IL23667A - Elastomeric compositions,process for their preparation,fibers,films and coatings made therefrom - Google Patents

Description

FOR FILMS The invention relates to elastomeric For there has been an extensive search to develop materials having the elasticity of rubber combined with the higher tensile strength and other properties needed to produce a high quality elastic More recently development of spandex materials has resulted in a variety of commercial products offering many advantages compared with natural rubber At the present there is still a need for an elastic material which will approach the high high return modulus and low set characteristics of the spandex materials while at the same time offering superior resistance to agein chlorine and organic combined with improved A number of elastic polymers based upon various acrylic and vinyl monomers are While some of the elastic polymers derived from such materials have improved solvent ageing characteristics and resistance to light compared with spandex polymers pared from such materials have not so far had completely factory properties of tensile return modulus and set The invention provides an elastomeric composition comprising from to by weight of a base elastomer containing at least weight of units of one or more acrylates or a mixture thereof with at most an equimolar amount of propylene isobutylene and from 50 to by weight of reinforcing polymer dispersed up to by weight of units of one more other unsaturated The polymer compositions of the invention may be prepared from an aqueous dispersion of a mixture of the base elastomer and of reinforcing polymer by coagulating the In one such a mixture is prepared mechanically by physical admixture of separate dispersions of the base elastomer and of the ing It is preferred however to prepare the tions by a sequential polymerization in which the monomer charge of the reinforcing polymer is emulsion polymerized an aqueous dispersion of the base If successive polymerizations may be carried out on the same if after tion of the latex mixture by sequential polymerization or by physical admixture as above a fresh portion of the monomers used in making the base elastomer may be polymerized onto the latex if by a fresh portion of the charge used for the reinforcing In addition to carrying out such successive other monomers may in addition be polymerized on the latex in a subsequent polymerization to impart specific properties Thus for example monomer or monomers containing carboxyl or other functional groups may be polymerized on to the latex to impart dyeability or other specific In the case of the sequential while the Applicants do not wish to be bound by any theories it is believed that some type of chemical bonding occurs between monomer molecules may be linked to the base elastomer by ing or layering or it may form a block copolymer A significant advantage of the sequential copolymers is that the fibers produced therefrom are usually transparent with good The base elastomer may contain units from other monomers which do not interfere with the elasticity such monomers are themselves acrylates or lates whose homopolymers display some there may be employed a minor for example 5 by weight based on the amount of acrylate of methyl acrylate or the acrylate content of the base elastomer is constituted by ethyl the base elastomer contains units of one or more unsaturated monomers to increase the glass transition temperature of the the method of determining the glass transition temperature of a see Bannerman and page 288 in Polymer Interscience Publishers 1 Monomers having this effect on the copolymer are termed mm Any he these whose are crystalline a high such as and also whose possess a high glass transition temperature Suitable hardeners include vinyl vinyl vinyl ethyl acrylic and A preferred aeryleai Many of the useful as are alas highly effeative as one embodiment of such are preparing the base tomer in amounts greatly in of that needed to aohiovo reaction is then controlled so that only portion available units are utilised for the reaaindor being retained in to a addition to as hardeners residual also dyeing n the stability of the resulting whore the of the invention are used in seating euoh nonenar the adhesion of to the the amount of hardener which nay he used in preparing the base elastomer will vary with the nature of the hardener or hardeners and the or and wit the properties desired in the genera the hardener will not sonstitute than weight of the a sufficiently glass when ethyl late is used for the rubbery no hardener may be In one preferred hardeners such as vinylidene chloride or methyl methacrylate are used one or more acidic hardeners to the desired total hardener The monomers used to copolyraeric backbone comprise from about to by weight of the copolymer although no more than about by weight of the backbone is used in the The use of excess amounts of the monomer greater than about in preparing the is in making possible more rapid in providing reactive groups in the resulting product to improve the dye receptivity and other properties of the and in acting hardeners as described the units no more than 10 by weight of the copolymeric When the constitutes more by weight of the care must be taken during curing to prevent excessive which would be detrimental to the v elasticity of the These monomers effective as may be monoethylenically unsaturated monomers copolyraerizable with the alkyl acrylates and containing one or more reactive groups by is meant that the group is capable of the methylolamide undergoing a condensation such as alcoholic carboxylic and epoxy Examples of monomers that may be used include the For alcoholic hydroxyl Hydroxyalkyl vinyl ethers or sulfides in which the hydroxyalkyl group contains 1 to hydroxyl groups and 2 to 18 carbon such as vinyl vinyl vinyl and vinyl A ester of unsaturated acid in which the hydroxy group may be in the acid or the alcoholic moiety of the ester or both such moieties may contain The unsaturated acid from which the ester is derived may 5 be monocarboxylic or Examples include and Representative esters are acrylate or methyl ethyl 10 butyl propyl acrylate or acrylate or methyl ethyl acrylate or acrylate or the corresponding hydroxyalkyl 15 or and or the corresponding itaconates mixed esters of dibasic such acids containing a single hydroxy monomethyl tho other substituents may be incorporated into the alkyl Such substituents and include secondary hydroxy halide to result in monomers such as and heptyl In all the hydroxyl of each alkyl group is at least two carbon atoms removed from the carbon atom of the adjacent radical in the Compounds of the 1 2 wherein n is or and R represent hydrogen atoms or and 1 2 with the proviso that at least one of R and R must be a hydrogen atom or a or group as above Aleo useful are compounds of the wherein R and R are as above Examples of suitable amides include and Amides and imides of dibasic acids may also be ureido Compounds of the wherein R is a hydrogen or a a hydroxyalkyl group or a is a alkylene It II Z is or R is H or a methyl 1 2 R and R are as defined and X is an oxygen or sulfur Examples of these compounds include vinyl vinyl vinyl vinyl and Among the those containing a cyclic ureido group of the follovdng formula are also ti X X being as defined above and A being a or alkylene One of the nitrogen atoms is connected to a polymerizable ethylenically unsaturated radical and the substituent on the other nitrogen may simply be or it may be or The preferred cyclic ureido compounds are those which contain the cyclic group of the Many monoethylenically unsaturated monomers cyclic ureido groups and are useful as in the Compounds of the following wherein Y represents the cyclic if group and is a hydrogen or meth lol or methoxymethyl but is preferably a hydrogen are wherein X and A are as defined and 0 II 1 5 5 Z represents or being a hydrogen atom or a and A and R are as hereinabove and 0 o wherein is a hydrogen atom or a l group and Y and are as defined and 0 0 o wherein R R Y and A are as defined Also useful are acids in which the nitrogen atom of maleamic chloromaleamic fumaramic itaconamic or citraconamic acid is substituted and directly connected a group of the X wherein X and R are as defined The amic acid and esters derived from maleamic acid are typical and have the following generic II X R 2 and R are as defined The internal cyclic imides derived from maleamic acid have the 0 II II 0 X Other such monomers have the II 0 wherein A and R are as defined hereinbefore and one R may be the same or different from the The unsaturated dicarboxylic acid monoesters of a compound of the II 1 wherein A A and R are as defined derived from or citraconic For epoxy Any monoethylenically unsaturated monomer containing a glycidyl radical may be Preferred monomers are glycidyl glycidyl and the vinyl ethers and sulfides containing a glycidyl as described by Murdoch in Patent For carboxylic acid Any unsaturated monocarboxylic or dicarboxylic acid may be Examples are methacrylic maleic fumaric itaconic citraconic and mesaconic Monoesters of the dibasic acids such and as monomethyl monobutyl itaconate may also be The such as maleic may be though generally hydrolysis occurs in the emulsion leading to formation of the free Other systems such as raethoxymethyl vinyl sulfide may be Other side chain systems analogous to the condensation systems may be unsaturated linkages pendant to the polymer chain may be used in coupling reactions by These monomers may be used alone or in Suitable combinations of reactive monomers result in a copolymer which is that the two types of reactive groups present in the copolymer react with each other to cure the Thus with one or more of the corresponding ethyl aerylate with itaconic glycidyl methacrylate with methacrylic acid hydroxypropyl are examples of such combinations of If a single monomer may be used which requires that the copolymer be treated with an additional chemical reagent to effect when an as and or methacrylamide is used as the sole the polymer must be treated with a curing agent such as another formaldehyde or a material during the forming materials such as or formaldehyde condensates may also be A single monomer which is such as the derivatives of and may also be Combinations of the same type of reactive monomer may also be methacrylamide and may be or glycidyl methacrylate with hydroxypropyl methacrylate and methacr lic or with or hydroxyethyl methacrylate with methacrylic acid and itaconic may be used in Mixed systems may also be used with a mechanical mixture of latexes for the one latex co olymer of butyl be mixed with a latex copolymer of butyl acrylatemethacrylic then the unsaturated modifier mixture polymerized on the mixed latex or a latex thereof added to the Such a system simplifies the handling of the more reactive The use of monoethylenically unsaturated compounds containing reactive groups to effect makes possible adequate without the introduction of unsaturated bonds into the copolymeric The reinforcing material may be a mixture of one or more of the following unsaturated halide vinylidene vinylidene vinylidene vinyl chloride and vinyl fluoride referred to as the as a any copolymerizable unsaturated monomer termed the While the nature of the modifier is not its concentration is the critical range of concentration varies with the nature of the modifier In the modifier constitutes to by weight of the combined unsaturated mixture and preferably from 1 to by Where an acidic monomer acrylic or methacrylic is used as the sole it is preferred to use from about to about modifier by polymer of the unsaturated halide serves as a reinforcing filler to improve the properties of the aer late base although the precise mechanism whereby it does this is not studies of fibers made from the composition of the invention indicate when vinylidene chloride is the unsaturated there are present particles to be the copolymer of vinylidene chloride polymerized on the which are though they are tiny as to be seen only under an electron Increasing the amount of modifier correspondingly decreases the degree of crystallinity of the After the vinylidene chloride particles shown by are both crystalline and On immersing a cured fiber in a swelling the swelling is approximately whereas the same fiber without shows isotropic shaped products produced according to the invention are believed to have an oriented backbone reinforced with macrocrystalline particles of a reinforcing which particles are both crystalline and The Applicants do not wish to be bound however by these theoretical The significance of orientation in the crystallites is not though it is believed that orientation is not necessary for the effective reinforcing action of the since reinforcing has been observed in materials which are not cured while orientation has been observed only after It has also been noted that too low a modifier content gives a product having undesirable physical on the other too high a modifier content also usually results in an undesirable if too much modifier is the physical properties the tensile of the resulting copolymer may be quickly and strongly On the other if no modifier is the resulting copolymer has a high residual lower tensile is hard to form and gives boardy In the the monomer a monomer is considered if the homopolymer duced from it is the more of that monomer can be used as the modifier without adversely affecting the tensile methyl methacrylate does not appear to lower the tensile strength at any excessive amounts of such hard monomers result in boardy Either one or a mixture of monomers may be used for the It is preferred to use at least one unsaturated carboxylic acid as part of the modifier Suitable monomers which serve as modiiers of vinylidene chloride for vinyl acrylic acid methacrylic acid maleic acid Vinyl acetate and other vinyl and A more complete list of suitable monomers copolymerizable with vinylidene chloride is given in Handbuch der Edwards the items indented under A similar list of monomers copolymerizable with vinyl chloride is given by at pages 735 to Vinyl fluoride and vinylidene fluoride are more difficult to In more highly polar modifiers such as acrylonitrile are preferred for use with the fluoride In the preferred embodiment wherein sequential polymerization of the monomer mixtures is the order of polymerization is critical in developing copolymers havi g the 1 desired In preparing the elastomeric sequential the monomers for the are first emulsion preferably using a free radical The art of emulsion polymerization is well known and the conditions of polymerization used herein are not These aqueous dispersions may be made by using one or more emulsifiers of cationic or nonionic Mixtures of two or more regardless of may be used except that it is generally undesirable to mix a cationic emulsifier with an anionic one in any appreciable amounts since they tend to neutralize each The amount of emulsifier may range from to by weight or sometimes even based on the weight of the total monomer When using a persulf te type of the use of emulsifier is often unnecessary and or the use of only a small less than about of may sometimes be desirable for economic The free radical catalyst may be either or The process of the invention contemplates the use of any of the free radical catalysts known the art as effective to catalyze the polymerization of the monomers used Particularly preferred are the peroxy catalysts and the Typical catalysts which may be used are peroxides such as hydrogen dibutyl acetyl benzoyl alkyl such as cumene and such as alkali metal and ammonium and such as the alkali metal and ammonium Other catalysts such as and j can be 17 The ef used eaa he depending on the and the method from to by teased of the If catalyst emitted and radiatloa used to promote the eatalyet with a A he weed for either stages the he nay ell he added initially er say he added as One type of eataXyst say he the ef the haee and a used for the of the charge used the the game catalyst he used fer as temperature ef eritieal he varied almost at Where a temperature a point as ethylene he added te The nay he eead at pressure er with the ef high the eheiee ef the particularly for the stage ef the will the eheiee ef the pressure te he Optimum times will vary alia with the aature the eatalyet the with the temperature aad and with the degree ef to it is It that the of residual This effected fer ey reaction Af ef the twee earrylag the te am high ef the aer e distilling it a ef of these ef the ef the ease for the forcing egether with te the ey the the Where the ef after the first is he all er pert ef the modifier the In this ease the d met he upon ef ef the ef the halide as the results in deereaeed ef the ef the as stated it is shaped ef the invention te prepare the fire and te aeriae the With the ef the ef residual the same general and are te the ef latexes the ease and ef the ef the reinforcing being latex the base aa a mixture siay be eepsrately prepared aa a and one important of the As the amount of base the becomes and the the base the haa lever tensile strength and It is preferred that the base elastomer up 60 to weight of the total preferred rubbery the la and the preferred is yinylidene prevent any unwanted ef the the the second stage should preferably not be greater than about while to obtain proper spinning with the the pH of the latex should preferably mot be lower than about After preparation of the the latter may be and Spinning and coagulation stay he out in a process of ning is described n Patents and 511 the of which incorporated herein by By reason of its rapid penetration and ity thereby eliminating any of undesirable is pre to use acid for the For this the bath should preferably contain from 9 hydrochloric by If A as he the la it spinning of the is tharete either or la the 20 While it is preferred to spin the emulsions into a coagulating bath they may also be dry spun as described in British Patent Specification To prevent thermal it is preferred to use lower temperatures than normal for dry spinning and to extrude the fibers onto a heated adhesive such as a steel belt coated with The elastomeric materials of the invention may need no fusion nor nor heating step to promote fusion of the particles in a separate fusion step as is conventional in spinning latexes of synthetic polymeric a latex of the elastomeric materials of the invention is similar to natural rubber latex in this The spinning and agulating bath may be maintained at a temperature of from to and preferably from to At higher the uncured fiber or film handle less while at lower temperatures coagulation may proceed very It is most for general ease of to maintain the spinning and coagulating bath at normal room On leaving the spinning and coagulating the fiber or film may be The washing need not be carried out to such a degree as to remove all traces of residual as such traces serve to catalyze many of the condensation reactions used in the polymer Where the polymer contains free carboxylic acid units in the polymer chain as by inclusion in the hardener or of the r rubbery backbone in the modified for the unsaturated such acidic units occurring in the polymer chain serve as a catalyst to promote the condensation it is not essential in the invention to retain trace amounts of the acid from the coagulating Curing may be accomplished by heating the fiber or film in the presence of a catalyst nature of the catalyst being determined by the though generally acid catalysts are at a temperature of from about to for from about hours to a few the longer time corresponding to the lower temperature and the shorter time of cure corresponding to the upper The precise time and temperature will depend on the properties desired in the final the nature of the monomers used in preparing the elastomeric the necessity of avoiding the evolution of steam at a rate which would create bubbles in the on the number and type of monomer units in the and on the concentration and nature of the catalysts provided for the curing In a preferred embodiment of the the fiber or film is cured while held in the stretched Where the unsaturated halide is vinylidene chloride and the elastomeric material is prepared by mechanically blending latexes of the base composition and of the reinforcing the curing is preferably carried out at temperatures above in order to develop the desired The highly crystalline nature of the polymer produced from vinylidene chloride appears to be a significant factor in this as the mum curing temperature needed to develop the desired properties appears to vary inversely with the amount of modifier in the vinylidene chloride The use of unsaturated halides giving less crystalline such as vinyl in mechanical blends does not show this property optimum ties only at high curing nor do sequential even when the unsaturated halide is vinylidene The curing may be carried out in the fiber or film may be partially cured to increase the strength of the fiber or film to permit handling of the material during the stretching and final cure The partial curing appears important to obtain the optimum results from a final though this need not be carried out as a separate step but may be the initial part of a continuous cure achieves a certain minimum stabilization of orientation in the backbone copolymer chains which assists the action of the unsaturated copolymer in improving tensile strength and As the conditions of curing tend to cause it is evident that the best properties for a particular use from a given system require careful control of the stretching and final Adequate partial curing to accomplish this may be achieved in from minutes to minute or at a temperature of from to the longer the time the lower the temperature while the shorter the time the higher the temperature Towards the upper temperature care must be taken that the temperature and duration of the heating step are not such as to cause of the fiber at room temperature achieves adequate partial though longer are the partial curing is accomplished in a few seconds to five minutes at a temperature of about to The fiber or may then be stretched from 100 to or higher while held in the stretched the cure may be Jet stretching by pullin the fiber away from the spinning appears to change only denier and may be used to stretch the fiber any desired more than to obtain the desired the final cure may be carried out in about hours to seconds at to temperatures specified in this discussion of curing refer to the temperature of the medium surrounding which temperature is not necessarily the temperature of the Where the polymer is to be processed in fiber the final operation may be carried out by winding the fiber on a bobbin under a sufficient tension to impart the desired degree of stretch and the curing may be carried out on the As will be obvious to those skilled in the a great variety of stretching operations may be the wash bath may be maintained at the temperature necessary to e fect cure and the stretching carried out in the wash The fibers or films may also be stretched directly while drawn from the coagulating bath onto the drying Or precuring may be effected in the wash bath and the stretch accomplished while drawn onto the drying Curing may take place on the drying rolls or while being drawn through a steam The stretching operation a or The significantly increases the tensile strength of the resulting products without adversely affecting the other desirable properties ef the She latexes produced by the invention be spun through a to produce a diameter be produced ay spinning abont 10 to 100 acre separate filaments in a coalescing the separate filaments to form a single large denier filaments from about 10 to denier say be as The latex nay also be span through a je to a jsaltifilaaent She fiber be chopped late it be blended with staple fibers natural and and fibers ef the are useful in and knitting in producing tricot knits and and in producing covered such as those cribed Patents or fibers may also be used in producing a plied fiber described in Patent Application and in Application ke wherein chloride is the unsaturated halide in reinforcing are particularly are transparent with good the conditions ef are not and they have physical While the compositions of the generally offer ultraviolet dry cleanability and with the ation and tensile strengtk useful elastic the ferred compositions have a good combination of elongation and tensile strength without sacrifice These processes fo covering or plying an elastic yam with a fiber restrict the maximum elongation of the composite Most commercial applications of elastic ya s require only low or medium elongation of the bathing suite are customarily made of yam having an elongation in the range of 120 to The knitting trade generally requires yarns having an elongation from about 180 to while the weaving trade generally requires yarns having an elongation of only from about 100 to The hosiery trade requires ya with an elongation of from 300 to The elastic fibers of the invention are suitable for use in most of these commercial applications of elastic ya compositions comprising reniforcing While the have described principally in fabricating fibers and they have a variety of other useful they may be used together with an or inert or complementary diluent in protective coatings for or coatings for ical binders for nonwoven and in other applications rubber latexes have been found The good tensile strength and elasticity of the products of the invention coupled with their high resistance to chlorine and peroxide ultraviolet render them particularly suitable for such Tensile strengths in the Examples of all fiber samples is a registered trade are determined on an are measured in pounds per square as used in the examples means elongation at It is measured by placing bench marks two meters apart on a uniformly cut sample and stretching it until it The elongation is then the distance between the marks at failure minus divided by 2 and multiplied by is the unrecovered stretch after an elastomer is stretched and allowed to relax It is determined by placing bench marks on the sample two centimeters apart and stretching it 300 and holding for ten Where the sample is stretched more or less than the amount of stretch is specifically The sample is released and measured after ten Set is recorded as the length of the sample at the minus divided by 2 and aultiplied by is the stress on the return cycle after a strain larger than that at the measured point has been In determining return the sample is placed in the Instron elongated to a point below the breaking the crosshead returned to the rest position and cycled in this manner for six On the sixth the return modulus is corded in pounds per square unless otherwise To a fiber or film in the Examples the fiber or is first partially cured and then held in a stretched condition during completion of the In the th is the amount of stretch a per cent of the length of the partially cured maintained during completion of the means the ultimate tensile strength of the fiber in grams per The invention will now be more particularly described in the following Examples in which all parts and percentages are by weight unless the contrary is Example 1 A solution of 8 parts of the sodium salt of an aryl polyether sulfonate and parts of ferrous sulphate in 120 parts of deionized water is A mixture of parts of ethyl parts of acrylamide and parts of is added with stirring to the solution which is maintained under a nitrogen The resulting mixture is o cooled to 20 and maintained at this temperature by a cooling A catalyst charge consisting of parts of ammonium parts of sodium metabisulfite and parts of peroxide is then After a short the temperature of the mixture rises to It is then allowed to fall to under the influence of the cooling At this 80 parts of 39 parts of vinylidene chloride and 1 part of methyl cr late are added and the mixture is stirred for 15 minutes and a catalyst charge consisting of parts of ammonium parts of sodium metabisulfite and parts of peroxide is After a short the temperature rises to and then falls A copolymer emulsion in a yield of of theory the An apparatus for spinning of the copolymer is shown in the accompanying The emulsion from a supply 1 is spun through a 12 mil internal diameter glase capillary 2 immersed in a bath 3 of HCl and the fiber 12 is carried out of the bath over a constant speed roll The fiber is washed by passage under a set of godets immersed in a fresh water bath 6 and is then passed onto a belt 7 through a zone 8 heated to The godets and belt are operated at the same linear rate as the The total residue time of the fiber on the belt is The fiber is taken from the passed round a godet 9 wound on a bobbin 10 by a collector samples are collected different the collector being run at different linear speeds relative to the belt for each The speed differential stretches the fiber When the desired amount of fiber has been the bobbin is removed from the fiber end is taped to the bobbin and the bobbin is placed for hour in a forced draught oven held at to complete the In another test the thread is passed around heated thread advancing rolle 11 and cured thereon prior to collection on the The amount of stretch applied to each fiber during curing and the properties of the fibers produced are shown in Table T ABL E I Example 2 A solution of parts of sodium lauryl sulfate and 0 parts of deionized water is A mixture of parts butyl parts of acr parts of acrylamide and parts of methylolmethacrylamide is added with The mixture is stirred for minutes while being purged with nitrogen and cooled to A solution of parts of ammonium persulfate in 2 parts of water and then a solution of parts of sodium formaldehyde sulfoxylate in 2 parts of water are Stirring is continued throughout the ensuing In a short the temperature climbs to where the temperature rise is contained by a cooling When the temperature has fallen to a solution of parts of ammonium persulfate in 1 part of water is added followed by addition of parts of After four a mixture of parts of vinylidene parts of ethyl acrylate and 60 parts of water is After a further 15 parts of ammonium persulfate in 2 parts of parts of sodium formaldehyde sulfox late in 3 parts of water and parts of hydroperoxide are The temperature quickly rises to and after one hour the is The total yield of emulsified copolymer is The copolymer emulsion is spun as in Example except that the coagulating bath contains hydrochloric The curing the preliminary cure on the is varied as well as the amount of stretch applied during as shown in Table A B L E II Example 3 The procedure of Example 2 is followed in preparing a polymer from the following monomers in the proportions parts parts acrylic 8 parts vinylidene and parts glycidyl methacrylate as the backbone onto which is polymerized 18 parts vinylidene chloride and 2 parts methyl The resulting latex is sprayed onto a cotton pile fabric to provide an elastic backing and the film cured by heating at for 10 The film has a thickness of about 5 mils and has good solvent resistance and ageing The latex is also useful as a binder for Example The procedure of Example 2 is followed in preparing a polymer from the following monomers in the proportions 57 parts methacrylic acid and parts of a mixture of pentenamide and as the backbone onto which is polymerized 39 parts vinylidene parts acrylic acid and The resulting latex is spun as in Example 1 and the resulting thread cured without any applied The fiber produced has a tensile strength of about 2000 an elongation of a set of after an elongation of and a return modulus of for 85 for and 200 for Example 5 The procedure of Example 2 is followed in preparing a polymer from the following monomers in the proportions parts 7 parts methyl methacrylate parts acr lamide and 2 parts as the backbone onto which is polymerized parts vinylidene chloride and parts ethyl The resulting emulsion is spun as in Example 1 except that the coagulating bath is a aqueous hydrochloric acid solution saturated with sodium The amount of stretch applied to each fiber during curing and the properties of the fibers produced are shown in Table B L HI Example 6 The procedure of Example 2 is followed in preparing a polymer from the following monomers in the proportions 60 parts parts methacrylamide and parts as the backbone onto which is polymerized parts vinylidene chloride and parts The latex so produced is sprayed onto Bonderite 100 is a registered trade mark panels and cured as in Example The resulting cured film has good solvent resistance and weathering The film is tough and possesses good abrasion The can also be used as a prime coat for hard surface coatings such as methyl Example 7 A solution of 5 parts of the sodium salt of a branched alkyl sulfate and 5 parts of the sodium salt of an alkyl aryl polyother sulfonate in parts of water is A mixture of parts 7 parts of acrylonitrile and parts of methacrylamide is added with The resulting mixture is cooled to by of a constant temperature bath and this cooling and stirring under a nitrogen atmosphere are naintained throughout the After thorough parts of ammonium persulfate in 1 part of water and parts of sodium formaldehyde sulfoxylate in parts of water are After a short the temperature climbs to and then falls to at which stage an additional parts of persulfate and parts of sodium formaldehyde sulfoxylate are The as determined by solids is more than after at which time a mixture of 60 parts parts vinylidene chloride and parts ethyl acrylate is After 15 parts of ammonium persulfate in 1 part of parts of sodium formaldehyde sulfoxylate in 3 parts of and parts of hydroperoxide are The temperature rises to after a short tiine and after 1 hour the mixture is filtered through cheesecloth and A copolymer emulsion results and the conversion as determined by a solids determination is to of To this emulsion is added parts of formaldehyde per 100 parts of polymer solids and the emulsion is allowed to mature for two The emulsion after the maturing period is spun as in Example The collector is run at a linear rate 3 times that of the belt so feat a stretch of is applied to the The bobbin is removed from the the fiber end is taped to the bobbin and the bobbin is placed for one hour in a forced draught oven held at to complete the The fiber has the following Tenacity elongation and return modulus at from of Examples The procedure of Example 7 repeated with the following Example The contents of the bath are changed to HC1 saturated with sodium Example The contents of the spin bath are changed to saturated Example formaldehyde is omitted from the emulsion and the spin bath composition is concentrated HC1 with formaldehyde An elastomeric fiber possessing good modulus and tensile strength with excellent resistance to chlorine bleaches and ultraviolet light is obtained in each The properties of the fiber can be controlled by the the time and temperatures of precure and the amount of stretch applied before the final Examples 11 and 12 For Example 11 the procedure of Example 2 is followed in preparing a polymer from the following monomers in the proportions parts butyl parts parts methacrylaraide and parts elastomer methacrylaraide as the on which is polymerized 29 parts vinylidene parts acrylate and parts acrylic For Example the procedure of Example 1 is followed in preparing a polymer from the following monomers in the portions parts vinylidene parts acrylic parts methacrylamide and parts base elastomer amide as the on which is polymerized parts vinylidene parts butyl acrylate and parts acrylic The latexes so produced are spun as in Example 1 and one batch cured while not under tension and a second batch The density of the fiber of Example 11 ia and that of Example 12 is The properties of the four fibers so produced are compared with the properties of a commercial natural rubber a commercial spandex and three different acrylic rubbers in TABLE IV a Available under the trademark Data from a commercial bulletin on Thiacril 44 compounded with 40 per hundred rubber FEF carbon 1 phr stearic phr ethylenetetramine phr benzothiazyl disulfide cured minutes at and tempered 24 hours b A butyl copolymer loaded 40 phr of cast from Data from Patent Specification of ot c Data for a butyl methacrylamide polymer compounded with 4o phr and a two molar excess of formaldehyde and cured one hour at Data from Nelson and Br 1053 1 The fiber of Example 12 and the commercial spandex fiber used as the control are then UV Stability On exposure to a carbon arc the fiber of Example 12 loses tenacity at a linear rate according to the duration of exposure while the spandex fiber at first is but little but then weakens more rapidly so after some the spandex fiber has less tenacity than the fiber of Example Both fibers show negligible Hypochlorite Bleach Both fibers are then tested for the effect of commercial sodium hypochlorite The manufacturer of this product recommends a concentration of to by weight for normal domestic The spandex fiber turns bright orange while the fiber of Example 12 shows no The per cent Changes of tenacity and elongation as a per cent of the original value are shown in TABLE A B V Sample did not survive the Chlorite and peroxide bleaches The fibers are then tested for the effect of immersion in a sodium chlorite solution for one hour at and for the effect of immersion in a hydrogen peroxide solution for one hour at The change in elongation and tenacity as a percentage of the original is shown in TABLE A B L E VI Exposure to bleach and the ultraviolet The fibers are then immersed for 6 hours at in a solution of sodium dried and exposed for 16 hours to ultraviolet The spandex fiber darkens as a result of this while the fiber of Example 12 shows negligible The per cent loss in tenacity of the fibers is shown in the following TABLE T A B L E VII Fiber Number of Cycles Loss in Tenacity Example 12 1 Example 12 2 30 Spandex 1 53 Dr cleanability The fibers are immersed in perchloroethylene for 30 minutes at The change in tenacity and elongation as a percentage of the original value and the amount of swelling are in TABLE VIII Carbonization The fibers are tested for resistance to the treatments used to carbonize In this the fibers are first immersed for 10 minutes in a aqueous solution of sulphuric acid at 7k0 The fibers are then dried at for 15 minutes and baked at for 15 The properties of the fibers so treated are shown in TABLE ABLE EC Fiber extended to of its breaking extension and then returned to of its breaking The fiber of Example 12 shows no change in color or hand as a result of this while the spandex fiber shows a slight browning and feels almost Example 13 The following materials are charged into a reactor maintained at Deicaized water 160 parts Ethoxylated phenol parts acrylate parts Acr lonitrile parts Methacrylaraide parts parts The system is purged for twenty minutes with Then a catalyst system consisting of one part of a aqueous solution of ammonium persulfate and one part of a aqueous solution of sodium formaldehyde sulfoxylate is An exothermic reaction occurs within ten After the temperature regains parts of deionized 29 parts of vinylidene parts acrylate and parts of acrylic acid are added and the mixture is stirred for 15 Then parts parts of ammonium persulfate solution and 2 parts of sodium formaldehyde sulfoxylate are A exothermic reaction occurs and a yield of polymer of of theory is obtained in The emulsion is formed into a fiber by extrusion through a 10 mil internal diameter glass capillary immersed under the surface of a bath consisting of a saturated sodium chloride solution held at The fiber so formed is removed from the washed with water and cured for one hour at The fiber so produced has an elongation of tensile strength of 1200 and recovers from stretching with less than permanent Example i A fiber was prepared as in Example 11 except that a acid phthalate buffer was used to give the reaction mixture in second stage of the polymerization a pH of about The fiber was stretched during curing as in Example The resulting fiber had an elongation of a tenacity of about a return modulus of and The set was Examples 15 16 For Example 1 the procedure of Example 2 is followed in preparing a polymer from the following monomers in the proportions parts parts and parts base elastomer methylolmethacrylamide as the on which is polymerized 29 parts vinylidene acrylate and parts acrylic For Example the procedure of Example 15 is followed in preparing a polymer of the same monomers except that the vinylidene acrylate and acrylic acid are polymerized base separately and the latex is then mechanically mixed with the latex in the same proportions as in preparing the sequential latexes produced by this means are spun as in Example 1 and cured for 60 minutes at while stretched The properties of the fibers so produced are set forth in TABLE A B E X Examples 18 For these the procedure of Example 16 is base elastomer followed in preparing separate latexes of the and polymer reinforcing which are then mechanically The latex base elastomer of the backbone copolymer is using the same monomers and process as in Example polymer In Example the reinforcing is a commercial latex of a copolymer of parts chloride and 10 parts diethyl maleate prepared with an anionic emulsifier and available 5 under the trademark polymer In Example the latex of the reinforcing material is prepared as Into a reactor are charged grams of water containing grams of sodium lauryl 0 sulfate and gram of ferrous This is frozen and 50 grams of vinyl chloride monomer condensed in the The reactor is purged with nitrogen and It is then placed in a bath maintained at and 5 When the contents of the reactor have all a charge consisting of gram of potassium persulfate in 5 of water and gram of sodium bisulfite in 5 of water is After 5 the reactor is vented and the latex The conversion based on solids is about The solids content of the latex is In each parts by weight of solids of the polymer reinforcing are added to 70 parts by weight of the solids base elastomer of the and the mixture The latexes produced by this means are spun as in Example upon emergence from the wash the fibers are cured for fifteen seconds at then stretched and cured at the temperature and time shown in TABLE XI folloved by hour at C and 16 hours at room temperature before being released from The properties of the fibers so produced under the different curing conditions are set forth in TABLE XI wherein is tenacity and is ABLE XI Examples base elastomer For these the latex of copolymer is using the monomers and process of Example To 70 base elastomer parts of the backbone are then added 30 parts of a latex prepared using the polymerization procedure of Example 16 but with the following monomers in the proportions In Example the monomers are 99 parts vinylidene chloride and 1 part ethyl In Example the monomers are 97 parts vinylidene chloride and 3 parts ethyl Λ Example 21 the monomers are parts vinylidene chloride and 6 parts ethyl base elastomer The parts of the and 30 parts of the inforcing copolymer are then mechanically mixed and the latexes produced by this means are spun and cured as in Examples and The properties of the fibers under the different curing conditions are set forth in TABLE XII wherein is tenacity and is ABLE XII As stated the importance of crystallinity in the reinforcing material is not In the case of the highly crystalline reinforcing such as those employing vinylidene excessive can be reduced the crystallinity by the inclusion of a small at least about by of a copolymerizable monomer termed a as can be seen polymers in these in the case of less crystalline reinforcing polymers of such inyl the unmodified homopolymers may be The term used in some of the denotes the elongation at which stress becomes zero on the sixth return cycle in the return modulus insufficientOCRQuality

Claims (1)

1. 44 What claim An composition comprising from 50 to by weight of a base elastomer containing at least by weight of units of one or more acrylatea or a mixture thereof with at most an equimolar amount of propylene isobutylene and from 50 to by weight of reinforcing polymer dispersed through the base the reinforcing mer containing units of one or more of the following saturated halide vinylidene vinylidene vinylidene vinyl chloride and vinyl and if required to reduce the of the reinforcing up to by weight of units of one or more other unsaturated A composition according to Claim wherein the base elastomer contains aerylate units and up to y by weight of units of one or more saturated monomers effective to increase the glass transition temperature of the base A composition according to Claim 1 or wherein the reinforcing polymer a containing from to by weight of units of vinylidene A composition according to any one of the preceding wherein the reinforcing polymer contains to by weight of units of one or more of said other ethylenioally unsaturated A composition according to Claim 1 or 2 wherein the units of unsaturated halide monomer are units of vinyl A composition according to any one of the preceding wherein the base elastomer is derived from a monomer mixture containining to by weight of one or store monoethylenically unsaturated monomers capable of linking the base elastomer by a condensation A composition according to Claim wherein the base elastomer contains at least by weight of units of ethyl acrylate and up to by weight of units unsaturated monomer for increasing the glass transition temperature and wherein the reinforcing polymer contains 88 to by weight of unite of vinylidene A composition according to Claim wherein the base elastomer contains units of A composition according to Claim 7 or wherein the base elastomer is through amido A composition according to any one of Claims wherein the base elastomer present in an amount of based on total polymer 46 A polymer composition to form a tion according to Claim 1 comprising from 50 to based on total polymer of base elastomer containing from 75 to by weight of units of one or more or a mixture thereof with at most an amount of propylene iaobutylenej and to by weight of units of one or more monomers to link the base elastomer by a condensation and from 50 to based on total polymer of reinforcing polymer containings units of one or more of the following unsaturated vinylidene vinylidene vinylidene vinyl and vinyl if required reduce crystallinity of the reinforcing up to by weight of units of one or more unsaturated monomers copolymerizable with the unsaturated halide the base elastomer and reinforcing polymer being prezent in the composition either in the form of a physical mixture of the two or in the form of particles of base elastomer sequentiall polymerized said reinforcing A composition according to Claim wherein the base elastomer contains up to by weight of units of one or more unsaturated monomers effective to increase the glass transition temperature of the base A composition according to Claim 11 or 12 in which 47 A composition according to Claim 12 or wherein the units of unsaturated monomer are vinylidene chloride A composition according to any of Claims which contains 60 to 70 based on the total polymer of base said baae elastomer containing up to by weight of unite of unsaturated monomer for increasing the glass transition temperature and units of butyl acrylate ethyl A composition according to any of Claims which contains from 40 based on total polymer of forcing said reinforcing polymer containing vinylidene chloride and from to by weight of units of one or more other unsaturated monomers merizable with vinylidene A composition according to any of the preceding wherein the base elastomer as units effective to increase its glass transition units of one or more of the followin vinylidene vinyl acr vinyl methyl vinyl toluene and ethyl A composition according to any of Claims in the units in the base elastomer contain at least one of the following reactive alcoholic ureide and epoxy A composition according to any of Claims in the base elastomer contains at least by weight of units of ethyl 48 A composition according to Claim wherein the base elastomer also contains unite of acrylonitrile A composition according to Claim 19 or wherein the base elastomer contains amide or amide A composition according to any of Claims wherein the reinforcing polymer contains 88 of units of dene A composition according to Claim substantially as described in any of the foregoing A fibre or film composed essentially of a composition according to any one of Claims 1 to A fibre or film composed essentially of a composition according to any one of Claims A process for the preparation of a shaped article which molding or casting a composition according to any one of Claims A process according to Claim 26 including a curing step to base elastome A process of preparing a composition according to Claim 11 which comprises forming a latex of the base elastomer by emulsion polymerizing an appropriate charge and then sequentially the base elastomer a monomer charge giving rise to the reinforcing process according to 2Θ as applied to the preparation of a composition according to any one of Claims 12 to 49 A process of preparing a or fibre which comprises extruding into a coagulating bath a composition according to any one of Claims in latex A process according to Claim wherein the coagulated shaped structure is stretched and then A process according to Claim wherein the coagulated shaped structure is partially stretched and then curing completed while the shaped structure is held in the stretched process according to Claim wherein a continuous rate of is applied to the coagulated shaped structure during A process according to any of Claims wherein the monomer effective to the base elastomer contains one or more amide groups and the coagulating bath is hydrochloric acid having formaldehyde dissolved A polymeric product when by a process according any one of Claims For the Applicants insufficientOCRQuality