP0432214A4 EP0432214A4 (en) | 1991-11-06 |
Family
ID=22904762
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890910284 Withdrawn EP0432214A4 (en) | 1988-09-02 | 1989-08-31 | Extrudable vinylidene chloride polymeric composition |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0432214A4 (en) |
JP (1) | JP3177894B2 (en) |
AU (2) | AU4212889A (en) |
CA (1) | CA1340932C (en) |
ES (1) | ES2016150A6 (en) |
WO (2) | WO1990002480A2 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2487099A (en) * | 1945-06-11 | 1949-11-08 | Stabelan Chemical Company | Treatment of polymerized chlorosubstituted ethylenes |
US2532245A (en) * | 1949-08-26 | 1950-11-28 | Dow Chemical Co | Thermoplastic compositions with reduced flow viscosity |
US2753321A (en) * | 1952-05-15 | 1956-07-03 | Dow Chemical Co | White or pastel pigmented vinylidene chloride copolymer with improved color retention properties |
US2948048A (en) * | 1955-11-04 | 1960-08-09 | Dow Chemical Co | Oriented thermoplastic filament having a satiny appearance |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2564292A (en) * | 1948-07-03 | 1951-08-14 | Goodrich Co B F | Polymerization of monomeric vinyl chloride in the presence of aqueous acetic acid solution and a peroxygen type catalyst |
US2604459A (en) * | 1950-12-04 | 1952-07-22 | Dow Chemical Co | Method of stabilizing vinyl or vinylidene chloride-containing polymers |
NL133351C (en) * | 1960-12-15 | |||
GB1351461A (en) * | 1970-03-09 | 1974-05-01 | Bp Chem Int Ltd | Polymerisation process |
US3813373A (en) * | 1972-10-17 | 1974-05-28 | Sumitomo Chemical Co | Method for producing high bulk density polyvinyl chloride |
JPS55127454A (en) * | 1979-03-27 | 1980-10-02 | Asahi Chem Ind Co Ltd | Stabilization of vinylidene chloride resin |
JPS56130762A (en) * | 1980-03-17 | 1981-10-13 | Konishiroku Photo Ind Co Ltd | Manufacture of toner for electrostatic charge development |
US4418168A (en) * | 1982-03-18 | 1983-11-29 | The Dow Chemical Company | Process for imparting stability to particulate vinylidene chloride polymer resins |
US4686148A (en) * | 1985-07-15 | 1987-08-11 | W. R. Grace & Co., Cryovac Div. | Vinylidene chloride composition and film made therefrom |
US4698111A (en) * | 1985-07-15 | 1987-10-06 | W. R. Grace & Co., Cryovac Div. | Vinylidene chloride composition and film made therefrom |
-
1989
- 1989-08-28 AU AU42128/89A patent/AU4212889A/en not_active Withdrawn
- 1989-08-28 WO PCT/US1989/003708 patent/WO1990002480A2/en not_active Application Discontinuation
- 1989-08-31 JP JP50939089A patent/JP3177894B2/en not_active Expired - Fee Related
- 1989-08-31 AU AU42099/89A patent/AU637582B2/en not_active Ceased
- 1989-08-31 EP EP19890910284 patent/EP0432214A4/en not_active Withdrawn
- 1989-08-31 WO PCT/US1989/003806 patent/WO1990002764A1/en not_active Application Discontinuation
- 1989-09-01 ES ES898903006A patent/ES2016150A6/en not_active Expired - Lifetime
- 1989-09-01 CA CA 610160 patent/CA1340932C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2487099A (en) * | 1945-06-11 | 1949-11-08 | Stabelan Chemical Company | Treatment of polymerized chlorosubstituted ethylenes |
US2532245A (en) * | 1949-08-26 | 1950-11-28 | Dow Chemical Co | Thermoplastic compositions with reduced flow viscosity |
US2753321A (en) * | 1952-05-15 | 1956-07-03 | Dow Chemical Co | White or pastel pigmented vinylidene chloride copolymer with improved color retention properties |
US2948048A (en) * | 1955-11-04 | 1960-08-09 | Dow Chemical Co | Oriented thermoplastic filament having a satiny appearance |
Non-Patent Citations (1)
Title |
---|
See also references of WO9002764A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU637582B2 (en) | 1993-06-03 |
ES2016150A6 (en) | 1990-10-16 |
WO1990002480A2 (en) | 1990-03-22 |
AU4209989A (en) | 1990-04-02 |
JP3177894B2 (en) | 2001-06-18 |
WO1990002764A1 (en) | 1990-03-22 |
EP0432214A4 (en) | 1991-11-06 |
JPH04501727A (en) | 1992-03-26 |
AU4212889A (en) | 1990-04-02 |
CA1340932C (en) | 2000-03-21 |
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