US3337652A - Modification of stereoregular polyolefins - Google Patents

Modification of stereoregular polyolefins Download PDF

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US3337652A
US3337652A US406631A US40663164A US3337652A US 3337652 A US3337652 A US 3337652A US 406631 A US406631 A US 406631A US 40663164 A US40663164 A US 40663164A US 3337652 A US3337652 A US 3337652A
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polyolefin
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pyrrolidone
phosphoric acid
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

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  • polyethylene is vastly unsuitable for the production of textile fibers due to the relatively poor properties imparted to the product.
  • staple polyethylene fiber will not hold a crimp and this is necessary for textile processing.
  • it is useless to make a textured or stretch yarn from continuous filament polyethylene yarn because the characteristics imparted to the yarn are not maintained during weaving, dyeing, or ordinary use.
  • the material from which a fabric is made must be thermally stable before it may be subjected to ordinary use. It must not have a relatively low melting point, and the final fabric must not have a high degree of heat sensitivity, nor relatively soft mechanical properties at elevated temperatures.
  • These secondary polar modifiers are generally low molecular weight additives or possess melting points somewhat lower than the polyolefin itself. These secondary additives associate themselves with the primary hydrophilic polymeric modifier in such a way as to give synergistic combinations that are fusible at temperatures not exceeding the temperature of processing of the polyolefin (150 C. to 350 C.) and have improved processability and dyeability.
  • the use of the secondary polar additives improves brightness and clarity of the final film or luster and brightness of the final fiber.
  • the whiteness of the fiber is also improved because a smaller amount of the primary polymeric modifier, which is responsible for the off-white color, is utilized.
  • An economic advantage is also associated with the use of the present composition for a smaller amount of the more expensive primary polymeric modifier is utilized in the composition while still maintaining or improving the affinity of the composition for dyes.
  • stereoregular polyolefin structures with increased affinity for dyes comprising a matrix of a stereoregular polyolefin taken from the group consisting of (a) polypropylene, (b) polymethylpentene, and (o) polymethylbutene, said matrix having dispersed therein between 2 and 20% of a synergistic combination consisting of:
  • modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between C. and 350 C.
  • said modifying copolymer being selected from the group consisting of:
  • alkyl esters of polyhydroxy compounds (a) alkyl esters of polyhydroxy compounds, (b) alkyl esters of polyglycols, 60 to 4000 M, (c) alkyl ethers of polyglycols, 60 to 4000 M, (d) alkyl ethers of polyhydroxy compounds, (e) alkoxylated alkyl amines,
  • said synergistic combination being fusible at a temperature of processing of the polyolefin (150 to 350 C.) and forming a complex in said polyolefin.
  • stereoregular polyolefins which may be used within the concept of this invention include isotactic and syndiotactic polyolefins. These materials are usually made by utilizing stereo-specific catalysts which give polymers which are substantially linear and which develop a high degree of crystallinity.
  • a preferred class of my primary polymeric modifiers consists of copolymers derived from oxygen containing N-alkenyl heterocyclic monomers, particularly alkenyl substituted lactams, oxazolidone, oxazolidinone and morpholinone monomers.
  • This class of polymers is highly desirable because it has little or no basicity and has very high levels of affinity for a Wide range of dyes.
  • My preferred primary modifiers are neutral or only very slightly basic and yet in polyolefins, surprisingly, have higher dyability with anionic (acid) dyes than the much more basic polymeric modifiers.
  • the alkenyl substituted nitrogen is part of an internal amide group and is essentially neutral. Additional ring and substituted oxygen containing groups are more acidic than the substituted amide nitrogen and further reduce basicity.
  • the secondary polar additives which may be used with the primary modifier to give synergistic combinations include the following:
  • Alkyl esters of polyhydroxy compounds such as:
  • Example I prepared discs of polyolefin in the following manner utilizing as modifier N-vinyl-S-methyl-2-oxazo1idinone in a balanced weight fraction copolymer with vinyl acetate (VOOM/Va) (Devlex A515, Dow Chemical Co.) alone and in combination with (GMS) g1ycerol monostearate.
  • VOOM/Va vinyl acetate
  • GMS g1ycerol monostearate
  • the mixtures were then air dried (to remove some solvent) and then heated in a drying oven at 80 C. until all of the solvent had been removed.
  • Each of the dried mixtures was prepared in the form of a disc in the following manner:
  • the powder of each sample was spread uniformly in a circular shouldered Pyrex glass dish with an inside diameter of 4 inches.
  • the dishes were then covered by an inner nesting circular shouldered Pyrex glass dish with a bottom outer separation rib projecting downwardly about 0.05 inch.
  • the assembly weighted with a preheated 5 pound weight was then placed in an oven at 250 C. for 6 to minutes. Then the weight was removed and the assembly was placed in a refrigerator at about 4 C. to cool.
  • the assembly dishes were then separated to give a fuzed disc.
  • AMRColour Index Acid Red 182, AR-Colour Index, Acid Red 127, DO-Colour Index, Disperse Orange 3, and DLVLatyl Violet 2R, Disperse Dye.
  • the dye baths were each heated over an hour to a temperature of about 95 C. and the temperature was"
  • an improvement in dyeability is achieved, although accompanied by a 20% reduction in the amount of copolymer utilized in the composition if a selected lower melting additive is substituted in part for the copolymer.
  • higher levels of dispersion and dyeability may be achieved with higher levels of addition. This is surprising because when the primary polymeric modifiers are utilized alone, one obtains poor dispersibility with higher levels of addition.
  • Example 2 In this example, tests similar to those of Example 1 were performed except that, in this case, the modifier containing polyolefin was extruded into fiber, drawn and then dyed using conventional equipment and processes.
  • the formulation was melt mixed in a continuous screw extruder, forced through a 60 mil die at 260 C. and collected at ambient temperature on a reel as a 30 denier filament.
  • the filament was then heat stretched 300% to give a strong, oriented 10 denier fiber.
  • Fiber skeins Were then scoured with detergent at 140 F., and dyed at the boil for one hour at 2-0/ 1 bath to fiber ratio.
  • the synergistic combination which was utilized as the modifier, consisted of a copolymer, 50% vinyl methyloxazolidinone with 50% vinyl acetate (VOOM/Va), in combination with (GMS)-glycerol monostearate.
  • Percent VOOM/Va 4 9.
  • Percent GMS 1 1. Dispersibility in Polyolefin Excellent Good/excellent.
  • Example 3 dispersion and depth of coloration. The results of these tests are tabulated below:
  • the modifier containing polyolefin was extruded into fiber, drawn, and then dyed using conventional equipment and processes.
  • the synergistic combination which was utilized as the modifier, consisted of a copolymer, 70% vinyl pyrrolidone with vinyl acetate (VP/Va), in combination with Dyeability with dyes Dispersibillty Secondary Additive in Polyolefin (b) a DLV, DO AMR, AR
  • ammonium chloride Tertiigry stearyl amine with 15 moles ethylene Excellent Dark Do.
  • the dispersibility was only fair while the depth of coloration lies in the medium range.
  • the dispersability was good to excellent and the depth of coloration was increased, in some cases, from medium to medium/dark and dark. This improvement, in all cases, is the direct result of the synergistic combination in the olefinic composition as taught by the present concept.
  • Example 5 I prepared discs using as modifiers the copolymers enumerated below, both alone, and in combination with selected secondary additives. The discs were dyed following the procedure heretofore described and the finished discs were judged subjectively In accordance with the procedure set forth in Example for uniformity of dispersion and depth of color.
  • my modifiers with polyolefins are readily available. They may be combined during formation of the polymeric modifier or during actual polymerization of the polyolefin, with or without melting. They may be added to freshly polymerized polyolefin, which is still in solution in a suitable solvent, in the powdered form, or as a solution in a compatible solvent, or merely as a dispersion. They may be added to the polyolefin during precipitation, washing, neutralizing or compounding of the freshly prepared polyolefin prior to drying.
  • modifiers may also be melt mixed during processing or blending of the polymer prior to use in extension of fiber, film, coating or plastic. It may also be added as a liquid or powder to finely ground or micronized polyolefin polymers and then melt dispersed in situ during hot dip or spray coating or during spreading and heat coating operation. They may be incorporated in polyolefin solutions or emulsion and then applied to surfaces with or without heating.
  • the level of additionto the polyolefin of the synergistic combination heretofore described should be between 2 and 20% of the weight of the overall composition. If less than 2% is utilized, significant improvement will not be achieved in dyeability. If an amount greater than 20% is added to the polyolefin, many of the physical properties of the final product will be adversely aifected. These include loss of strength and a lower resistance to repeated flexing.
  • the synergistic combination it is desirable to use a minimum amount of secondary lower molecular weight additive to minimize any adverse effects on the properties of the fibers.
  • An addition of the secondary additive above the limit stated (50%) may be in excess of that required to associate and complex with the primary modifier which makes up 50% to by weight of the synergistic combination. As a result, the excess secondary additive may sweat out of the polyolefin and interfere with processing.
  • the addition of the secondary additive not go below 5% by weight because below this level very little improvement is achieved in dyeability.
  • the primary polymeric modifier of the combination should comprise at least 25% by weight of an oxygen containing N-heterocycle monomeric unit in combination with not more than 75% of an ethylenically unsaturated monomeric unit having no basic groups. If the latter unit is present in an amount over 75 you obtain very low levels of dyeability. It is therefore necessary to use very excessive amounts of modifier to achieve desired results.
  • the ethylenically unsaturated unit is present between 50 to 75 by weight, higher levels of addition are required.
  • the melting point of the overall composition may be reduced to such an extent that the modifier, particularly at higher levels of addition, may give some problems 111 processing.
  • hydrophilic polymeric primary modifiers as part of my synergistic combination which may be soluble in either water or an oxygenated solvent but which are not soluble in the polyolefin.
  • modifiers which are fusible and can be dispersed in the polyolefin.
  • My hydrophilic primary polymeric modifiers must be fusible with the polyolefin. This is necessary for the formation of a continuous network of modifier throughout the polyolefin in order to permit dye penetration and efiicient coordination of the dye and modifier throughout the film or fiber.
  • the synergistic combination of this invention may be used to increase opacity and the afiinity of the polyolefin for finishes. They may also be used to improve the printability of the polyolefin, increase the adhesion of the polyolefin to other materials, or to reduce the overall static propensity of the final product. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced th erwise than as specifically described.
  • a polymeric composition having improved aflinity for dyes consisting essentially of:
  • a matrix of stereoregular polyolefin taken from the group consisting of: polypropylene, polymethylpentene, and polymethylbutene;
  • said matrix having dispersed therein between 2 and 20 percent by weight of a synergistic combination consisting of:
  • modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between 150 12 C. and 350 C.
  • said modifying copolymer being selected from the group consisting of:
  • N-vinyl p-yrrolidone/ 10% ethylene said percent being by weight
  • composition of claim 1 wherein:
  • said copolymer consists of 50% by weight N-vinyl methyloxazolidinone in combination with 50% by Weight of vinyl acetate, and said lower molecular weight organic substance consists of fatty esters of polyhydroxy compounds.
  • composition of claim 1 wherein:
  • said copolymer consists of 30 to 70% by Weight of N-vinyl pyrrolidone in combination with 30 to 70% vinyl acetate, and said lower molecular weight organic substance consists of alkoxylated fatty amines.
  • composition of claim 1 wherein:
  • said copolymer consists of 60% by weight of N-vinyl morpholinone in combination .with 40% by weight of methyl acrylate, and said lower molecular weight organic substance consists of fatty esters of polyglycols.
  • composition of claim 1 wherein: References Cited said copolymer consists of 70% by weight of N-vinyl UNITED STATES PATENTS pyrrolidone in combination with 30% by weight of ethyl acrylate, and said lower molecular weight 3,153,680 10/1964 Guisfiniani et 260 897 organic substance consists of fatty ethers of poly- 5 FOREIGN PATENTS glycols. l
  • composition of claim 1 wherein: 83416O 5/1960 Great Bntam' said copolymer consists of 60% by weight of N-acrylyl pyrrolidone in combination with 40% by weight MURRAY TILLMAN Pnmary Exammer' ethyl acrylamide, and said lower molecular Weight 10 D. J. BREZNER, Assistant Examiner. organic substance consists of alkyl phosphoric acid.

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Description

United States Patent M 3,337,652 MODIFICATION OF STEREOREGULAR POLYOLEFINS Jack J. Press, 12-18 E. Laurelton Parkway, Teaneck, NJ. 07666 No Drawing. Filed Oct. 26, 1964, Ser. No. 406,631 6 Claims. (Cl. 260-895) I particularly, this invention relates to polymeric compositions having improved afiinity for dyes, said compositions containing a major amount of stereoregular polyolefins.
It is known that polyethylene is vastly unsuitable for the production of textile fibers due to the relatively poor properties imparted to the product. For one thing, staple polyethylene fiber will not hold a crimp and this is necessary for textile processing. For another, it is useless to make a textured or stretch yarn from continuous filament polyethylene yarn because the characteristics imparted to the yarn are not maintained during weaving, dyeing, or ordinary use. Further, the material from which a fabric is made must be thermally stable before it may be subjected to ordinary use. It must not have a relatively low melting point, and the final fabric must not have a high degree of heat sensitivity, nor relatively soft mechanical properties at elevated temperatures. However, the thermal properties of a polyethylene fabric are such that it is impossible to subject it to ordinary ironing without physically damagingthe fabric and it has been found to shrink in the conventional dryer. As is apparent from the foregoing, polyethylene cannot be utilized in the manufacture of everyday fabrics for ordinary use.
In recent times, it has been found that certain linearcrystalline hydrocarbon polymers containing stereoregular macromolecules and having melting points between 150 and 300 C. can be used for the production of textile fibers without the inherent diificulties encountered with the use of polyethylene polymers for this purpose. Aside from melting point differences, polypropylene with a tertiary carbon and a methyl side chain, crystallizes differently and has a much higher resilience and elasticity. These properties are esesntial in generally useful textile fiber. Further, polymers of olefinic hydrocarbons containing stereoregular macromolecules, such as polypropylene, polymethylpentene, and polymethylbutene, offer considerable advantages in the production of fibers, particularly because of their good mechanical properties and light weight. However, such polmyers have not been satisfactory because of their poor afiinity for dyes, this poor afiinity being due to the particular chemical nature of such polyolefinic hydrocarbons.
Many processes have been proposed in order to improve the aflinity of such polyolefinic hydrocarbons for dyes, such as the addition of soluble solid substances to the molten polyolefin before spinning. The addition of basic substances facilitates dyeing with acid dyes, whereas the addition of acid substances favors dyeing with basic dyes. However, such processes have not been completely satisfactory because soluble modifiers interfere with crystallization, impair strength and thermal stability, and are not sufficiently available in the amorphous regions where dyeing takes place.
It has also been proposed to increase the afiinity of dyes for polyolefin fibers by grafting monomers onto the fibers after subjecting the fibers to a preliminary peroxida- Patented Aug. 22, 1967 tion or to high energy radiation. When such processes are applied to the polyolefin after it is in filamentary form the surface properties of the grafted fibers are considerably modified and the dye receptivity is improved. However, when such processes are applied to highly crystalline filaments, any grafting onto the preformed fibers takes place only at the surface. Therefore, subsequent dyeing is limited to the surface portion of the fiber and the dye does not penetrate inside the fiber.
In my copending application titled Modification of Stereoregular Polyolefins With Hydrophilic Copolymers, Ser. No. 400,612, filed Sept. 30, 1964, I teach that the affinity of polyolefins for dyes may be enhanced through the use of selected hydrophilic, nonsoluble copolymers consisting of oxygen containing N-heterocyclic monomeric units in combination with neutral ethylenically unsaturated monomeric units. The level of addition ranges from 2 to 20% by weight based on the polyolefin.
Now, I have discovered that the affinity of polyolefins for dyes may be further improved, over and above the improvement achieved with the above polymeric materials, if the modifier incorporated in the polyolefin is one of a specified class of copolymers in combination with selected class of secondary polar additives. Surprisingly, I have found that even at low levels of addition, I obtain synergistic improvements in dyeability by replacing between 5% and 50%, preferably only up to 25%, of the above primary hydrophilic copolymeric modifiers with selected liquid, wax, or polymeric secondary polar modifiers having negligible dyeability by themselves.
These secondary polar modifiers are generally low molecular weight additives or possess melting points somewhat lower than the polyolefin itself. These secondary additives associate themselves with the primary hydrophilic polymeric modifier in such a way as to give synergistic combinations that are fusible at temperatures not exceeding the temperature of processing of the polyolefin (150 C. to 350 C.) and have improved processability and dyeability.
As an added advantage, the use of the secondary polar additives improves brightness and clarity of the final film or luster and brightness of the final fiber. The whiteness of the fiber is also improved because a smaller amount of the primary polymeric modifier, which is responsible for the off-white color, is utilized. There is also an improvement in the ease and uniformity of dispersion of the composition. There is less blockage of filters and spinerette holes by the composition and this tends towards an improvement in processability. An economic advantage is also associated with the use of the present composition for a smaller amount of the more expensive primary polymeric modifier is utilized in the composition while still maintaining or improving the affinity of the composition for dyes.
It is therefore an object of this invention to provide polymeric compositions having improved affinity for dyes devoid of difficulties of the prior art.
Included in this invention are stereoregular polyolefin structures with increased affinity for dyes comprising a matrix of a stereoregular polyolefin taken from the group consisting of (a) polypropylene, (b) polymethylpentene, and (o) polymethylbutene, said matrix having dispersed therein between 2 and 20% of a synergistic combination consisting of:
(l) 50 to of a modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between C. and 350 C., said modifying copolymer being selected from the group consisting of:
(a) 30 to 70% N-vinyl pyrro1idone/30 to 70% vinyl acetate,
(b) 60% N-vinyl pyrrolidone/40% vinyl methyl ether,
(c) 80% N-vinyl pyrrolidone/20% styrene,
(d) 70% N-vinyl pyrrolidone/30% ethyl acrylate,
(e) 70% N-isoprenyl pyrrolidone/30% ethylene oxide,
(f) 60% N-acrylyl pyrrolidone/40% ethyl acrylamide,
all said percentages being percent by weight; and
(2) 5 to 50% of a lower molecular weight organic substance having at least one alkyl group with 6 to 30 carbons, said substance selected from the group consisting of:
(a) alkyl esters of polyhydroxy compounds, (b) alkyl esters of polyglycols, 60 to 4000 M, (c) alkyl ethers of polyglycols, 60 to 4000 M, (d) alkyl ethers of polyhydroxy compounds, (e) alkoxylated alkyl amines,
(f) di (2ethylhexyl)phosphoric acid,
(g) stearyl phosphoric acid,
(h) salts of dodecylbenzene sulfonic acid,
(i) salts of naphthalene sulfonic acid,
(j) N-lauryl trimethylene diamine, and
(k) salts of di (2-ethylhexyl) phosphoric acid,
said synergistic combination being fusible at a temperature of processing of the polyolefin (150 to 350 C.) and forming a complex in said polyolefin.
The stereoregular polyolefins which may be used within the concept of this invention include isotactic and syndiotactic polyolefins. These materials are usually made by utilizing stereo-specific catalysts which give polymers which are substantially linear and which develop a high degree of crystallinity.
A preferred class of my primary polymeric modifiers consists of copolymers derived from oxygen containing N-alkenyl heterocyclic monomers, particularly alkenyl substituted lactams, oxazolidone, oxazolidinone and morpholinone monomers. This class of polymers is highly desirable because it has little or no basicity and has very high levels of affinity for a Wide range of dyes. My preferred primary modifiers are neutral or only very slightly basic and yet in polyolefins, surprisingly, have higher dyability with anionic (acid) dyes than the much more basic polymeric modifiers. In these monomers and polymers, the alkenyl substituted nitrogen is part of an internal amide group and is essentially neutral. Additional ring and substituted oxygen containing groups are more acidic than the substituted amide nitrogen and further reduce basicity.
The secondary polar additives which may be used with the primary modifier to give synergistic combinations include the following:
(1) Alkyl esters of polyhydroxy compounds such as:
(21) glycerol monostearate, (b) glycerol distearate, (c) glycerol tristearate, (d) glycerol mono/dilaurate, (e) sorbitan monostearate, and (f) sorbitan dilaurate. (2) Alkyl esters of polyglycols (M 60 to 4000) such as:
(a) ethylene glycol monostearate, (b) polyethylene glycol 200 monostearate, (c) polyethylene glycol 200 distearate,
(d) polyethylene glycol 4000 distearate, (e) propylene glycol monostearate, (f) polypropylene glycol 600 monooctate, (g) butylene glycol monostearate, (h) polybutylene glycol 800 monostearate, (i) hexylene glycol monooctate, (j) hexylene glycol adipate, and (k) poly(hexylene glycol adipate) 800 to 5000 M. (3) Alkyl ethers of polyglycols (60 to 4000 M) such as:
(a) ethylene glycol monostearyl ether, (b) ethylene glycol monolauryl ether, (c) polyethylene glycol 200 monostearyl ether, (01) polyethylene glycol 200 monolauryl ether, (e) polyethylene glycol 200 distearyl ether, (f) polyethylene glycol 200 monononylphenol ether, (g) polyethylene glycol 4000 monostearyl ether, (h) polyethylene glycol 4000 distearyl ether, (i) propylene glycol monostearyl ether, (j) propylene glycol monolauryl ether, (k) polypropylene glycol 600 monolauryl ether, (1) butylene glycol monostearyl ether, (m) hexylene glycol monooctyl ether. (4) Alkyl ethers of polyhydroxy compounds such as:
(a) glycerol monostearyl ether, (b) glycerol distearyl ether, (0) glycerol dilauryl ether, (d) glycerol dihexyl ether, (e) sorbitan monostearyl ether, and (f) sorbitan dioctyl ether. (5) Alkyloxylated amines such as:
(a) tertiary stearyl amine with '15 moles ethylene oxide, (b) tertiary stearyl di (hydroxyethyl) amine, (c) tertiary stearyl di (hydroxypropyl) amine, (d) tertiary stearyl di (hydroxybutyl) amine, (e) tertiary lauryl di (hydroxypropyl) amine, (f) tertiary lauryl amine with 15 moles of ethylene oxide, (g) tertiary stearyl amine with 15 moles of propylene oxide, (h) quaternary stearyl di (hydroxyethyl) methyl ammonium sulfate, (i) quaternary stearyl di (hydroxyethyl) methyl ammonium chloride, and (j) quaternary stearyl methyl ammonium chloride with 15 moles of ethylene oxide. (6) Alkyl phosphoric acids and salts such as:
(a) di (Z-ethylhexyl) phosphoric acid, (b) sodium salt of di (2-ethylhexyl) phosphoric acid, (c) potassium salt of di (2-ethylhexy1) phosphoric acid, (d) isopropyl amine salt of di (2-ethylhexyl) phosphoric acid, (e) triethanolamine salt of di (2-ethylhexyl) phosphoric acid, (f) monostearyl phosphoric acid, (g) potassium salt of monostearyl phosphoric acid, (h) distearyl phosphoric acid, (i) sodium salt of distearyl phosphoric acid, (j) monolauryl phosphoric acid, (k) lauryl ethyl phosphoric acid, and (l) dioctyl phosphoric acid. (7) Miscellaneous compounds such as:
(a) N-lauryl trimethylene amine, (b) N-stearyl trimethylene diamine, (c) perfluorononylic acid, (d) dihydrogenated tallow-methyl amine, (e) stearic acid, (f) alkylene (2 to 4 carbon) oxide derivatives of alkyl (6 to 30 carbons) amide, (g) polyalkylene glycols having 2 to 4 carbons and 4 to 50 alkylene oxide groups. (8) Alkyl and aryl sulfonic acids and salts such as:
(a) dodecylbenzene sulfonic acid,
(b) sodium salt of dodecylbenzene sulfonic acid,
(c) potassium salt of dodecylbcnzene sulfonic acid,
(d) isopropyl amine salt of dodecylbenzene sulfonic acid,
(e) trialkanolamine salt of dodecylbenzene sulfonic acid,
(f) lauryl sulfonic acid,
maintained for 2 hours. The dye samples were then rinsed, given a minute 95 C. launder in the dye pot at a 20 to 1 bath to sample ratio with a 5 gram per gallon Tide detergent solution. The samples were then rinsed, dried, and judged for depth and uniformity of shades. The results of such test are set forth in the table below:
All percentages are by weight.
(g) sodium salt of lauryl sulfonic acid,
(h) naphthalene sulfonic acid,
(i) sodium salt of naphthalene sulfonic acid,
(j) potassium salt of naphthalene sulfonic acid, and
(k) formaldehyde condensate of naphthalene sulfonic acid.
The following examples set forth typical synergistic combinations of primary and secondary modifiers falling within the concept of this invention. Each is followed by results quite clearly illustrating the synergism en countered when each combination is introduced into the stereoregular polyolefin.
Example I I prepared discs of polyolefin in the following manner utilizing as modifier N-vinyl-S-methyl-2-oxazo1idinone in a balanced weight fraction copolymer with vinyl acetate (VOOM/Va) (Devlex A515, Dow Chemical Co.) alone and in combination with (GMS) g1ycerol monostearate.
Various percent additions, as indicated in the table which follows, were each uniformly mixed, as solutions or as finely divided solid, with separate 5 gram samples of a finely powdered (SO -200 mesh) commercial, unin hibited isotactic polypropylene (molecular weight about 350,000, melting point about 170 C., melt index of 3, and isotacticity of 95%).
The mixtures were then air dried (to remove some solvent) and then heated in a drying oven at 80 C. until all of the solvent had been removed.
Each of the dried mixtures was prepared in the form of a disc in the following manner: The powder of each sample Was spread uniformly in a circular shouldered Pyrex glass dish with an inside diameter of 4 inches. The dishes were then covered by an inner nesting circular shouldered Pyrex glass dish with a bottom outer separation rib projecting downwardly about 0.05 inch. The assembly weighted with a preheated 5 pound weight was then placed in an oven at 250 C. for 6 to minutes. Then the weight was removed and the assembly was placed in a refrigerator at about 4 C. to cool. The assembly dishes were then separated to give a fuzed disc.
A portion of each of the fusion discs after water rinsing were individually placed in a separate dye pot together with times its weight of distilled Water and from 0.5 to 2% of the dye on the weight of the sample.
The following dyes were utilized in separate baths, viz.
AMRColour Index, Acid Red 182, AR-Colour Index, Acid Red 127, DO-Colour Index, Disperse Orange 3, and DLVLatyl Violet 2R, Disperse Dye.
The dye baths were each heated over an hour to a temperature of about 95 C. and the temperature was" As indicated, an improvement in dyeability is achieved, although accompanied by a 20% reduction in the amount of copolymer utilized in the composition if a selected lower melting additive is substituted in part for the copolymer. As an added advantage, higher levels of dispersion and dyeability may be achieved with higher levels of addition. This is surprising because when the primary polymeric modifiers are utilized alone, one obtains poor dispersibility with higher levels of addition.
Example 2 In this example, tests similar to those of Example 1 were performed except that, in this case, the modifier containing polyolefin was extruded into fiber, drawn and then dyed using conventional equipment and processes.
The formulation was melt mixed in a continuous screw extruder, forced through a 60 mil die at 260 C. and collected at ambient temperature on a reel as a 30 denier filament.
The filament was then heat stretched 300% to give a strong, oriented 10 denier fiber. Fiber skeins Were then scoured with detergent at 140 F., and dyed at the boil for one hour at 2-0/ 1 bath to fiber ratio.
The fiber, as spun, was judged subjectively for uniformity of dispersion of the modifiers in the polyolefin and the dyeings were judged for level of dyeability (depth of shade) with the following dyes:
DLV-Latyl Violet 2R, Disperse Dye, DO-Colour Index, Disperse Orange 3, AMR-Colour Index, Acid Red 182, AR-Colour Index, Acid Red 127.
The synergistic combination, which was utilized as the modifier, consisted of a copolymer, 50% vinyl methyloxazolidinone with 50% vinyl acetate (VOOM/Va), in combination with (GMS)-glycerol monostearate.
TABLE* Percent VOOM/Va; 4 9. Percent GMS 1 1. Dispersibility in Polyolefin Excellent Good/excellent.
Dyeability with:
(a) DLV,DO Medium/dark--. Dark.
(b) MAR,AR Medium Medium/dark.
All percentages being by weight.
As indicated above, one obtains improvement in dyeability even when the combination is reduced to fiber form.
Example 3 dispersion and depth of coloration. The results of these tests are tabulated below:
2, the modifier containing polyolefin was extruded into fiber, drawn, and then dyed using conventional equipment and processes.
The synergistic combination, which was utilized as the modifier, consisted of a copolymer, 70% vinyl pyrrolidone with vinyl acetate (VP/Va), in combination with Dyeability with dyes Dispersibillty Secondary Additive in Polyolefin (b) a DLV, DO AMR, AR
Blank Fair Polyethylene glycol 200 nonylphenol. Good/excellent. Ethylene glycol monostearate Excellent Polyethylene glycol 200 distearate .do Do. Dihydrogenated tallow methyl amine Good Medium/dark. Lauryl di (hydroxy propyl) amine Good/excellent. Medium. Tertiary lauryl amine with 15 moles of ethyl- Excellent Medium/dark.
ene oxide. Quaternary hydrogenated tallow di (hy- ...do do D0.
droxymethyl) methyl ammonium sulfate. Stearyl di (hydroxy ethyl) amine. Good/excellent.. do Medium. Quaternary stearyl di (hydroxyethyl) methyl -do Medium/dark... Medium/dark.
ammonium chloride. Tertiigry stearyl amine with 15 moles ethylene Excellent Dark Do.
ox e. Di (2'ethylhexyl) phosphoric acid. "do... do Medium. Stearic acid do do D0.
Note that, in all cases, the affinity of the polyolefin composition for dyes was increased by addition of a (TSA)tertiary stearyl amine with 15 moles ethylene All percentages being by weight.
selected secondary additive. In the case of the blank, the dispersibility was only fair while the depth of coloration lies in the medium range. With the addition of the selected secondary additive, the dispersability was good to excellent and the depth of coloration was increased, in some cases, from medium to medium/dark and dark. This improvement, in all cases, is the direct result of the synergistic combination in the olefinic composition as taught by the present concept.
Example 4 sition.
Example 5 In accordance with Example I, I prepared discs using as modifiers the copolymers enumerated below, both alone, and in combination with selected secondary additives. The discs were dyed following the procedure heretofore described and the finished discs were judged subjectively In accordance with the procedure set forth in Example for uniformity of dispersion and depth of color.
Dyeability with dyes Copolymer Percent Percent Secondary Additive Percent* Dispersibility Ratio Addition Addition in Polyolefin (a) DLV, DO (b) AMR, AR
(a) N-vinyl pyrrolidone- /40 4 Light/medium.. Light.
vinyl methyl ether. (13).... do 60/40 4 Ethylene glycol 1 Excellent Medium/dark Medium.
monostearate. (c) N-ginyl pyrrolidone- 80/20 4 Light/mediunn, Light.
5 yrene. (d) -do 80/20 4 Di(2 ethylhexyl) 1 Good Medium/dark Medium.
phosphoric acid. (e)- N-vinylpyrrolidone- 70130 4 Medium- Light.
ethyl acrylate. (t) d0 /30 4 Tertiary stearyl 1 Excellent Dark. Medium/dark.
amine with 15 moles of ethylene oxide. (g) N-isoprenyl pyrroli- 70/30 4 Medium Light.
done-ethylene oxide. (h) d0 70/30 4 Ethylene glycol 1 Excellent Dark. Medium/dark.
distearate. (i) N-acrylyl pyrroli- 60/40 4 Medium Light.
done ethyl acrylamide.
' Dyeability with dyes Gopolymer Percent? Percent* Secondary Additive Percent? Dispersibility Ratio Addition Addition in Polyolefin (a) DLV, DO (1)) AMR, AR
(j) .d 60/40 4 Dihydrogenated l Good/exeellent Dark Medium.
tallow-methyl amine. (k) N-vinyl oxazolidone- 60/40 4 Medium Light.
aerylonitrile. (l) v do 60/40 4 Stearyl di-(hydroxy 1 Good/excellent. Dark Medium.
ethyl) amine. (m) N-vinyl methyl 70/30 7 4 Light/medium. Light.
oxazolidinonean na a ami e. (n) "333m 70/30 4 Darlg Medium/dark. (0),--- N-vinyl morpho- 60/40 4 Medlum Light.
linerl ile-melthtyl me ac a e. v (p) .do 60/40 4 Tertiary stearyl 1 Good/excellent" Medium/dark--. Medium.
amine with moles ethylene oxide. I (q) N-vinyl l pyrrolidone- 90/10 4 Medium Light/medium. eth one I (r) "iii; 90/10 4 Tertiary stearyl 1 Good Medium/dark- Medium.
amine with 15 moles ethylene oxide.
*All percentages being by weight.
Note that the affinity of the polyolefin for dyes is increased, when one of the above selected secondary additives are utilized, in conjunction with the copolymers listed, to modify the composition of the polyolefin. This being an improvement, in all cases, over the use of the copolymer alone for the same purpose.
Many alternate methods of combining my modifiers with polyolefins are readily available. They may be combined during formation of the polymeric modifier or during actual polymerization of the polyolefin, with or without melting. They may be added to freshly polymerized polyolefin, which is still in solution in a suitable solvent, in the powdered form, or as a solution in a compatible solvent, or merely as a dispersion. They may be added to the polyolefin during precipitation, washing, neutralizing or compounding of the freshly prepared polyolefin prior to drying. This may be accomplished by adding the modifier as a powder or as a solution which is a non-solvent for the The modifiers may also be melt mixed during processing or blending of the polymer prior to use in extension of fiber, film, coating or plastic. It may also be added as a liquid or powder to finely ground or micronized polyolefin polymers and then melt dispersed in situ during hot dip or spray coating or during spreading and heat coating operation. They may be incorporated in polyolefin solutions or emulsion and then applied to surfaces with or without heating.
In may copending application, I show the use of selected hydrophilic polymers to improve the dyeability of the stereoregular, high melting polyolefin. The level of addition of these primary modifiers should be between 2 and of the weight of the overall composition including polyolefin. As shown and substantiated herein by the results which follow each of the examples, the utility of these primary modifiers may be vastly improved by replacing from 5 to 50%, preferably not more than of the primary modifier by a secondary modifier, heretofore listed, which has limited utility by itself.
The synergistic effects of the combinations, as taught, on the polyolefin includes vastly improved dyeability. However, the listed secondary modifiers also enhance the compatibility of the primary polymeric modifier in the polyolefin. These advantages are also accompanied by improvements in processing of the overall combination and, surprisingly, many infusable primary modifiers are rendered fusible and may be utilized within the concept of this invention to improve the dyeability of a polyolefin structure as heretofore taught.
The level of additionto the polyolefin of the synergistic combination heretofore described should be between 2 and 20% of the weight of the overall composition. If less than 2% is utilized, significant improvement will not be achieved in dyeability. If an amount greater than 20% is added to the polyolefin, many of the physical properties of the final product will be adversely aifected. These include loss of strength and a lower resistance to repeated flexing.
As to the synergistic combination, it is desirable to use a minimum amount of secondary lower molecular weight additive to minimize any adverse effects on the properties of the fibers. An addition of the secondary additive above the limit stated (50%) may be in excess of that required to associate and complex with the primary modifier which makes up 50% to by weight of the synergistic combination. As a result, the excess secondary additive may sweat out of the polyolefin and interfere with processing.
I prefer however to use not more than 25% by weight of the secondary polar additive, since even between 25 and 50% there might be excessive reduction in the melting point of the combination and this would result in difficulties in processing, particularly drying.
It is also preferred that the addition of the secondary additive not go below 5% by weight because below this level very little improvement is achieved in dyeability.
The primary polymeric modifier of the combination should comprise at least 25% by weight of an oxygen containing N-heterocycle monomeric unit in combination with not more than 75% of an ethylenically unsaturated monomeric unit having no basic groups. If the latter unit is present in an amount over 75 you obtain very low levels of dyeability. It is therefore necessary to use very excessive amounts of modifier to achieve desired results.
If the ethylenically unsaturated unit is present between 50 to 75 by weight, higher levels of addition are required. The melting point of the overall composition may be reduced to such an extent that the modifier, particularly at higher levels of addition, may give some problems 111 processing.
However, if the latter monomeric units are present below 50% by weight of the overall primary modifier, lower levels of addition can be used to improve dyeability without processing problems resulting from an excessive reduction in melting point. This represents the optimum from a commercial point of view.
Under present concept, I prefer hydrophilic polymeric primary modifiers as part of my synergistic combination which may be soluble in either water or an oxygenated solvent but which are not soluble in the polyolefin. I do prefer modifiers which are fusible and can be dispersed in the polyolefin.
Prior experience with comparatively less hydrophobic fiber forming polymers, such as polyacrylonitrile polymers and polyamides, have shown that the use of hydro philic, water soluble or dispersible, modifiers is impractical. Mainly, because excessive amount of the modifier are leached out in scouring and dyeing processes. Surprisingly, I have found that my hydrophilic polymeric modifiers, when melt dispersed in the more hydrophobic polyolefin, have good dispersion stability and are not susceptible to leachage.
I have found that at comparatively low levels of addition, my synergistic combination, as taught, confers good dyea bility on the polyolefin Without the necessity for costly and sometimes impractical post treatments.
My hydrophilic primary polymeric modifiers must be fusible with the polyolefin. This is necessary for the formation of a continuous network of modifier throughout the polyolefin in order to permit dye penetration and efiicient coordination of the dye and modifier throughout the film or fiber.
The use of a non-fusible cross-linked modifier, which results in poor dispersion, is ineffectual. The required modifier network in such a case cannot be formed and the discrete, separate particles are surrounded by unmodified areas within the polyolefin matrix. As as result, dyeing is limited to the fiber surface and the dye cannot penetrate into the interior of the fiber where it is most desired.
It is generally recognized that dyeing takes place almost entirely in the more open and readily accessible amorphous areas. When a soluble modifier is utilized, it is usually spread throughout the amorphous and crystalline areas of the polyolefin. As a result, the modifier in the crystalline areas is not available for improvement in dyeability. It also interferes with crystallization and adversely affects strength and thermal stability. However, my synergistic combination is not sufficiently compatible to be a part of the more uniform and denser crystalline areas. It appears to concentrate in the more amorphous areas where it is necessary for dyeability. It has also been found that an increase in molecular weight of my modifiers, further reduces compatibility with stereoregular polyolefins and promotes concentration of the modifier in the more amorphous regions where it may improve the dyeability of the polyolefinic matrix.
Obviously, many modifications and variations of the present invention are possible in the light of the above teaching. For instance, the synergistic combination of this invention may be used to increase opacity and the afiinity of the polyolefin for finishes. They may also be used to improve the printability of the polyolefin, increase the adhesion of the polyolefin to other materials, or to reduce the overall static propensity of the final product. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced th erwise than as specifically described.
I claim:
1. A polymeric composition having improved aflinity for dyes consisting essentially of:
a matrix of stereoregular polyolefin taken from the group consisting of: polypropylene, polymethylpentene, and polymethylbutene;
said matrix having dispersed therein between 2 and 20 percent by weight of a synergistic combination consisting of:
(1) 50 to 95% by weight of a modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between 150 12 C. and 350 C., said modifying copolymer being selected from the group consisting of:
(a) 30 to 70% N-vinyl pyrrolidone/ 30 to 70% vinyl acetate, (b) 60% N-vinyl pyrrolidone/40% vinyl methyl ether, (c) N-vinyl pyrrolidone/20% styrene, (d) 70% N-vinyl pyrrolidone/ 30% ethyl acrylate, (e) 70% N-isoprenyl pyrrolidone/ 30% ethylene oxide,
(f) 60% N-acrylyl pyrrolidone/ 40% ethyl acrylamide,
(g) 50% N-vinyl methylpyrrolidone/50% vinyl methyl ether, (h) 60% N-vinyl oxazolidone/ 40 acrylonitrile, (i) 70% N-vinyl oxazolidinone/ 30% hydroxypropyl methacrylamide,
(j) 50% N-vinyl- 5 -methyl-2-oxazolidinone/ 5 0% vinyl acetate,
(k) 60% N-vinyl morpholinone/ 40% methyl acrylate, and
(1) N-vinyl p-yrrolidone/ 10% ethylene, said percent being by weight, and
(2) 5 to 50% by weight of a lower molecular Weight polar organic substance having at least one alkyl group with 6 to 30 carbons, said substance selected from the group consisting of:
(a) alkyl esters of polyhydroxy compounds,
(b) alkylene amines,
(0) fatty amides,
(d) alkyl ethers of polyhydroxy compounds,
(e) alkoxylated amines,
(f) di (Z-ethylhexyl) phosphoric acid,
(g) stearyl ester of phosphoric acid,
(h) salts of dodecylbenzene sulfonic acid,
(i) salts of naphthalene sulfonic acid,
(j) salts of di (2-ethylhexyl) phosphoric acid; said synergistic combination being fusible with said polyolefin at processing temperatures up to 350 C.
2. The composition of claim 1 wherein:
said copolymer consists of 50% by weight N-vinyl methyloxazolidinone in combination with 50% by Weight of vinyl acetate, and said lower molecular weight organic substance consists of fatty esters of polyhydroxy compounds.
3. The composition of claim 1 wherein:
said copolymer consists of 30 to 70% by Weight of N-vinyl pyrrolidone in combination with 30 to 70% vinyl acetate, and said lower molecular weight organic substance consists of alkoxylated fatty amines.
4. The composition of claim 1 wherein:
said copolymer consists of 60% by weight of N-vinyl morpholinone in combination .with 40% by weight of methyl acrylate, and said lower molecular weight organic substance consists of fatty esters of polyglycols.
5. The composition of claim 1 wherein: References Cited said copolymer consists of 70% by weight of N-vinyl UNITED STATES PATENTS pyrrolidone in combination with 30% by weight of ethyl acrylate, and said lower molecular weight 3,153,680 10/1964 Guisfiniani et 260 897 organic substance consists of fatty ethers of poly- 5 FOREIGN PATENTS glycols. l
6. The composition of claim 1 wherein: 83416O 5/1960 Great Bntam' said copolymer consists of 60% by weight of N-acrylyl pyrrolidone in combination with 40% by weight MURRAY TILLMAN Pnmary Exammer' ethyl acrylamide, and said lower molecular Weight 10 D. J. BREZNER, Assistant Examiner. organic substance consists of alkyl phosphoric acid.

Claims (1)

1. A POLYMERIC COMPOSITION HAVING IMPROVED AFFINITY FOR DYES CONSISTING ESSENTIALLY OF: A MATRIX OF STEROREGULAR POLYOLEFIN TAKEN FROM THE GROUP CONSISTING OF: POLYPROPYLENE, POLYMETHYLPENTENE, AND POLYMETHYLBUTENE; SAID MATRIX HAVING DISPERSED THEREIN BETWEEN 2 AND 20 PERCENT BY WEIGHT OF A SYNERGISTIC COMBINATION CONSISTING OF: (1) 50 TO 95% BY WEIGHT OF A MODIFYING COPOLYMER WHICH IS HYDROPHILIC, NON-SOLUBLE IN THE POLYOLEFIN, AND FUSIBLE AT A TEMPERATURE BETWEEN 150* C. AND 350*C., SAID MODIFYING COPOLYMER BEING SELECTED FROM THE GROUP CONSISTING OF: (A) 30 TO 70% N-VINYL PYRROLIDONE/ 30 TO 70% VINYL ACETATE, (B) 60% N-VINYL PYRROLIDONE/40% VINYL METHYL ETHER, (C) 80% N-VINYL PYRROLIDONE/20% STYRENE, (D) 70% N-VINYL PYRROLIDONE/30% ETHYL ACRYLATE, (E) 70% N-ISOPRENYL PYRROLIDONE/ 30% ETHYLENE OXIDE, (F) 60% N-ACRYLYL PYRROLIDONE/ 40% ETHYL ACRYLAMIDE, (G) 50% N-VINYL METHYLPYRROLIDONE/50% VINYL METHYL ETHER, (H) 60% N-VINYL OXAZOLIDONE/ 40% ACRYLONITRILE, (I) 73% N-VINYL OXAZOLIDINONE/ 30% HYDROXYPROPYL METHACRYLAMIDE, (J) 50% N-VINYL - 5 - METHYL-2-OXAZOLIDINONE/50% VINYL ACETATE, (K) 60% N-VINYL MORPHOLINONE/ 40% METHYL ACRYLATE, AND (1) 90% N-VINYL PYRROLIDONE/10% ETHYLENE, SAID PERCENT BEING BY WEIGHT, AND (2) 5 TO 50% BY WEIGHT OF A LOWER MOLECULAR WEIGHT POLAR ORGANIC SUBSTANCE HAVING AT LEAST ONE ALKYL GROUP WITH 6 TO 30 CARBONS, SAID SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF: (A) ALKYL ESTERS OF POLYHYDROXY COMPOUNDS, (B) ALKYLENE AMINES, (C) FATTY AMIDES, (D) ALKYL ETHERS OF POLYHYDROXY COMPOUNDS, (E) ALKOXYLATED AMINES, (F) DI (2-ETHYLHEXYL) PHOSPHORIC ACID, (G) STEARYL ESTER OF PHOSPHORIC ACID, (H) SALTS OF DODECYLBENZENE SULFONIC ACID, (I) SALTS OF NAPHTHALENE SULFONIC ACID, (J) SALTS OF DI (2-ETHYLHEXYL) PHOSPHORIC ACID; SAID SYNERGISTIC COMBINATION BEIN FUSIBLE WITH SAID POLYOLEFIN AT PROCESSING TEMPERATURES UP TO 350*C.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468864A (en) * 1965-10-18 1969-09-23 Continental Oil Co Oil soluble alkaryl sulfonate lithium and polyvalent metal salts in polyolefin fibers and films
US3530201A (en) * 1966-12-06 1970-09-22 Uniroyal Inc Dyeable polyolefins containing thermoplastic nitrogen containing polymers and polyethylene oxide
US3652198A (en) * 1968-09-13 1972-03-28 Uniroyal Inc Mixture of filaments capable of being dyed to a multicolor pattern with anionic disperse dyes
US4133844A (en) * 1977-07-22 1979-01-09 E. I. Du Pont De Nemours And Company Product and process
US5714258A (en) * 1992-07-02 1998-02-03 Hoechest Celanese Corporation Fiber having improved properties, compositions for producing such fibers, and process for improving properties of fibers
WO2022210543A1 (en) * 2021-03-29 2022-10-06 Tdk株式会社 Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB834160A (en) * 1957-04-10 1960-05-04 Gen Aniline & Film Corp Pigment composition
US3153680A (en) * 1959-08-03 1964-10-20 Montedison Spa Poly-alpha-olefin compositions having improved dye affinity

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB834160A (en) * 1957-04-10 1960-05-04 Gen Aniline & Film Corp Pigment composition
US3153680A (en) * 1959-08-03 1964-10-20 Montedison Spa Poly-alpha-olefin compositions having improved dye affinity

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468864A (en) * 1965-10-18 1969-09-23 Continental Oil Co Oil soluble alkaryl sulfonate lithium and polyvalent metal salts in polyolefin fibers and films
US3530201A (en) * 1966-12-06 1970-09-22 Uniroyal Inc Dyeable polyolefins containing thermoplastic nitrogen containing polymers and polyethylene oxide
US3652198A (en) * 1968-09-13 1972-03-28 Uniroyal Inc Mixture of filaments capable of being dyed to a multicolor pattern with anionic disperse dyes
US4133844A (en) * 1977-07-22 1979-01-09 E. I. Du Pont De Nemours And Company Product and process
US5714258A (en) * 1992-07-02 1998-02-03 Hoechest Celanese Corporation Fiber having improved properties, compositions for producing such fibers, and process for improving properties of fibers
WO2022210543A1 (en) * 2021-03-29 2022-10-06 Tdk株式会社 Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element
CN115413283A (en) * 2021-03-29 2022-11-29 Tdk株式会社 Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element
CN115413283B (en) * 2021-03-29 2024-05-07 Tdk株式会社 Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element

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