US3422050A - Copolymers of conjugated diolefins and partial esters of unsaturated polybasic acids - Google Patents

Copolymers of conjugated diolefins and partial esters of unsaturated polybasic acids Download PDF

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US3422050A
US3422050A US384536A US3422050DA US3422050A US 3422050 A US3422050 A US 3422050A US 384536 A US384536 A US 384536A US 3422050D A US3422050D A US 3422050DA US 3422050 A US3422050 A US 3422050A
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Robert R Brown
George F Schmidt
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Standard Brands Chemical Industries Inc
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/942—Polymer derived from nitrile, conjugated diene and aromatic co-monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/911—Emulsifying agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2738—Coating or impregnation intended to function as an adhesive to solid surfaces subsequently associated therewith

Definitions

  • This invention relates to latex compositions of certain conjugated diolefinic copolymers exhibiting enhanced fiber bonding properties and improved unified non-woven fibrous articles such as fiborus webs or mats internally bonded, with said conjugated diolefinic copolymers.
  • the invention relates to latices of copolymers comprising conjugated diolefins and partial esters of unsaturated polybasic acids, and to flexible non-woven fibrous sheeting, such as paper, non-woven fabrics, and the like, containing these copolymers.
  • this invention relates to impregnated paper backing sheets suitable for fabrication into pressuresensitive adhesive tapes and the tapes so produced, such sheets being characterized by unexpected development of unusually high wet strength and a high resistance to delamination of the paper backing in combination with other desirable properties.
  • nonwoven fibrous materials refers to a mat, web or sheet of fibers which has been laid down by mechanical, pneumatic, electrical, or vacuum means, or otherwise deposited.
  • the typically open, highly porous, and unbonded structure of webs or mats made of such fibrous materials inherently has little or no resistance to delamination, splitting and tearing.
  • the internal bond strength be highly developed in order to avoid splitting or delamination of the fiber structure when subjected to the stresses of normal use.
  • the internal bond strength should also be retained after storage under normal conditions.
  • the ability of such impregnated or saturated fibrous masses to tolerate pigmentation with retention of high internal bond strength; to exhibit good elongation characteristics, resistance to oils and solvents, and non-discoloration are often necessary or desirable properties for the many end-product forms of such fibrous materials.
  • non-woven fibrous articles having highly improved internal bond strength are obtained by unifying the fibrous materials with latices comprising copolymers of conjugated diolefins with certain partial esters of unsaturated polybasic acids. It has also been found that utilization of the latices of this invention provide an impregnant composition for saturating fibrous materials wherein resulting product has the characteristics of improved tensile strength (wet and dry), elongation, edge tear, as well as the above-mentioned resistance to delamination.
  • the copolymers particularly suitable for use in the unifying compositions of this invention are prepared from monomeric materials at least predominantly comprising one or more aliphatic conjugated dienes and, preferably, one or more ethylenically unsaturated monomers copolymerizable with the diene.
  • ethylenically unasturated monomers includes copolymerizable monoolefinic monomers and is to be construed as excluding conjugated dienes, but may include other polyolefinic monomers.
  • the monomeric aliphatic conjugated dienes suitable for use include the butadiene-l,3 hydrocarbons such as butadiene-l,3 itself; Z-methyl butadien'e-1,3 (isoprene); 2,3-dimethyl butadiene-l,3; piperylene; 2-neopentyl butadiene-1,3; and other hydrocarbon homologs of butadiene-l,3.
  • the substituted dienes such as 2- chloro butadiene-l,3; Z-cyano butadiene-1,3; the straight chain conjugated pentadienes; the straight chain and branch chain conjugated hexadienes, and the like, are found suitable.
  • dienes containing more than 10 carbon atoms polymerize very slowly, if at all, in the present polymerization systems; consequently, it is preferred to employ a diene having ten carbon atoms or less. Dienes having from 4 to 6 carbon atoms have particularly advantageous reaction rates and polymerization characteristics and, therefore, are preferred.
  • the butadiene-1,3 hydrocarbons, and butadiene-1,3, in particular, are preferred.
  • the monomer mixture to be polymerized may also contain one or more interpolymerizable monoolefinic monomeric materials.
  • the monoolefinic monomer, which together with the aliphatic conjugated diene constitutes a major portion of the monomeric material for directly preparing the copolymers useful in the latices of this invention, may be any such monomer which is copolymerizable with the diene.
  • Such monoolefinic monomers are well known in the art and are indicated by typical monomers set forth below.
  • the monoolefinic monomers copolymerizable with the dienes in aqueous dispersion and characterized by the presence of such groups are the aliphatic unsaturated nitriles, such as the lower molecular weight nitriles, acrylonitrile, alphachloro acrylonitrile, methacrylonitrile, ethacrylonitrile; the low molecular
  • copolymerizable monoolefinic monomers selected from the group consisting of nitriles, styrenes, and lower molecular weight alcohol esters of acrylic and alpha-substituted acrylic acids.
  • the partial esters of unsaturated polybasic acids employed in this invention may be prepared from unsaturated acids having two or more carboxylic groups or the anhydrides thereof.
  • the partial esters employed are the half esters or monoesters prepared from unsaturated acids containing two carboxylic groups.
  • the monoesters of dibasic acids which are suitably employed have the structural formula:
  • X represents the acid residue of a dibasic acid having from 4 to 8 carbon atoms and preferably from 4 to carbon atoms and R represents an alkyl radical having from 1 to 2 and most preferably 1 carbon atom, and wherein the R group may be substituted on either of the carboxylic groups of the acid residue.
  • acids suitable for use include fumaric, maleic, glutaconic, citraconic, itaconic, mesaconic, aconitic, and the like, with fumaric, maleic, and itaconic acids being preferred.
  • unsaturated polybasic acid includes in addition to the acids exemplified above, dimers, trimers and like condensation products of unsaturated monocarboxylic acids having two or more carboxyl groups, e.g., dimers and trimers of methacrylic acid.
  • the R group is advantageously an alkyl radical of two carbon atoms and preferably one carbon atom, inasmuch as partial esters containing a greater number of carbon atoms in the alcohol portion thereof do not exhibit the enhanced fiber bonding properties of the partial esters of this invention.
  • the monomethyl ester of itaconic acid is preferred. This monoester is prepared simply by refluxing methanol with itaconic acid in the presence of small amounts of an esterification catalyst, such as sulfuric acid, paratoluene sulfonic acid, cation exchange resins containing sulfonic acid groups, and the like.
  • the unexpectedly high internal bond strength is advantageously obtainable with a relatively small content of partial ester of an unsaturated polybasic acid in the diene copolymer and effective amounts may be as low as about 0.5 percent by weight based on the total monomer charge.
  • the partial ester content in the copolymer may be much higher, if desired.
  • suitable polymers have been prepared containing as high as about 20 percent by weight of such partial ester content based on the total monomer charge. For many applications, however, little is to be gained above about 10 percent by weight of partial ester based on the total monomer charge.
  • copolymer latices herein described in admixture with other copolymers, such as diene-nitrite and diene-styrene copolymers and other copolymers containing carboxyl groups derived from monocarboxylic acids such as diene-nitrile-methacrylic acid, diene-styrenemethacrylic acid copolymers.
  • a strength imparting monomeric material such as acrylic and substituted acrylic acid and other copolymerizable ethylenieally unsaturated monocarboxylic acids, such as crotonic acid, alpha-chlorocrotonic acid, hydrosorbic acid, cinnamic acid, m-chlorocinnamic acid, p-chlorocinnamic acid, acrylic acid, alphachloroacrylic acid, methacrylic acid, ethacrylic acid, vinyl thiophenic acid, alphafuryl acrylic acid, vinyl furoic acid, p-vinylbenzoic acid, vinyl-naphtho
  • a strength imparting monomeric material such as acrylic and substituted acrylic acid and other copolymerizable ethylenieally unsaturated monocarboxylic acids, such as crotonic acid, alpha-chlorocrotonic acid, hydrosorbic acid, cinnamic acid, m-chlorocinnamic acid,
  • the synthetic copolymer latices utilized in this invention are also advantageously compatible with various resins used in compounding, such as wet strength resins well known to those skilled in the art, for example, melamine-formaldehyde.
  • various resins used in compounding such as wet strength resins well known to those skilled in the art, for example, melamine-formaldehyde.
  • the impregnated material is subjected to temperatures encountered in drying and in subsequent heat treatment. Such procedures are advantageous in the various applications of the present invention in that the internal bond strengths developed are usually enhanced rather than impaired.
  • the amounts of monoolefinic and diolefinic monomeric materials advantageously may vary within very wide limits.
  • the invention provides for the preparation of copolymers from monomeric mixtures of from about 20 to about percent by weight of the conjugated diene and from about to about 75 percent by weight of the total monomer charge of one or more of the monoolefinic monomers, the combined weight of these two monomeric materials being a major portion of the total monomeric mixture.
  • the partial ester of an unsaturated polybasic acid employed in the direct emulsion copolymerization of the copolymer economically constitutes from about 0.5 to about or more percent by weight of the monomer charged since it has been found that the major advantages of this invention can be achieved With such amounts. It is a distinct advantage of the invention that the fiber bonding properties of the copolymers are obtainable With relatively small quantities of partial esters of unsaturated polybasic acid.
  • the copolymerization of the copolymers is advantageously effected by emulsification of the monomers in an acid aqueous medium using emulsifiers which are stable therein.
  • Suitable emulsifiers include the ethers and esters of polyglycols with aliphatic acids having from 10 to 20 carbon atoms; alkyl sulfonates or sulfates and alkaryl sulfonates where the alkyl group contains from 10 to 20 carbon atoms; alkaryl polyether sulfates or sulfated monoglycerides and similar emulsifiers that will occur to those skilled in the art.
  • a particularly effective type of emulsifier has been found to be the sodium salts of alkaryl sulfonates.
  • the polymerization system may also include small amounts of stabilizers also known to the art.
  • the polymerization reaction may be promoted by the addition of free radical yielding initiators such as the alkali persulfates, percarbonates, perborates, and the like; organic peroxides, such as benzoyl peroxide, acetyl peroxide and the like; alkyl peroxides such as di-t-butyl peroxide; and organic hydroperoxide such as di-isopropyl benzene hydroperoxide.
  • Redox systems of initiation may be employed utilizing the above-mentioned substances with suitable reducing agents well known in the art.
  • the monomeric reaction mixture may also contain small amounts of the sulfhydryl-group-containing compounds termed modifiers in the synthetic rubber industry such as alkyl mercaptans containing from about 10 to 22 carbon atoms, for example, n-dodecyl mercaptan, the commercially available mixed tertiary mercaptans containing from 12 to 16 carbon atoms, thiophenol, alphaor beta-thionaphthol, and the like.
  • the polymerization can be effected within a wide range of temperatures, for example, within the range of from to about 175 F.
  • the above method conveniently results in the formation of polymer in the form of a latex or suspension of small drops or globules.
  • the synthetic latex thus prepared is ready for use as a non-woven fibrous material saturant or impregnant without the necessity of neutralization.
  • the polymerization may also be effected using well-known anionic or nonionic emulsifiers followed by neutralizing or alkalizing of the latex, for example with ammonium hydroxide, to pH 7 or above without coagulation and with retention of the enhanced adhesiveness and fiber bonding property.
  • nitriles such as acrylonitrile when copolymerized in amounts of from about 10 to about percent, preferably about 15 to about 35 percent, with at least about percent of the diene provide high internal bond in the impregnated fibers with excellent oil and solvent resistance.
  • styrene and substituted styrenes amounts of from about 10 to about 75 percent, preferably about 15 to about 70 percent, may advantageously be used.
  • a major advantage of the invention is the ability to use a lower degree of saturation of the fibers, for example 50 percent pickup, while still obtaining internal bond strength comparable to those obtainable with higher total saturation, that is to percent pickup, with butadiene-nitrile and butadiene-styrene latex saturants containing no partial esters of unsaturated polybasic acids.
  • the copolymer latices employed in this invention permit the development of unique combinations of properties with the high internal bond strength which are not obtainable with the ordinary synthetic latices when used as saturants.
  • those which have not heretofore been mentioned are the retention of high internal bond strength with pigmentation, high elongation with retention of internal bond strength and tensile strength, resistance to oils, solvents and discoloration on exposure ultraviolet light, and in some tape applications, the avoidance of a tie or primer coat for securing the pressure-sensitive adhesives to bonded fibrous backing, depending on the particular copolymer employed.
  • the fibrous masses may have a suitable copolymer content imparted by impregnation, such as dip saturation of preformed webs or sheets or by beater addition of an aqueous dispersion of copolymer directly to the fibers prior to formation of any web or sheeting.
  • the copolymer is deposited from an aqueous dispersion onto the fibers and within the interstices of the open porous web or sheeting.
  • the dispersions for impregnation may be acid, that is, they may be used after acid polymerization without neutralization or, if desired, they may be neutralized prior to impregnation of the fibrous articles while still retaining the enhanced adhesiveness and fiber binder properties.
  • the carboxylic acid groups are formed from, or introduced into, the preformed copolymer
  • the copolymerization of the diene and the comonomer is effected in an acidic aqueous medium.
  • the pH employed in the preparation of the latices is preferably from about 2 to 5.
  • the material is freed of excess saturant usually by passing through squeeze rolls or the like, and it is then subjected to a drying operation.
  • the polymer content on a dry solids basis may be from about 30 percent to about 60 percent by weight of the dry unified web or sheeting.
  • the internal bond strength varies with polymer content. This corresponds approximately to 40 to percent saturation or pickup (based on the dry weight of the fibrous material before impregnation).
  • copolymer latices of the invention are further illustrated in the following examples and their application to unified paper backings, e.g., creped masking tape base, rope tape stock, low-tensile flatback base, etc.,
  • the backings being internally bonded with the copolymers deposited from aqueous dispersions.
  • the invention has application to various fibrous masses, webs, flexible and rigid sheeting, and other fibrous articles which are customarily internally bonded, including non-woven textile fabrics made with fibers such as cotton, rayon, nylon, polyester, and other natural and synthetic fibers. Accordingly, the examples are not to be construed as a limitation of the invention but merely illustrative of specific embodiments. Unless otherwise noted, all references to parts or percentages in these examples refer to parts or percent by weight.
  • Example I An aqueous solution consisting of 150 parts of water, an emulsifying agent (4 parts of sodium salt of dodecyl benzene sulfonate), a chelating agent (0.04 part of ethylene diamine tetra acetic acid), a peroxygen type initiator (0.1 part of potassium persulfate), and a modified (0.9 part n-dodecyl mercaptan) was placed in a reaction vessel along with 65 parts of butadiene, 20.1 parts of acrylonitrile, 12 parts of styrene and 2.9 parts of monomethyl itaconate. The reaction vessel was initially brought to 125 F. and then raised to 160 F.
  • an emulsifying agent 4 parts of sodium salt of dodecyl benzene sulfonate
  • a chelating agent 0.04 part of ethylene diamine tetra acetic acid
  • a peroxygen type initiator 0.1 part of potassium persulfate
  • Example II Various half ester-containing copolymer latices were prepared in the manner set forth in Example I with variations in the monoolefinic monomer utilized in the copolymer. The composition of each of the copolymers is indicated in the following table in terms of percentage by weight of the various monomers charged.
  • Sheets of creped masking tape base (Duracel 301M) were submerged in each of the copolymer latices. Each sheet was dipped for a period sufficient to obtain complete saturation of the tape base with the latex. The impregnated sheets were then withdrawn from the latex and excess latex removed by passing the sheets through squeeze rolls maintained under light pressure. After squeeze rolling, the impregnated paper was dried at a temperature of about 220 F. for a period of about minutes to produce a paper having a polymer content of 75 percent on a dry basis of the weight of the untreated masking tape base. This paper was cured for about one minute at about 375 F.
  • the paper sheets were then subjected to a series of tests to determine the tensile strength (both wet and dry), internal bond strength represented as delamination resistance, and elongation properties developed by the impregnation with the particular copolymer.
  • comparison tests were performed utilizing synthetic latex saturants containing equivalent amounts (based on carboxyl content) of monomethyl itaconate, itaconic acid, and methacrylic acid.
  • the polymer types included commercial butadiene-acrylonitrile copolymers with two different compositions, and butadiene-styrene copolymers.
  • the copolymers employed in the comparisons were prepared by wellknown methods of emulsion polymerization. The description of the polymerization recipes employed in each of the tests performed on polymers referred to, Nitrile, Styrene and Low-Acid Nitrile polymers, is set forth below in tabular form.
  • Internal bond tests Internal bond strength is determined by measurement of resistance to delamination of the polymer impregnated sheets. The test is identified as the Permacel Tape Corporation Ply Adhesion Test. Such tests were conducted by taking sample sheets and sealing heat sensitive adhesive cloth backed tape to the front and back surfaces of the sample. The sample was reduced to 1 inch by 8 inches in size and placed in the jaws of a tensile machine. By operation of the machine, the two outer pieces of cloth backed tape were pulled apart at the rate of 12 inches per minute and the splitting or delamination of the impregnated paper sheet took place.
  • the force required to continue the failure of the sheet by splitting or delamination was measured on a tensile testing machine (a Thwing-Albert Tensile machine with a recording device) and this measured force was reported as the internal bond strength of the saturated paper in ounces per inch of width of test sample.
  • Tests for tensile strength of the impregnated paper were conducted by taking 1 inch by 8 inch samples of the impregnated paper and placing the ends thereof in the jaws of a standard tensile testing machine. The tensile strength was recorded by stretching the paper at the rate of 12 inches per minute in the machine direction of the paper and the pounds per inch of width at which the sample failed in tension were recorded as the tensile strength of the sample. In like manner, the percentage elongation was measured by recording the percentage of elongation which took place before failure of the sample, the elongation being measured in the machine direction (MD) and cross direction (CD) of the paper sheet.
  • MD machine direction
  • CD cross direction
  • Example III The advantage of the invention which permits development of good delamination resistance as well as wet tensile strength is further illustrated in Table 2 below.
  • the latices of the copolymers of butadiene-acrylonitrile and butadiene-styrene prepared in Example II with the addition of monomethyl itaconate, itaconic acid, or methacrylic acid were again employed for purpose of com- TABLE 2.PHYSIGAL PROPERTIES OF ROPE TAPE STOCK BACKIN GS pickup; cured one minute at 375 E] Reactive Carboxylic Monomer MMI IA MAA Nitrile Polymer:
  • Example IV The superior elongation characteristics of the copolymer latices prepared in Example II when used in base papers made with a low degree of fiber bonding is shown in Table 3.
  • Example V The development of improved edge tear in rope base sheets employing latices comprising monomethyl itaconate in comparison with itaconic acid and methacrylic acid in butadiene-acrylonitrile copolymers is demonstrated in Table 4 below.
  • the copolymer latices were prepared according to Example II except the polymers containing itaconic acid or monomethyl itaconate each contain the same number of equivalents of carboxyl groups while the methacrylic acid variation does not; it containing considerably greater amounts (5:3).
  • Example VI A series of experiments was effected in an effort to illustrate the superiority of the use of monomethyl itaconate polymers over monobutyl itaconate.
  • the compositions of the polymers and the base papers employed are set forth below, along with the comparative data resulting from such experiments.
  • Example VII A series of experiments was efiected in order to illustrate the operability of the monoesters of maleic acid in the latices of this invention.
  • the compositions of the polymers and the base papers employed are set forth below in tabular form. The results are compared with monomethyl itaconate-containing latices.
  • An impregnating composition characterized by enhanccd adhesiveness and fiber-bonding properties, comprising a stable latex consisting essentially of an aqueous dispersion of a copolymer prepared by emulsion polymcrization in an aqueous acid medium of a monomeric mixture containing about 20 to about 84.5 percent by Weight of butadienel,3, from about 0.5 to about 20 percent by weight of monomethyl itaconate, and a balance of from about 10 to about 75 percent by weight of at least one monoolefinic monomer copolymerizable with said butadiene and selected from the group consisting of nitriles, styrenes and lower molecular weight alcohol esters of acrylic or alpha-substituted acrylic acids; the monomeric mixture containing at least about 50 percent by weight of said butadiene when the monoolefinic monomer is a nitrile.
  • composition of claim 1 in which the copolymer is prepared from a monomeric mixture containing from about 50 to about 75 percent by weight of butadiene-1,3, from about 0.5 to about 10 percent by weight of monomethyl itaconate, and the balance being from about 15 to about 35 percent by weight of acrylonitrile.
  • composition of claim 1 in which the copolymer is prepared from a monomeric mixture containing from about 20 to about 75 percent by weight of butadienel,3, from about 0.5 to about 10 percent by weight of monomethyl itaconate and the balance being from about 15 to about 70 percent by weight of styrene.
  • a fibrous article comprising a nonwoven fibrous mass with high resistance to delamination, said mass being internally bonded with from 30 to 60 percent by weight of an impregnating composition
  • an impregnating composition comprising a copolymer prepared by emulsion polymerization of a monomeric mixture containing from about 20 to about 84.5 percent by weight of an aliphatic conjugated diene having from four to ten carbon atoms, from about 0.5 to about 20 percent by weight of a partial alkyl ester of itaconic acid, the alkyl portion of the ester containing from 1 to 2 carbon atoms and a balance of from about 10 to about 75 percent by weight of at least one monoolefinic monomer selected from the group consisting of nitriles, styrenes and lower molecular weight alcohol esters of acrylic or alpha-substituted acrylic acids; the monomeric mixture containing at least about 50 percent by weight of said diene when the monoolefinic monomer is a nitrile.

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US384536A 1964-07-22 1964-07-22 Copolymers of conjugated diolefins and partial esters of unsaturated polybasic acids Expired - Lifetime US3422050A (en)

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JP (1) JPS5136293B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE667259A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE1570118A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR1511560A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1112888A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
LU (1) LU49130A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL6509511A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6110525A (en) * 1997-09-12 2000-08-29 Pro-Sol, Inc. Coating composition for protecting surfaces and method of using same
US20070149693A1 (en) * 2004-03-31 2007-06-28 Misao Aida Composition for dip forming and molding obtained by dip forming
WO2022193837A1 (zh) * 2021-03-15 2022-09-22 北京化工大学 一种富马酸酯/共轭二烯共聚物型生物基橡胶及其制备方法和其硫化胶制品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372675B1 (en) * 1995-09-28 2002-04-16 Omnova Solutins Inc. Nonwoven fabric non-cellulose fibers having improved wet tensile strength
CN112521553B (zh) * 2019-09-19 2022-02-01 北京化工大学 一种衣康酸酯/苯乙烯/丁二烯共聚物及其制备方法和橡胶组合物

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891039A (en) * 1954-06-05 1959-06-16 Bayer Ag Terpolymers of diolefins with halfesters of maleic acid and a monoolefinic monomer
US2947733A (en) * 1957-04-19 1960-08-02 Firestone Tire & Rubber Co Process of curing a rubbery copolymer of a conjugated diene and a carboxylic acid oranhydride with dicyandiamide, and cured product obtained thereby
US2959821A (en) * 1955-02-11 1960-11-15 Bayer Ag Dipping process wherein cross-linking agent is applied in coagulating bath
US2967174A (en) * 1955-03-24 1961-01-03 Bayer Ag Process for the production of polymerization products
US3256234A (en) * 1958-08-01 1966-06-14 Internat Latex & Chemical Corp Latex compositions
US3259601A (en) * 1963-07-31 1966-07-05 Koppers Co Inc Baked metal primers of ternary butadiene polymer and phosphoric acid
US3300431A (en) * 1963-04-20 1967-01-24 Takeda Chemical Industries Ltd Non-woven fabric and adhesive composition therefor
US3305500A (en) * 1962-07-12 1967-02-21 Ici Ltd Coating compositions comprising butadiene-1, 3 copolymer, starch and mineral pigment
US3321432A (en) * 1963-10-04 1967-05-23 Dow Chemical Co Textile backing agent comprising an aqueous dispersion of a carboxylcontaining copolymer and the reaction product of epichlorohydrin with an alkylene polyamine
US3345204A (en) * 1963-06-06 1967-10-03 Johnson & Johnson Process of impregnating an instantaneously wettable paper with a rubber latex

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891039A (en) * 1954-06-05 1959-06-16 Bayer Ag Terpolymers of diolefins with halfesters of maleic acid and a monoolefinic monomer
US2959821A (en) * 1955-02-11 1960-11-15 Bayer Ag Dipping process wherein cross-linking agent is applied in coagulating bath
US2967174A (en) * 1955-03-24 1961-01-03 Bayer Ag Process for the production of polymerization products
US2947733A (en) * 1957-04-19 1960-08-02 Firestone Tire & Rubber Co Process of curing a rubbery copolymer of a conjugated diene and a carboxylic acid oranhydride with dicyandiamide, and cured product obtained thereby
US3256234A (en) * 1958-08-01 1966-06-14 Internat Latex & Chemical Corp Latex compositions
US3305500A (en) * 1962-07-12 1967-02-21 Ici Ltd Coating compositions comprising butadiene-1, 3 copolymer, starch and mineral pigment
US3300431A (en) * 1963-04-20 1967-01-24 Takeda Chemical Industries Ltd Non-woven fabric and adhesive composition therefor
US3345204A (en) * 1963-06-06 1967-10-03 Johnson & Johnson Process of impregnating an instantaneously wettable paper with a rubber latex
US3259601A (en) * 1963-07-31 1966-07-05 Koppers Co Inc Baked metal primers of ternary butadiene polymer and phosphoric acid
US3321432A (en) * 1963-10-04 1967-05-23 Dow Chemical Co Textile backing agent comprising an aqueous dispersion of a carboxylcontaining copolymer and the reaction product of epichlorohydrin with an alkylene polyamine

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6110525A (en) * 1997-09-12 2000-08-29 Pro-Sol, Inc. Coating composition for protecting surfaces and method of using same
US20070149693A1 (en) * 2004-03-31 2007-06-28 Misao Aida Composition for dip forming and molding obtained by dip forming
US7662890B2 (en) * 2004-03-31 2010-02-16 Zeon Corporation Composition for dip forming and molding obtained by dip forming
WO2022193837A1 (zh) * 2021-03-15 2022-09-22 北京化工大学 一种富马酸酯/共轭二烯共聚物型生物基橡胶及其制备方法和其硫化胶制品

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NL6509511A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1966-01-24
JPS5136293B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1976-10-07
FR1511560A (fr) 1968-02-02
GB1112888A (en) 1968-05-08
DE1570118A1 (de) 1970-08-13
LU49130A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1965-09-21
BE667259A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1966-01-24

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