US2616867A - Composition for and method of sizing yarns - Google Patents

Composition for and method of sizing yarns Download PDF

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US2616867A
US2616867A US182399A US18239950A US2616867A US 2616867 A US2616867 A US 2616867A US 182399 A US182399 A US 182399A US 18239950 A US18239950 A US 18239950A US 2616867 A US2616867 A US 2616867A
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yarns
water
solution
dicarboxylic
copolymer
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Elmer H Rossin
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Monsanto Chemicals Ltd
Monsanto Chemical Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

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  • Thepresent invention relates to improvements in'the art of sizing water-insoluble synthetic linear polymer warp yarns such as synthetic linear polyamide warp yarns. It more particularly relates to improvements in the art of sizin polyhexamethylene-adipamide warp yarns and polyacrylonitrile warp yarns.
  • a further object of this invention is to provide an improved method of sizing water-insoluble synthetic linear polymer yarns of the nature of synthetic linear 'polyamide yarns and polyacrylonitrile yarns.
  • a further object of this invention is to provide sized water-insoluble synthetic linear polymer yarns which are produced at relatively low cost and have a high weaving efiiciency when woven in customary looms undernormal conditions of humidity.
  • a polyhexamethyleneadipamide yarn a water solution of a water-soluble choline salt'of' a copolymer consisting of the copolymerization product of an ethylene 11,5 dicarboxylic anhydride or acid, or partial alkyl esters of such acid having not more than 3 carbon atoms in the alkyl group, or combinations thereof, and
  • the solution of the choline salt of the copolymer may be slightly acid or alkaline, but, preferably, should have a pH between 4.5 and 9.5.
  • the temperature of the size solution is generally within the rang of to 205 F., but preferably is within the range of to F.
  • the amount of choline salt of thecopolymer applied to the yarn will vary to some extent depending upon the construction of the yarn and the amount of twist put in the yarn as Well as the construction of the fabric, but i generally within the range of about 1 to 15% by weight based on the weight of the yarn. Best results are obtained --by applying between 5 and 15% by weight of the choline salt of the copolymer based on the yarn and such amounts are preferred.
  • water-insoluble synthetic polymer yarn as used herein is intended to includ the Water-insoluble synthetic linear polyamide yarns which show orientation along the fiber axis by characteristic X-ray diffraction patterns.
  • synthetic linear polyamide yarns may b mentioned pclyhexamethylene-adipamide yarns and polyhexamethylenesebacamide yarns, these being preferred in this particular class .of synthetic polymer yarns.
  • Other Water-insoluble synthetic linear polyamide yarnsx which are "also satisfactorily sized in accordance with the methods of this invention are described in U. S. Patents Nos. 2,071,250, 2,130,523 and 2,130,948.
  • water-insoluble synthetic polymer yarns as used herein is also intended to include yarns prepared from copolymers of vinyl chloride and vinyl acetate, polyvinylidene chloride, copolymen; of vinylidene chloride and vinyl chloride, and. pfllyfiic fylonitrile which may contain up to 20% of a comonomer or other modifying agent, but. isnot intended to include yarns prepared from na ural polymers such as cellulose or cellulose derivatives.
  • those prepared from polyacrylonitrile or modified-polyacrylonitrile are preferably sized in accordance with the methods of this invention.
  • yarns as used herein is intended to include monoor .multi-filament continuous filaments, or threads or yarns containing substantial amounts, that is, from 75 to 100% of staple fibers of the polymers hereinbefore described.
  • the synthetic polymer "yarns which are sized inaccordance with the methods of this invention have :a tough elastic and smooth coating-thereon which coating does not substantially dust-or shed from theyarns when the;yarnsare subsequently woven "in a loom at 5,0 to 80% relative humidity.
  • Woven fabrics prepared frcm'the sized yarns are substantially free of defects normally attributable to poor sizing per se.
  • the weaving efflciency of'the sized yarns of this invention is very high andthe number ofyarns breaks-attributable to poor sizing is reduced to a minimum.
  • the size is readily removed from the yarns or the woven fabric by washing the sized materialin warm 'water'or in warm water containing synthetic detergents.
  • an ethylene t e dicarboXylic acid such as maleic acid, or an anhydride of such acid such as maleic anhydri-d-e, or alkyl acid esters of such acid, for example, methyl acid maleate or mixtures of such compounds.
  • the vinyl aromatic compound and the dicarboxylic compound or compounds are copolymerized in a mol ratio between 1-21 and :2:1 and preferably, in a mole ratio of 1:1 to 1.511. Althoughvarious ratios of monomers maybe used to prepare the copolymer within the range described above, the
  • copolymer will normally contain the vinyl .conrpoundand the dicarboxylic compound combined in substantially equi-mclecular proportions.
  • the resulting copolymer is then reacted in water with choline to iorm "the choline salt, using an amountof cholinesufiicient to dissolve the co polymer in the water, and preferably to provide a solution having a pH between 4.5 and 9.5.
  • the solutions which are slightly acidic, that is, between a pH of about 4.5 and 7.0 are highly viscous and decrease in viscosity as the pH is increased.
  • the solutions which are alkaline reacting generally have a relativelylow'viscosityand decrease in viscosity with an increase in pH.
  • the copolymers employed in preparing the choline salt for sizing purposes are suitably produced by mass "polymerizing the vinyl aromatic compound and the dicarboxylic compound.
  • the monomeric vinyl aromatic compound and the dicarboxylic compound are generally heated to temperatures within the range of 40 to C. and maintained at such temperatures :until the major portion of :the monomers have reacted, after which the temperature of the mass ;is ,raised to to Cutocomplete the polymerization of theremaim ing-monomers.
  • Thernass polymerization process is preferably carried out by polymerizing the monomers in the presence of a small amount of polymerization catalyst, particularly a peroxide catalyst such as benzoyl peroxide.
  • the mass is substantially free .of solvents or diluents for the monomers.
  • the copolymer is obtained in the form of a hard glassy resin which is preferably comminuted before it :is used.
  • Another suitable method for preparing the copolymers for use in making the choline salt is the so-called sumble-non-solvent process which involves heatinga solution of the vinyl aromatic compound and the dicarboxylic compound in a hydrocarbon liquid which is a solvent for the monomers but -a non-solvent for the copolymer formed by the polymerization of the monomers.
  • Benzene, tolueneand xylene have been successfully used as thehydrocarbon liquid.
  • the process is preferably carried out in the presence of a small amountofapolymerization catalystparticuljarly a peroxide-catalyst. such as benzoyl peroxide.
  • the copolymer precipitates from the by drocarbon liquid in the form of fine particles as it is formed, and is afterwards separated from th hydrocarbon liquid by filtering or the like and then the hydrocarbon liquid is evaporated from the copolymer solids.
  • Styrene is preferred because of its low cost and availability and superior properties for this partic ular purpose.
  • ethylene apdicarboxylic compounds which arev useful in preparing the copolymers may be mentioned .maleic acid, .maleic, anhydride, fumaric acid, citraconic anhydride. itaconic anhydride and the like and alkyl half esters of the corresponding acids, which con tain from 1 to 3 carbon atomsin the alkyl group, for example methyl, ethyl and propyl acid maleate and the corresponding 'fumarates, citraconates and itaconates.
  • alkyl acid esters of ethylene (1,5 dicarboxylic acids When the alkyl acid esters of ethylene (1,5 dicarboxylic acids are used it is preferred to use a mixture of dicarboxylic compounds containing at least '50 mol per cent of an ethylene 11,5 dioarboxylic acid or :anhydride, more V spectively. ,1
  • maleic anhydride is the preferred dicarboxylic compound because of its low cost and ready availability and its superiority over the other dicarboxylic compounds as a component of the copolymer. Mixtures of maleic anhydride and methyl acid maleate containing from 99 to 50 mol per cent of maleic anhydride are also preferred over the other dicarboxylic compounds or mixtures thereof.
  • the water solution of choline salts of the copolymer are normally the sole sizing agents used in the practice of this invention. However, in some instances it is possible to use up to 20% by weight of an alkali metal salt of a styrenemaleic acid copolymer to replace a part of the choline salt.
  • the water solutions of the choline salt of the copolymer generally contain from 4 to 35% by weight of the choline salt and have a viscosity between about 50 and 20,000 centipoises at 25 C. depending on the concentration of the solution, thepH of the solution and the particular copolymer used in preparing the choline salt.
  • the viscosity'of the solution may be modified by adding glycerine.
  • the glycerine increases the desirable in some instances where the viscosity of choline salt solution is too low for sizing purposes. Amounts of 1 to 40% by weight of glycerine, on the weight of the choline salt, are generally satisfactory for this purpose. The glycerine also improves the adhesion of the size to I the yarns.
  • the solutions may also contain plasticizers such as polyethylene or polypropylene glycols and softeners such as Twitchell oil, sulfonated tallow and sulfonated vegetable oil.
  • the size solutions be free of reactive substances, that is substances which react with the choline salt at normal drying temperatures to form water-insoluble resins.
  • Example I One hundred and twenty parts of a finely divided styrene-maleic anhydride-methyl acid maleate copolymer (containing 51% of combined styrene, 37.4%" of combined maleic anhydride and 11.4% of combined methyl acid maleate) were added to 1188 parts of water at a tempera ture of 40 to C. The resulting mixture was well agitated and 192 parts of a 40% water solution of choline were added. The mixture was heated to 90 C. and then boiled for one hour to dissolve thecopolymer as the choline salt. The
  • the sized yarns were then dried by passing them over five rotating drying cans heated to temperatures of 180, 200, 200, 200 and 160 LFE, re-
  • Example II Unsized 70/34/7Z/100 bright polyhexamethylone-adipamide warp yarns were sized with the above solution using the procedure described in paragraph 2 of Example I.
  • the dry sized yarns were considerably stiffer than those prepared in accordance with the procedure of Example I, but were similar to those yarns in weaving eificiency, ease of removal of the size and in the adhesion of the size to the individual filaments of the yarns. 7
  • Example III A water solution of the choline salt of a copolymer of styrene-maleic anhydride-methyl acid maleate was prepared as described in the first paragraph of Example I and to this was added sufficient glycerine to provide 30% of glycerine on the weight of the copolymer. The solution was diluted with water to 8% solids and at this concentration had a pH of 7.3 and a viscosity of 650 centipoises at a temperature of 25 C.
  • Unsized 70/34/7Z/100 bright polyhexamethylene-adipamide warp yarns were sized with the above solution using the procedure described in paragraph 2 of Example I.
  • the dry sized yarns were quite supple and flexible but yet were sufiiciently stiff to handle well in a loom.
  • the size coating on yarns was tough and elastic and adhered to the yarn without dusting or shedding when the yarn was quickly stretched and immediately relaxed.
  • the yarns had excellent weaving efiiciency and few yarn breaks were encountered during weaving.
  • the woven fabric was substantially free of defects.
  • Example IV One hundred and twenty parts of a finely diadded to 1188 parts of water at a temperature of,
  • Unsized 70/34/7Zr/1OQ bright polyhexameth-ylene-adipamide warp yarns were sized with the above: solution using the procedure described in aragraph 2. of Example 1;...
  • the d y siz d yarns had properties similar to, those of the. ized yarns prepared as. described in Example III.
  • Example VI Four hundred and fifty-two parts of a finely divided styrene-maleic anhydride-methyl acid maleate copolymer (containing 51% of combined styrene, 37.4% of combined maleic anhydride and 11.4% of combined methyl acid maleate) were added rapidly to 2548 parts of a Water solution containing 298 parts of choline at a temperature of C;. The resulting mixture was heated to a temperature of'90 C; over a period ofone hour and then maintained at that temperature for another hour, after which time the copolymer dissolved: in the. formo-- its choline salt. The resulting: solution was diluted; with water until it contained l8,%- of the cholinev salt of the copolymer. The pH of this solution was 7.44 (glass electrode) and the viscosity was 735 centipoises a t. C;
  • Seven ends of spun yarn prepared from polyacrylonitril'e staple fiber were passed at the rate of 15 yardsper minute through the 18% solution of choline salt of the copolymer which was maintained at a temperature of 140 to 150 FL, after which the yarns were squeezed by passing them between squeeze rolls and applying a pressure or 6.66 pounds. per linear inch. About 15% of the cholinesalt was deposited on the yarn based on the yarn weight. The sized yarns were then dried by passing them over five rotating drying cans heated to temperatures of 180, 200, 200, 200 and 160 F., respectively.
  • the dry yarns were sufiiciently stiii ened to handle well in a loom and had excellent weaving efficiency when Woven in a conventional loom. Moreover, the size coating was tough and flexible and had excellent adhesion to the yarn. The size was readily removed from the yarns by Washing the woven fabric in warm water.
  • the sized" yarns possessed increased tensile strength and excellent abrasion resistance as indicated by the following; tests. A portion of one of the sized yarns was first conditioned for 24 hours at a relative humidityof and a temperature of '70 F. and then tested for tensile strength and; abrasion resistance. A control sam ple of unsized yarn was conditioned andtested in the same manner. The following table shows the results obtained.
  • a method oi sizing water-insoluble synthetic linear polymer yarns which comprises applying to said yarns a water solution of a choline salt of a copclymer consisting of the copolymerizaticn product of styrene and maleic anhydride, and drying said yarn preparatory to wearing the same.
  • a method of sizing water-insoluble synthetic linear polymer yarns which comprises applying to said yarns a Water solution of a choline salt of a copolymer consisting of the copolymerization productof styrene and a mixture of maleic anhydride and methyl acid maleate, said mixture containing from 50 to 99 mol per cent of maleic anhydride, and drying said yarn preparatory to weaving the same.
  • a method of sizing water-insoluble polyhexamethyl'ene-adipamide yarns which comprises applying to said yarns a water solution of a choline salt of a copolymer consisting of the copolymerization product of styrene and maleic anhydride, said solution being applied in an amount sufiicient to provide from 1 to 15% by weight of said choline salt on the weight of the yarns, and drying said yarns preparatory to solution contains an amount of glycerine sufficient to increase the viscosity of the solution over and above the viscosity obtained with the choline salt per se.
  • a method of sizing water-insoluble polyhexamethylene-adipamide yarns which comprises applying to said yarns a water solution of a choline salt of a copolymer consisting of the copolymerizationproduct of styrene and a mixture of maleic anhydride and methyl acid maleate, said mixture containing from 50 to 99 mol per cent of maleic anhydride, said solution being applied in an amount suflicient to provide from 1 to 15% by Weight of said choline salt on the weight of the yarns, and drying said yarns preparatory to weaving the same.
  • a choline salt of a copoylmer consisting of the copolymerization product of styrene and maleic anhydride.

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Description

Patented Nov. 4, 1952 COMPOSITION FOR AND METHOD OF SIZING YARNS I Elmer H. Rossin, Melrose, Mass., assignor to,
Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application August 30, 1950, Serial No. 182,399
: Thepresent invention relates to improvements in'the art of sizing water-insoluble synthetic linear polymer warp yarns such as synthetic linear polyamide warp yarns. It more particularly relates to improvements in the art of sizin polyhexamethylene-adipamide warp yarns and polyacrylonitrile warp yarns.
One of the difficulties heretofore experienced in the weaving of synthetic linear polymer yarns as, for example, polyhexamethylene-adipamide yarns and similar yarns, which stretch under slight stress and regain their original length quickly when the stress is removed, is that the size tends to dust or shed from the yarns during the weaving operation due to poor adhesion of the size with the result that the yarns ar not adequately protected during weaving. Natural Sizing agents such as starch or gelatin which are generally suitable for sizing cotton and regenerated cellulose yarns are not satisfactory for sizing synthetic linear polymer yarns such as polyhexamethylene-adipamide yarns.
Various water-soluble artificial polymeric materials as, for example, polyvinyl alcohol have been suggested for sizing synthetic polymer yarns but these'generally are only satisfactory for sizing low twist knitting yarns. Polymethacrylic acid has been suggested heretofore as a size for polyhexamethylene-adipamide yarns but has the disadvantages of being difiicultly soluble in water and also quite expensive. Also solutions of polymethacrylic acid are acidic and'this makes them unsatisfactory from the standpoint of corrosion of the machinery used in sizing and weaving the yarns.
It has also been proposed heretofore to employ water solutions of quaternary ammonium hydroxide salts of styrene-maleic anhydride copolymers together with a reactive substance such as formaldehyde, alkylene polyamines or thermosetting resins for the treatment of nylon fabrics and other nylon textile materials for the purpose of producing a water resistant, permanently stiffened finish on the fabric. These quaternary ammonium hydroxide salts as a class are not satisfactory for sizing nylon textiles and they have only been useful when used in conjunction with the aforementioned reactive materials, namely, formaldehyde or' the like. The use of a reactive substancewith such salts, however, results in the formation of a water-insoluble resin which cannot be removed from the fabric by simple washing.
In accordance with the present invention, it ispossible to size linearpolymer .yarns with a a 17 Claims. (o1. 26029.6)
new essentially neutral, water-soluble polymeric material which provides sized yarns having high weaving efiiciency. and. excellent, abrasion resist!- ance. t
It is accordingly one object of this invention to provide a novel composition for sizing water-insoluble synthetic linear polymer yarns.
A further object of this invention is to provide an improved method of sizing water-insoluble synthetic linear polymer yarns of the nature of synthetic linear 'polyamide yarns and polyacrylonitrile yarns.
A further object of this invention is to provide sized water-insoluble synthetic linear polymer yarns which are produced at relatively low cost and have a high weaving efiiciency when woven in customary looms undernormal conditions of humidity.
Still further objects and advantages of this invention will appear in the following description and the appended claims.
The objects of this invention are attained, in general, by first applying to the naked or presizedwater-insoluble synthetic linear polymer yarn as, for example, a polyhexamethyleneadipamide yarn, a water solution of a water-soluble choline salt'of' a copolymer consisting of the copolymerization product of an ethylene 11,5 dicarboxylic anhydride or acid, or partial alkyl esters of such acid having not more than 3 carbon atoms in the alkyl group, or combinations thereof, and a polymerizable vinylaromatic compound having a single C=CH2 group as, for example, styrene. The solution of the choline salt of the copolymer may be slightly acid or alkaline, but, preferably, should have a pH between 4.5 and 9.5. The temperature of the size solution is generally within the rang of to 205 F., but preferably is within the range of to F. After the solution has been applied to the synthetic polymer yarn in a suitable manner as, for example, by passing the Warp yarns'through a conventional size box containing the sizing solution, the sized yarns are dried to render them substantially nontacky, preferably by passing them over heated drying cans of the type conventionally employe in warp slashing machinery.
The amount of choline salt of thecopolymer applied to the yarn will vary to some extent depending upon the construction of the yarn and the amount of twist put in the yarn as Well as the construction of the fabric, but i generally within the range of about 1 to 15% by weight based on the weight of the yarn. Best results are obtained --by applying between 5 and 15% by weight of the choline salt of the copolymer based on the yarn and such amounts are preferred.
The term water-insoluble synthetic polymer yarn as used herein is intended to includ the Water-insoluble synthetic linear polyamide yarns which show orientation along the fiber axis by characteristic X-ray diffraction patterns. As examples of such synthetic linear polyamide yarns may b mentioned pclyhexamethylene-adipamide yarns and polyhexamethylenesebacamide yarns, these being preferred in this particular class .of synthetic polymer yarns. Other Water-insoluble synthetic linear polyamide yarnsxwhich are "also satisfactorily sized in accordance with the methods of this invention are described in U. S. Patents Nos. 2,071,250, 2,130,523 and 2,130,948.
The term water-insoluble synthetic polymer yarns as used herein is also intended to include yarns prepared from copolymers of vinyl chloride and vinyl acetate, polyvinylidene chloride, copolymen; of vinylidene chloride and vinyl chloride, and. pfllyfiic fylonitrile which may contain up to 20% of a comonomer or other modifying agent, but. isnot intended to include yarns prepared from na ural polymers such as cellulose or cellulose derivatives. Of the synthetic polymer yarns described immediately above, those prepared from polyacrylonitrile or modified-polyacrylonitrile are preferably sized in accordance with the methods of this invention.
The term yarns as used herein is intended to include monoor .multi-filament continuous filaments, or threads or yarns containing substantial amounts, that is, from 75 to 100% of staple fibers of the polymers hereinbefore described.
The synthetic polymer "yarns which are sized inaccordance with the methods of this invention have :a tough elastic and smooth coating-thereon which coating does not substantially dust-or shed from theyarns when the;yarnsare subsequently woven "in a loom at 5,0 to 80% relative humidity. Woven fabrics prepared frcm'the sized yarns are substantially free of defects normally attributable to poor sizing per se. The weaving efflciency of'the sized yarns of this invention is very high andthe number ofyarns breaks-attributable to poor sizing is reduced to a minimum. Moreover, the size is readily removed from the yarns or the woven fabric by washing the sized materialin warm 'water'or in warm water containing synthetic detergents.
The water-soluble cholinesalt sizing agents of this invention may be prepared in various ways. In general, they are prepared by first forming a copolymeric material by the conjoint polymerization of a polymerizable vinyl aromatic compound having a single C=CH2 group as, for example, styrene, and an ethylene t e dicarboXylic acidsuch as maleic acid, or an anhydride of such acid such as maleic anhydri-d-e, or alkyl acid esters of such acid, for example, methyl acid maleate or mixtures of such compounds. The vinyl aromatic compound and the dicarboxylic compound or compounds are copolymerized in a mol ratio between 1-21 and :2:1 and preferably, in a mole ratio of 1:1 to 1.511. Althoughvarious ratios of monomers maybe used to prepare the copolymer within the range described above, the
copolymer will normally contain the vinyl .conrpoundand the dicarboxylic compound combined in substantially equi-mclecular proportions. The resulting copolymer is then reacted in water with choline to iorm "the choline salt, using an amountof cholinesufiicient to dissolve the co polymer in the water, and preferably to provide a solution having a pH between 4.5 and 9.5. The solutions which are slightly acidic, that is, between a pH of about 4.5 and 7.0 are highly viscous and decrease in viscosity as the pH is increased. .The solutions which are alkaline reacting generally have a relativelylow'viscosityand decrease in viscosity with an increase in pH. In order to bring about a rapid reaction between the choline and the oopolymer it is preferred to heat the water in which the reaction is carried out to a temperature of 70 to 100 C.
The copolymers employed in preparing the choline salt for sizing purposes are suitably produced by mass "polymerizing the vinyl aromatic compound and the dicarboxylic compound. In lthejnass polymerization process, the monomeric vinyl aromatic compound and the dicarboxylic compound are generally heated to temperatures within the range of 40 to C. and maintained at such temperatures :until the major portion of :the monomers have reacted, after which the temperature of the mass ;is ,raised to to Cutocomplete the polymerization of theremaim ing-monomers. 'Thernass polymerization process is preferably carried out by polymerizing the monomers in the presence of a small amount of polymerization catalyst, particularly a peroxide catalyst such as benzoyl peroxide. The mass is substantially free .of solvents or diluents for the monomers. The copolymer is obtained in the form of a hard glassy resin which is preferably comminuted before it :is used.
Another suitable method for preparing the copolymers for use in making the choline salt is the so-called soivent-non-solvent process which involves heatinga solution of the vinyl aromatic compound and the dicarboxylic compound in a hydrocarbon liquid which is a solvent for the monomers but -a non-solvent for the copolymer formed by the polymerization of the monomers. Benzene, tolueneand xylene have been successfully used as thehydrocarbon liquid. The processis preferably carried out in the presence of a small amountofapolymerization catalystparticuljarly a peroxide-catalyst. such as benzoyl peroxide. The copolymer precipitates from the by drocarbon liquid in the form of fine particles as it is formed, and is afterwards separated from th hydrocarbon liquid by filtering or the like and then the hydrocarbon liquid is evaporated from the copolymer solids.
As examples of vinyl aromatic compounds containing a single C==CH2 group which are useful in preparing the copolymers may be mentioned styrene, halogen substituted styrene such -as p-ohloro styrene, dichloro-styrene and the like, and alkyl substituted styrenes such as p-methyl styrene, dimethyl styrene and the like. Styrene is preferred because of its low cost and availability and superior properties for this partic ular purpose.
.As examples of ethylene apdicarboxylic compounds which arev useful in preparing the copolymers may be mentioned .maleic acid, .maleic, anhydride, fumaric acid, citraconic anhydride. itaconic anhydride and the like and alkyl half esters of the corresponding acids, which con tain from 1 to 3 carbon atomsin the alkyl group, for example methyl, ethyl and propyl acid maleate and the corresponding 'fumarates, citraconates and itaconates. When the alkyl acid esters of ethylene (1,5 dicarboxylic acids are used it is preferred to use a mixture of dicarboxylic compounds containing at least '50 mol per cent of an ethylene 11,5 dioarboxylic acid or :anhydride, more V spectively. ,1
particularly an anhydride. Maleic anhydride is the preferred dicarboxylic compound because of its low cost and ready availability and its superiority over the other dicarboxylic compounds as a component of the copolymer. Mixtures of maleic anhydride and methyl acid maleate containing from 99 to 50 mol per cent of maleic anhydride are also preferred over the other dicarboxylic compounds or mixtures thereof.
The water solution of choline salts of the copolymer are normally the sole sizing agents used in the practice of this invention. However, in some instances it is possible to use up to 20% by weight of an alkali metal salt of a styrenemaleic acid copolymer to replace a part of the choline salt. The water solutions of the choline salt of the copolymer generally contain from 4 to 35% by weight of the choline salt and have a viscosity between about 50 and 20,000 centipoises at 25 C. depending on the concentration of the solution, thepH of the solution and the particular copolymer used in preparing the choline salt. The viscosity'of the solution may be modified by adding glycerine. viscosity of the solution and this is particularly The glycerine increases the desirable in some instances where the viscosity of choline salt solution is too low for sizing purposes. Amounts of 1 to 40% by weight of glycerine, on the weight of the choline salt, are generally satisfactory for this purpose. The glycerine also improves the adhesion of the size to I the yarns. The solutions may also contain plasticizers such as polyethylene or polypropylene glycols and softeners such as Twitchell oil, sulfonated tallow and sulfonated vegetable oil.
However, it is essential that the size solutions be free of reactive substances, that is substances which react with the choline salt at normal drying temperatures to form water-insoluble resins. f
A further understanding of the methods and compositions of this invention will be obtained from the following specific examples which are. intended to illustrate the invention but not to. limit its scope, parts and percentages being by.
weight unless otherwise specified.
Example I One hundred and twenty parts of a finely divided styrene-maleic anhydride-methyl acid maleate copolymer (containing 51% of combined styrene, 37.4%" of combined maleic anhydride and 11.4% of combined methyl acid maleate) were added to 1188 parts of water at a tempera ture of 40 to C. The resulting mixture was well agitated and 192 parts of a 40% water solution of choline were added. The mixture was heated to 90 C. and then boiled for one hour to dissolve thecopolymer as the choline salt. The
' resulting solution had a pH of 7.3 (glass elecof the size between the filaments in the yarn.
The sized yarns were then dried by passing them over five rotating drying cans heated to temperatures of 180, 200, 200, 200 and 160 LFE, re-
. 6 The dry yarns were quite supple and flexible, but yet sufilciently stiff to handle well in a loom.
They were covered with a tough, elastic coating which adhered to the yarn without dusting when the yarn was quickly stretched and then immediately relaxed. After being conditioned for 24 hours at a temperature of 70 F. and a relative humidity of 65%, a number of the sized yarns were broken and the broken ends of the yarns were examined. They were found to be free of loose or fluffy filaments which indicates that the size has excellent adhesion to the yarns and also binds the individual filaments together thus affording maximum protection against yarn defects during weaving. The yarns had excellent weaving efiiciency when woven in a conventional loom, and the size was readily removed from the woven fabric by washing the fabric in warm water.
Example II Unsized 70/34/7Z/100 bright polyhexamethylone-adipamide warp yarns were sized with the above solution using the procedure described in paragraph 2 of Example I. The dry sized yarns were considerably stiffer than those prepared in accordance with the procedure of Example I, but were similar to those yarns in weaving eificiency, ease of removal of the size and in the adhesion of the size to the individual filaments of the yarns. 7
Example III A water solution of the choline salt of a copolymer of styrene-maleic anhydride-methyl acid maleate was prepared as described in the first paragraph of Example I and to this was added sufficient glycerine to provide 30% of glycerine on the weight of the copolymer. The solution was diluted with water to 8% solids and at this concentration had a pH of 7.3 and a viscosity of 650 centipoises at a temperature of 25 C.
Unsized 70/34/7Z/100 bright polyhexamethylene-adipamide warp yarns were sized with the above solution using the procedure described in paragraph 2 of Example I. The dry sized yarns were quite supple and flexible but yet were sufiiciently stiff to handle well in a loom. The size coating on yarns was tough and elastic and adhered to the yarn without dusting or shedding when the yarn was quickly stretched and immediately relaxed. The yarns had excellent weaving efiiciency and few yarn breaks were encountered during weaving. Moreover, the woven fabric was substantially free of defects.
Example IV One hundred and twenty parts of a finely diadded to 1188 parts of water at a temperature of,
40.1 to. .10 G; The esult n xture was well a itated and. 1.92 nartsof; a 40% water so u ion at holine were. added aft r wh h. the-mixt re as boiled for 1,; hour to dissolve the copolymer in the; form, of; its; choline salt. The solution was c oled andsnfficien -chohne; was added to i the. DH; up to 9 .2,- after which sufficient glycerine was; added to provide 30% of glycerine on the weight of the copolymer in the solution. The, solution Was thendiluted with water until it contained=8;%, copolymer solids and at this concentration hadta viscosity of 26 3 centipoisesat 25 C.
Unsized 70/34/7Zr/1OQ bright polyhexameth-ylene-adipamide warp yarnswere sized with the above: solution using the procedure described in aragraph 2. of Example 1;... The d y siz d yarns had properties similar to, those of the. ized yarns prepared as. described in Example III.
Ex mple V $i QQ1ul I SWB 1 n e a as, described in he. precedin am es x p a a. copolymer oiistyrene-maleie anhydride (containing 52% of combined styrene and"48% of combined maleic anhydride-methyl acid maleate). The resulting solutions were used to size 70/34/72/100 bright unsized polyhexamethylene adipamide warp yarns using the procedure described in paragraph 2 of Example I. The resulting sized yarns had propcrti'eswhich were similar to the corresponding sized yarns of the preceding examples.
Example VI Four hundred and fifty-two parts of a finely divided styrene-maleic anhydride-methyl acid maleate copolymer (containing 51% of combined styrene, 37.4% of combined maleic anhydride and 11.4% of combined methyl acid maleate) were added rapidly to 2548 parts of a Water solution containing 298 parts of choline at a temperature of C;. The resulting mixture was heated to a temperature of'90 C; over a period ofone hour and then maintained at that temperature for another hour, after which time the copolymer dissolved: in the. formo-- its choline salt. The resulting: solution was diluted; with water until it contained l8,%- of the cholinev salt of the copolymer. The pH of this solution was 7.44 (glass electrode) and the viscosity was 735 centipoises a t. C;
Seven ends of spun yarn prepared from polyacrylonitril'e staple fiberwere passed at the rate of 15 yardsper minute through the 18% solution of choline salt of the copolymer which was maintained at a temperature of 140 to 150 FL, after which the yarns were squeezed by passing them between squeeze rolls and applying a pressure or 6.66 pounds. per linear inch. About 15% of the cholinesalt was deposited on the yarn based on the yarn weight. The sized yarns were then dried by passing them over five rotating drying cans heated to temperatures of 180, 200, 200, 200 and 160 F., respectively.
The dry yarns were sufiiciently stiii ened to handle well in a loom and had excellent weaving efficiency when Woven in a conventional loom. Moreover, the size coating was tough and flexible and had excellent adhesion to the yarn. The size was readily removed from the yarns by Washing the woven fabric in warm water.
The sized" yarns possessed increased tensile strength and excellent abrasion resistance as indicated by the following; tests. A portion of one of the sized yarns was first conditioned for 24 hours at a relative humidityof and a temperature of '70 F. and then tested for tensile strength and; abrasion resistance. A control sam ple of unsized yarn was conditioned andtested in the same manner. The following table shows the results obtained.
Indicates number of' cycles required in abrasion resistance tester necessary to break the yarn.
Various modifications and changes may be made in the methods and compositions set forth in the foregoing description as will be apparent to those skilled in the art to which this invention appertains without-departing from the spirit and intent ofthis invention. It is to be understood therefore that the present invention is to be limited only by the scope of the appended claims.
Whatisclaimed is:
1 A method of sizing water-insoluble synthetic linear polymer yarns which comprises applying to said yarns a Water solution of a choline salt of a copolymer consisting of the copolymerization product of a polymerizable vinyl aromatic compound having a single C=CH2 group and an ethylene a, ,8 dicarboxylic compound selected from the group consisting of ethylene a, ,8 dicarboxylic anhydrides, ethylene a, B dicarboxylic acids and partial alkyl esters of said acids having not more than 3 carbon atoms in the alkyl group, and mixtures of, said dicarboxylic compounds, and drying said yarn preparatory to weaving the same.
2. A method oi sizing water-insoluble synthetic linear polymer yarns which comprises applying to said yarns a water solution of a choline salt of a copclymer consisting of the copolymerizaticn product of styrene and maleic anhydride, and drying said yarn preparatory to wearing the same.
3. A method of sizing water-insoluble synthetic linear polymer yarns which comprises applying to said yarns a Water solution of a choline salt of a copolymer consisting of the copolymerization productof styrene and a mixture of maleic anhydride and methyl acid maleate, said mixture containing from 50 to 99 mol per cent of maleic anhydride, and drying said yarn preparatory to weaving the same.
4. A method of sizing water-insoluble synthetic linear polyamide yarns which comprises applying to said yarns a water solution of a choline salt of a copolymer consisting of the copolymerization product of a polymerizable vinyl aromatic compound having a single C=CH2 group and an ethylene 02,3 dicarhoxylic compound selected from the group consisting of ethylene 11,5 dicarboxylic anhydrides, ethylene 11, 6 dicarboxylic acids and partial alkyl esters of said acids having not more than 3 carbon atoms in the 'alkyl group, and mixtures of said dicarboxylic compounds, and drying said yarns preparatory to weavingthe same.
5. A method substantially according to claim 4, butfurther characterizedin that the synthetic linear polyamide yarns are polyhexamethylene-adipamide yarns.
6. A method of sizing water-insoluble polyhexamethyl'ene-adipamide yarns which comprises applying to said yarns a water solution of a choline salt of a copolymer consisting of the copolymerization product of styrene and maleic anhydride, said solution being applied in an amount sufiicient to provide from 1 to 15% by weight of said choline salt on the weight of the yarns, and drying said yarns preparatory to solution contains an amount of glycerine sufficient to increase the viscosity of the solution over and above the viscosity obtained with the choline salt per se.
8. A method of sizing water-insoluble polyhexamethylene-adipamide yarns which comprises applying to said yarns a water solution of a choline salt of a copolymer consisting of the copolymerizationproduct of styrene and a mixture of maleic anhydride and methyl acid maleate, said mixture containing from 50 to 99 mol per cent of maleic anhydride, said solution being applied in an amount suflicient to provide from 1 to 15% by Weight of said choline salt on the weight of the yarns, and drying said yarns preparatory to weaving the same.
9. A method substantially according to claim 8, but further characterized in that the water solution contains an amount of glycerine sufficient to increase the viscosity of the solution over and above the viscosity obtained with the choline salt per se.
10. A method of sizing water-insoluble polyacrylonitrile yarns which comprises applying to said yarns a water solution of a choline salt of a copolymer consisting of the copolymerization product of a polymerizable vinyl aromatic compound having a single C=CH2 group and an ethylene 11, 3 dicarboxylic compound selected from the group consisting of ethylene 1,5 dicarboxylic anhydrides, ethylene 1,5 dicarboxylic acids and partial alkyl esters of said acids having not more than 3 carbon atoms in the alkyl group, and mixtures of said carboxylic compounds, said solution being supplied in an amount sufficient to provide from 1 to 15% of said choline salt on the weight of the yarns, and drying the yarns preparatory to weaving the same.
11. A method of sizing water-insoluble polyacrylonitrile yarns substantially according to claim 10, but further characterized in that the copolymer consists of the copolymerization product of styrene and maleic anhydride.
12. A method of sizing water-insoluble polyacrylonitrlle yarns substantially according to claim 10, but further characterized in that the copolymer consists of the copolymerization product of styrene and a mixture of maleic anhydride and methyl acid maleate, said mixture containing from to 99 mol per cent of maleic anhydride.
13. A choline salt of a copolymer consisting of the copolymerization product of a polymerizable vinyl aromatic compound having a single C=CH2 group and an ethylene 11,5 dicarboxylic compound selected from the group consisting of the ethylene 11,3 dicarboxylic anhydrides, ethylcm; 11,5 dicarboxylic acids and partial alkyl esters of said Iacids having not more than 3 carbon atoms in the alkyl group and mixtures of said dicarboxylic compounds.
14. A choline salt of a copoylmer consisting of the copolymerization product of styrene and maleic anhydride.
15. A water solution of a choline salt of a copolymer consisting of the copolymerization product of styrene and maleic anhydride, said solution containing sufiicient glycerine to increase the viscosity of the solution over and above the viscosity obtained with the choline salt per se.
16, A choline salt of a copolymer consisting of the copolymerization product of styrene and a mixture of maleic anhydride and methyl acid .maleate, said mixture containing from 50 to 99 mol per cent of maleic anhydride.
17. A water solution of a choline salt of a copolymer consisting of the copolymerization product of styrene and a mixture of maleic anhydride and methyl acid maleate, said mixture containing from 50 to 99 mol per cent of maleic anhydride, said solution containing suflicient glycerine to increase the viscosity of the solution over and above the viscosity obtained with the choline salt per se.
ELMER H. ROSSIN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 351,890 Waite Nov. 2, 1886 2,286,062 Condo et a1 June 9, 1942 2,469,407 Powers et al. May 10, 1949 FOREIGN PATENTS Number Country Date 726,670 Germany Oct. 17, 1942 OTHER REFERENCES Karrer, Organic Chemistry, 2nd ed., pages 234- 235.

Claims (1)

1. A METHOD OF SIZING WATER-INSOLUBLE SYNTHETIC LINEAR POLYMER YARNS WHICH COMPRISES APPLYING TO SAID YARNS A WATER SOLUTION OF A CHOLINE SALT OF A COPOLYMER CONSISTING OF THE COPOLYMERIZATION PRODUCT OF A POLYMERIZABLE VINYL AROMATIC COMPOUND HAVING A SINGLE <C=CH2 GROUP AND AN ETHYLENE A, B DICARBOXYLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ETHYLENE A, B DICARBOXYLIC ANHYDRIDES, ETHYLENE A, B DICARBOXYLIC ACIDS AND PARTIAL ALKYL ESTERS OF SAID ACIDS HAVING NOT MORE THAN 3 CARBON ATOMS IN THE ALKYL GROUP, AND MIXTURES OF SAID DICARBOXYLIC COMPOUNDS, AND DRYING SAID YARN PREPARATORY TO WEAVING THE SAME.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743193A (en) * 1953-08-10 1956-04-24 Eastman Kodak Co Treated cellulose organic acid ester fibers
US2848357A (en) * 1954-12-15 1958-08-19 Monsanto Chemicals Aqueous terpolymer sized nylon yarns
US2854357A (en) * 1955-09-06 1958-09-30 Monsanto Chemicals Sized nylon yarns and method for producing same
US2855387A (en) * 1954-12-20 1958-10-07 Monsanto Chemicals Terpolymer of maleic anhydride, vinyl acetate and alkyl acrylate
US2864808A (en) * 1954-12-15 1958-12-16 Monsanto Chemicals Terpolymer system
US3410720A (en) * 1965-07-12 1968-11-12 Monsanto Co Modified textile material resistant to penetration by aqueous media

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US351890A (en) * 1886-11-02 Compound for preparing starch or flour size for yarn
US2286062A (en) * 1940-06-01 1942-06-09 Du Pont Process for copolymerizing malkic anhydride and polymerizable vinyl compounds
DE726670C (en) * 1936-11-01 1942-10-27 Ig Farbenindustrie Ag Process for the production of salt-like condensation products
US2469407A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US351890A (en) * 1886-11-02 Compound for preparing starch or flour size for yarn
DE726670C (en) * 1936-11-01 1942-10-27 Ig Farbenindustrie Ag Process for the production of salt-like condensation products
US2286062A (en) * 1940-06-01 1942-06-09 Du Pont Process for copolymerizing malkic anhydride and polymerizable vinyl compounds
US2469407A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743193A (en) * 1953-08-10 1956-04-24 Eastman Kodak Co Treated cellulose organic acid ester fibers
US2848357A (en) * 1954-12-15 1958-08-19 Monsanto Chemicals Aqueous terpolymer sized nylon yarns
US2864808A (en) * 1954-12-15 1958-12-16 Monsanto Chemicals Terpolymer system
US2855387A (en) * 1954-12-20 1958-10-07 Monsanto Chemicals Terpolymer of maleic anhydride, vinyl acetate and alkyl acrylate
US2854357A (en) * 1955-09-06 1958-09-30 Monsanto Chemicals Sized nylon yarns and method for producing same
US3410720A (en) * 1965-07-12 1968-11-12 Monsanto Co Modified textile material resistant to penetration by aqueous media

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