KR20010012536A - Polyolefin containing polyetheramine modified functionalized polyolefin - Google Patents

Abstract

The present invention relates to a composition consisting of a mixture of polyolefins with the reaction of the functionalized polyolefins with polyetheramines by grafting the polyetheramines into functionalized polyolefins in conventional mixing equipment. The polypropylene is melted in a conventional mixing apparatus to provide a process for preparing the reaction product of the functionalized polypropylene and polyetheramine. The mixtures of the present invention have the advantage that they are useful for producing colorable automotive body parts. In addition, the present invention contains colored polyolefin compositions containing reaction products of functionalized polyolefins and polyetheramines. Colored polyolefin fibers, including polypropylene fibers, are colored polyolefin fibers made by melt spinning and used to make woven fabrics, and nonwoven fibers. The polyolefin used in the embodiment of the present invention is a flexible polyolefin.

Description

Polyolefins containing polyetheramines modified with functionalized polyolefins {POLYOLEFIN CONTAINING POLYETHERAMINE MODIFIED FUNCTIONALIZED POLYOLEFIN}

While polypropylene has many other beneficial physical properties, the coloration properties are very poor. Instead, polypropylene has often been the ideal choice when non-colored plastics were needed. For many years, the need for colored polypropylene compositions has continued. Despite the considerable effort to provide colored polypropylene, this need remains inadequate. This need is particularly important in the textile industry.

The most frequently used technique for obtaining colored polypropylene in fibrous form is the addition of solid pigments to the polypropylene. Unfortunately, fibers mixed with solid pigments are never as sharp as dyed fibers. In addition, due to its limited number, pigments provide a significantly reduced spectrum in selection compared to dyeing. Likewise, the use of pigments limits the patterns that can be applied to articles of clothing made of polypropylene. Some pigments, in addition, affect the pullability and final physical properties of polypropylene fibers. Other polyolefins, such as polypropylene, have similar drawbacks.

In view of the above, there is a clear need for coloring polyolefins, including polypropylene compositions.

The present invention relates to novel olefin polymers produced by the reaction of functionalized polypropylene with polyetheramines. The present invention relates to thermoplastic resin mixtures comprising the novel olefin polymer and polypropylene. The present invention also relates to a colored composition containing the reaction product of polypropylene and functionalized polyethylene with polyetheramine, which composition may be in the form of fibers.

The present invention is a mixture consisting of a mixture of functionalized polypropylene and polyetheramine reaction product and polypropylene (“PP”) in which polyetheramine is grafted to functionalized polypropylene. By graft, the amine functionality of the polyetheramine reacts with the anhydrous component of the functionalized polypropylene forming the reaction product. For example, primary amines are reacted with maleic anhydride to form imides. The invention is also a process for melting polypropylene in conventional mixing equipment such as extrusion molding machines to produce reaction products of functionalized polypropylene and polyetheramines. In this regard, the mixtures of the present invention are for example polyetheramines, functionalized polypropylenes and polypropylenes at temperatures which react the functionalized polypropylenes with polyetheramines which give a reaction product containing imide groups. Can be supplied to an extruder to produce reactive extrusion.

In another aspect, the present invention is a composition consisting of a reaction product of polypropylene, crosslinked thermoplastic polyolefin vulcanizates, and functionalized polypropylene and vulcanized amines.

The compositions of the invention are also useful for molding automotive body parts based on direct paintable thermoplastic olefins (“TPOs”) and automotive body parts based on thermoplastic polyolefin vulcanizates (“TPVs”).

The present invention also comprises a colorable composition comprising functionalized polyolefins, such as polypropylene and maleated polypropylene, and an amount of polyetheramine effective to improve the colorability of the composition as compared to the polyolefin alone. In one embodiment of the invention, the composition is a fiber. As used herein, “fiber” is a flexible, synthesized, macroscopic homogenate that has a large aspect ratio and a small cross section. Such fibers are not limited to direct external extrusion, but are made by one of the conventional processes including tapes with slits or fine fibers. Therefore, it is contemplated that the compositions of the present invention will be useful for the production of colored fibers comprising colored fabrics and nonwoven polyolefin fibers.

The present invention also provides a method for producing colored fibers, which forms a colored composition consisting of a reaction product of polyolefins and functionalized polyolefins with polyetheramines, and extruding the colored composition into fibers.

Applications of fibers and filaments made from the polyester modified polyolefins include, but are not limited to, textile garments (outerwear and underwear); Carpet; Furniture and automotive upholstery, weaving industrial fabrics; Nonwoven absorbent pads used in diapers, sanitary napkins, incontinence pads, stain removers, and medical absorbent pads; Nonwoven clothing including disposable medical clothing; felt; Press sheets; Geo-textile; Filter (bipolar); Includes packaging materials including envelopes and artificial paper.

In addition, polyetheramines are believed to improve the washability of fibers or nonwoven mats based on polyolefins. Non-polar polyolefins retain dust due to the hydrophobic nature of both sides. Polyetheramine will facilitate the penetration of detergent into fibers or matrices, allowing the detergent to disperse and clean dirt and oil.

It is also contemplated that mixing polyetheramines will increase the adsorption and wicking properties of polyolefin fabrics or nonwovens. One example is a nonwoven absorbent that dissolves and is used in baby diapers. It is expected that polar polyetheramines will be mixed with polyolefins to make the nonwoven calcined surface more hydrophilic, thereby greatly improving the water absorption properties of the diaper.

In addition, the mixing of polyetheramines will increase the frictional resistance of fibers, fabrics and other items. Friction resistance is important for the tension of the fibers formed. Generally, grass feed is applied to reduce the friction between the tensile fiber and the metal surface.

The composition is also believed to be useful for making molded parts comprising fillers such as glass. In addition, the composition of the present invention can be prepared by producing a film comprising a packaging film, wherein the bonding layer is removed and the colorability and water permeability are improved; As a packaging material for electronic components such as circuit boards or semiconductor chips, the packaging material would be useful because it dissipates static electricity to protect the component from injury. It is further contemplated that the compositions of the present invention will be useful for improving the water impermeability of polyethylene and for transforming the bonding layer polyethylene into a multilayer film. The compositions of the present invention are believed to be useful as additives to polypropylene based reinforcing fibers used in concrete. In addition, the present invention will be useful for packaging films having improved colorability and having improved adhesion to metal or glass substrates, expanded coatings.

It is also contemplated that the compositions of the present invention will be useful for substrates used for electroplating, such as colored ribbons, paintable foams, antistatic foams, sticky adhesive PP compositions, and electromagnetic obstructions or decorations.

The present invention addresses the one or more disadvantages and needs discussed above. In this respect, the present invention provides a colored polyolefin composition with surprisingly good elasticity and processability. The present invention also provides polyolefin compositions having additionally improved properties, including one or more of improved performance, such as washability, wettability, electrostatic retention, adhesion of materials such as carpet backing, and flammability as expected benefits. It is expected to do.

Plastics have been increasingly used in automobile manufacturing. Collision modified polypropylene is believed to be particularly suitable for applications such as bumpers, spoilers, fenders, side bump strips and the like. Therefore, thermoplastic resin mixtures having improved properties of the present invention have significant potential compatibility. According to the present invention, such resin compositions include transportation devices (such as automobiles and ships), devices, tools, electronics, electrical appliances, sporting goods, leisure goods and the like; And reinforced plastics, which are structurally part of the field in the field of connectors, tubes and the like.

The reaction product of maleated polypropylene and polyetheramine and the mixture of polypropylene show improved coloring power, improved impact resistance, and excellent molding fluidity over the mixture of polypropylene and maleated polyethylene.

Furthermore, polyolefins have been used in the products of the fibers and fabrics made therefrom and will continue to be used in the future. However, polyolefins are not inherently colorable. Therefore, colored polyolefins are necessary. Mixtures of polypropylene and reaction products of functionalized polyolefins with polyetheramines provide a solution to this problem. Suitable thermoplastic resin compositions useful for the production of fibers and nonwovens are those which enhance the colorability of the compositions as compared to compositions containing polypropylene alone or containing only functionalized polypropylene such as polypropylene and maleized polypropylene. Must contain an effective amount of polyetheramine.

In one embodiment of the invention, the thermoplastic resin composition contains up to about 12 weight percent polyetheramine and up to about 30 weight percent functionalized polyolefin. In particular, the thermoplastic resin composition contains up to about 8 weight percent polyetheramine and up to 20 weight percent functionalized polyolefin. In a preferred embodiment, the thermoplastic resin composition contains from 0.1 to 5% by weight of polyetheramine and from 2 to 12% by weight of functionalized polyolefin.

Compositions containing the reaction products of polyolefins and functionalized polyolefins with polyetheramines will further mix different materials used to make the fibers, depending on the various end-use applications. For example, the composition can be mixed with other polymers such as polyesters and polyamides (nylons).

Polyolefins used in the present invention are well known. In general, certain polyolefins can be used to make plastic parts, fibers, and the like as described above in embodiments of the present invention. Generally, polyolefins have a melt flow index in the range of about 0.7 to about 1500. Representative polyolefins are polypropylene and polyethylene. Polyethylene is a well known material. The polyethylene used in the practice of the present invention is made of typical Ziegler-Natta catalysts, metallocene catalysts, or single point geometry catalysts, the last two being available from Exxon Chemical and Dow Chemical Company, respectively. Such polyolefins may have other monomers contained in polymers such as propylene, butylene and octene. As such, polypropylene is described, for example, in Kunststoff-Handbuch, Volume 4, Polyolefins, R. Vieweg A. Schley and A. Schwarz. As it is well known and commercialized in polymer chemistry as described by Carol Hanser Verlag, Munich, 1969, a detailed description is not provided. Commercialized polypropylenes are under the trade name AMOCO 1016 polypropylene from Amoco Chemical. In addition, flexible polyolefins are used in all embodiments of the present invention. Representative examples of such flexible polyolefins include REXflex ^™ flexible polyolefins commercialized from Rexene products division of Rexene Corporation of Dallas, Texas, and flexible homopolymers of trade names W101, W102, W103, W104, W105, W106, W107, W108 and W109; Flexible copolymers under the trade names W201 and W202. These elastic homopolymers and copolymers have a melt flow index (ASTM D1238, at 230 degrees Centigrade, measured in dg / minute) of 1.5 (high crystalline homopolymer) to 30 (medium crystalline homopolymer), 40 to 90%. Various crystallinity, melting point 154 ~ 160 ℃ (DSC), Vicat softening point (ASTM D 1525) 40 ~ 112, Shore D hardness (ASTM D2240) 34 ~ 63, tensile modulus (ASTM D638) range 35 ~ 279Mpa, tensile recovery force ( ASTM D412, 300 ° C., after 24 hours) is known to have a range of greater than 135% to 220% of a single polymer and 160% to 250% of copolymer, and a final elongation of 1,000% (ASTM D 638).

Functionalized polyolefins are polyolefins grafted with monomers. In the practice of the present invention, certain functionalized polyolefins are generally compatible with the resulting polyolefin after reacting with the polyetheramine and after reacting with the polyetheramine. The general method of the graft is by a free radical reaction. In the practice of the present invention, the functionalized polyolefin is not, for example, a copolymer of male anhydride and polypropylene, wherein half of the male anhydride is mainly in the backbone of the copolymer. Representative examples of monomer grafted polyolefins consist of a single polymer and copolymers of various olefins such as ethylene, propylene, butylene, pentene, hexylene, heptene and octene. Suitable monomers for preparing functionalized polyolefins are, for example, single carboxylic acids having less than 12 olefinically unsaturated carbon atoms, such as acrylic acid, or methacrylic acid, and tert-butylester. Related to, for example, tert-butyl (meth) acrylic salts, olefinically unsaturated dicarboxylic acids having less than 12 carbon atoms, such as fumaric acid, maleic acid, and itaconic acid and mono- And / or di-tert-butylesters such as mono- or di-tert-butylfumal salts, and mono- or di-tert-butyl maleate salts, olefinically unsaturated carbon atoms of less than 12 carbon atoms Olefinically unsaturated monomers having less than 12 carbon atoms containing dicarbonyl anhydrides, for example maleic anhydride, sulfo- or sulfonyl- groups, for example p-styrenesulfonic acid, 2- (meth Acrylamide-2-methylpropenesulfonic acid or 2-sulfonyl (meth) acrylic salt, 2- (meth) Olefinically unsaturated monomers having less than 12 carbon atoms containing acrylamide-2-methylpropenesulfonic acid or 2-sulfonyl (meth) acrylic salt, oxazolinyl-groups, for example vinyloxa Sleepy and vinyloxazoline derivatives, and olefinically unsaturated monomers having less than 12 carbon atoms containing epoxy-groups, for example glycidyl (meth) acrylic salts or allyl glycidyl ethers. The most preferred monomer for preparing functionalized polyolefins is maleic anhydride. Most preferred polyolefin is polypropylene. Therefore, the most preferred functionalized polypropylene is maleated polypropylene. Maleized polypropylene is well known and is produced by various manufacturers. Maleized polypropylene, for example, is commercialized under the trade name EPOLENE E-43 from Eastman Chemical.

The functionalized polyolefins used in the practice of the present invention have a wide variety of average molecular weights. In the practice of the present invention, certain functionalized polyolefins are used to provide polyolefin fibers that have been reacted with polyetheramines to improve the colorability of both polyolefins and mixtures of functionalized polyolefins and polypropylenes. When functionalized polyolefins are used to prepare colored compositions such as those used to make fibers, the functionalized polyolefins have various average molecular weights of greater than about 3,000, preferably less than about 50,000. Within this range, certain ranges of molecular weights are best colored depending on the amount and form of polyolefins and polyetheramines, as well as other conditions such as processing conditions, spinning properties of the fibers, and other desirable physical properties of the resulting colored composition. Make a composition with Therefore, in certain embodiments, there are excellent advantages such as low molecular weight functionalized polyolefins having an average molecular weight of 10,000 or less than 20,000. In other relationships, materials with higher molecular weight may have more advantages.

It should be appreciated that one or two monomers when the polyolefin is linear may bind, while the polyolefin may also bind to two or more monomers, including when the polyolefin is branched. Typically, one or two monomers are present.

The polyetheramines used in the present invention have a molecular weight of about 150 to 12,000 and are chemicals that are not limited to polyether materials functionalized with hydroxyl groups, amines, and aminoalcohols, including monoamines, diamines and triamines. Preferred polyetheramines have a molecular weight of about 1,000 to about 3,000. Suitable monoamines are JEFFAMINE ^™ M-1000, JEFFAMINE ^™ M-2070, and JEFFAMINE ^™ M-2005. Suitable diamines include JEFFAMINE ^™ ED-6000, JEFFAMINE ^™ ED-4000, JEFFAMINE ^™ ED-2001 including XTJ-502, TXJ-418, and JEFFAMINE ^™ D-2000, JEFFAMINE ^™ D-4000, JEFFAMINE ^™ ED-900, JEFFAMINE ^™ ED-600, and JEFFAMINE ^™ D-400. Suitable triamines are JEFFAMINE ^™ ET-3000, JEFFAMINE ^™ T-3000, and JEFFAMINE ^™ T-5000. Preferred polyetheramines are JEFFAMINE ^™ M-2070 and JEFFAMINE ^™ ED-2001. For the structure of the polyetheramines see the term dictionary. More preferred polyetheramines of the present invention have a molecular weight ranging from about 1,500 to 2,000. Particularly preferred polyetheramines are polyethermonamines comprising 36 to 44 ethylene oxide units and 1 to 6 propylene oxide units. In one embodiment, such polyethermonoamines are in the range of 2,000-2,200 molecular weight. In another embodiment, the polyethermonoamine comprises about 40 to 43 ethylene oxide units and 2.4 to 3 propylene oxide units. It is the structure of a polyether monoamine.

Wherein m is 36 to 44, n is 1 to 6, and not only is a mixture of the formula having a molecular weight of about 2,000 to 22,000, but also includes a polyethermonoamine having m of 40 to 43 and n of 2.4 to 3. do,.

In the practice of the present invention, monoamines and diamines are preferred. Polyether blocks of suitable polyetheramines are polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly (1,2-butylene glycol), and poly (tetramethylene glycol). . These glycols are aminated by conventional methods of preparing polyetheramines. In general, these glycols are produced in methoxy or conventional ethylene oxide such as hydroxy initiation, propylene oxide and mixtures of both. When both ethylene oxide and propylene oxide are used, the oxides can be reacted at the same time if a random polyether is desired, or can be reacted continuously if a block polyether is desired.

In one embodiment of the invention, the polyetheramine is produced from ethylene oxide, propylene oxide, or a mixture of both. In general, when the polyetheramine is produced from ethylene oxide, propylene oxide, or a mixture of both, the amount of ethylene oxide in molar units exceeds 50% of polyetheramine, preferably exceeds 75%, and more Preferably greater than 90%. In one embodiment of the present invention, polyols and amines, including polyalkylene polyamines and alkanol amines, or other amines not disclosed herein, are not included in the composition. Similarly, functional groups and amine groups other than ether bonds are not included in the polyetheramines. The polyetheramines used in the examples of the present invention are U.S. Pat. And well known amination techniques as described in US Pat. No. 5,457,147. In general, polyetheramines are prepared by amination of polyols, such as polyetherpolyols, with ammonia in the presence of a catalyst such as nickel, including a catalyst such as Ni / Cu / Cr.

Further mixing of the functionalized polyolefins and polyetheramines, and optionally the polyolefins, is carried out using conventional mixing apparatuses including batch mixers, continuous mixers, kneaders and extrusion molding machines.

The coloring composition of the present invention is made of fibers using a variety of known methods. Therefore, typical techniques such as melt spinning, dry spinning, and wet spinning for making fibers can be used. "Spinning" as used herein refers to the entire process of polymer melting or melting, extrusion, and fiber manufacture. For example, in melt spinning, the colored composition described in the above cast form is forcibly pushed out through the spinneret (mold) used in the technique. The size and shape of the spinnerets vary depending on the desired denier of the final fiber. The fine jet resulting from the hole in the spinneret is cooled (by air quenching) to solidify the composition by polymerization. Melt spinning is typically performed at high temperatures, such as 240-310 ° C. Dry spinning dissolves the coloring composition in a suitable solvent and extrudes the solution under pressure through a spinneret. The jet from the spinneret is heated to remove the solvent to produce solid fibers. In wet spinning, the polymer is also dissolved in a solvent, stretched through the spinneret, and precipitates the resulting jet of stretched material in the coagulation bath.

The filaments remaining in the spinneret holes are typically air quenched together with the filaments wound with a device that thins out radiation of the desired linear density. Such a device can lead to more suitable braided thread through further processing. Bar wheels are often used to control the winding speed, for example, from 10 to 33 m / s for fine fibers. The fibers are rolled, or directly unthreaded and / or transported to a weaving machine and stacked in a can.

Filaments produced in a melt, dry, or wet spinning process generally undergo one or more stretching processes. Therefore, the elementary wire is molecularly aligned along the fiber axis, and thus the fine structure of the fiber appears, leading to irreversible stretching and stretching. Stretching polyolefin fibers typically increases the orientation and otherwise modifies the physical properties of the fibers. The linear density is thus generally reduced during stretching. Stretching is typically performed transverse to the spinning installation in a continuous spin-drawing process, or in a second process step. Conventional melt spinning apparatuses often provide both spinning (extrusion molding) and stretching processes in a single high speed process. Similarly, bi-component fibers can also be produced with side-by-side structures or surface / core structures using known devices.

The resulting fibers may optionally be modified by weaving such as thermodynamic heat cooling. Weaving also provides the volume and flexibility of products made from fibers. The fibers may also use known techniques to form fibers with proper degree of twist to facilitate interwire bonds. Similarly, conventional methods generally disrupt the alignment and parallelization of continuous stranded synthetic fibers to produce yarns related to fiber yarns.

Spinning is processed using conventional techniques by knitting or knitting processes to produce woven fibers. In addition, conventional techniques are also used to make nonwovens for fibers that are chemically, mechanically bonded to each other, or both. For example, the raw length fibers are dispersed in a fluid (wet-laid nonwoven, or air-laid nonwoven, depending on the chosen technique) and deposited in a cardboard-like planar shape on a support base prior to bonding and interconnecting.

The size of the fiber depends on the end use purpose. For example, heavy fibers are often used on the back of carpets as opposed to fibers used in garments and the like. The latter draws the fibers after the added processing step, optionally applying something like spin polishing.

Conventional methods are used for dyeing the fibers of the present invention. For example, the fibers can be dyed using both conventional and disperse dye techniques. In general, dyeing can be easily done by applying the form of a dye solution, by quenching the fiber passing through it, for example by immersing in a dye solution, or spraying a dye solution on the fiber, or by using a multi-stage roll technique. Can be used. In general, the dye solution is in the form of a printing paste to apply a typical dyeing process such as roller printing or screen printing. Fibers can be dyed several times using one or more dyeing process techniques.

Water-soluble dye containers typically have a pH between 2 and 11, and generally acidic dyes have values between 2 and 6. pH is formic acid, acetic acid, sulfamic acid, citric acid, phosphoric acid, nitric acid, sulfuric acid, sodium phosphate, 4- Various compounds such as sodium phosphate, 3-sodium phosphate, ammonia water, sodium hydroxide, and mixtures thereof can be adjusted. Surfactants are used for the purpose of saving and dispersing water-soluble disperse dyes in dye containers. Typically, nonionic surfactants are used for this purpose. During the dyeing step, the dye container is stirred to promote the dyeing rate. The dyeing step can be carried out at various temperatures, with higher temperatures generally increasing the dyeing speed.

Another conventional technique is spray dyeing, in which a dye is bombarded onto a moving knitted fabric using a hot dyeing and Venturi spraying mechanism. The carrier allows for faster staining at atmospheric pressure and below 100 ° C. Carriers are typical organic compounds that are emulsified in water and have affinity for fibers. Representative examples of such carriers are aromatic hydrocarbons such as diphenyl and methylnaphthalene, phenols such as phenylphenol, chlorinated hydrocarbons such as dichloro- and tricolor-benzene, and methylsalicylic salt, butyl benzoate, diethylphthalate, and benzaldehyde It consists of an aromatic ester such as. Carriers are generally removed after staining.

In the dyeing sequence using the dye mixed with the additive as described above, the drying heat may be applied to the fiber at a wide range of elevated temperatures to infiltrate and fix the dye into the fiber. The dye fixing step is a process of exposing the fibers to dry with heat, such as in an oven. The temperature may vary up to the melting of the composition fibers, or the glass transition temperature. In general, high drying temperatures shorten the drying time. Typically the heating time is from about 1 minute to about 10 minutes. Residual dye is removed from the fibers.

Disperse dye mixtures can be applied to polypropylene fibers in a variety of ways. The dye mixture can be applied intermittently along the length of the yarn formed from the fiber using various conventional techniques to create the desired effect. One suitable method of dyeing fibers is the "knit-deknit" dyeing technique. According to this method, the fibers are knitted and then again in the form of spinning, typically having a tube structure. Dye mixtures are used intermittently in knitted tubes. After staining, the tube is loosened and the radiation has an intermittent pattern. According to the two printing methods, the fibers first take the form of a yarn, either knitted or woven into the carpet or decorated with tufts on the carpet. Commonly used flat screen printing machines can be used to apply dye mixtures to fabrics or carpets.

Continuous dyeing is performed in a dyeing range where the fabric or carpet continues to pass through a dye solution of effective length to reach initial dye penetration. Some disperse dyes are sublimation by thermal and partial vacuum to the polymer in a conventional manner. The printing of the polyolefin composition prepared by the present invention can be dyed by dispersing it with heat transfer printing by applying appropriate heating and pressure to diffuse and disperse the dye into the polyolefin. Blocks, flat screen and heat transfer batch processes, and plated roller and rotary screen printing continuous techniques can be used. The other dye solution is sprayed onto the fabric or carpet made of the composition of the present invention by passing the fabric under the sprayer to form a pattern, according to the planned order. The dye solution is metered, broken or cut into a drop pattern that is allowed to fall on the colored carpet passing through the bottom surface in order to disperse the over-colored pattern on the carpet. Competitive dyeing of polyolefins is useful when dyeing styles carpets made of nylon, polyester, and the like and some other fibers such as polyolefins. Other styling effects can be produced by adjusting the depth of concentration, depending on the type of fiber present. Acidic, disperse, premetalized dyes, or combinations thereof, for the present fibers can be used to achieve the styling effect. It will be possible to produce a tweed effect by controlling the amount of the reaction product and / or polyetheramine of the coloring composition. Print dyeing, space dyeing, and continuous dyeing can be done on textile articles made from such yarns.

There are many commercialized disperse dyes. Dyes are subdivided into methods of application and smaller ranges and classified according to chemical composition by the Society of Dyers and Colorist. A variety of disperse dyes are designated by Textile Chemists and Colorists, published by the American Association of Textile Chemists and Colorists. Colorants and dyes and pigments by common name ". Dyes are dark colored materials used to color various substrates such as paper, plastic, or fiber materials. The dyes remain in these substrates by physical adsorption, salt or metal-complex formation, or covalent chemical bonds. The methods used to apply the dye to the material vary considerably depending on the substrate and the classification of the dye. Depending on the method of application, rather than chemical composition, the dye loses its crystal structure by dissolution or evaporation. In some cases, the crystal structure may be restored during the last stage of the staining process. On the other hand, pigments continue to maintain their crystal or particulate form throughout the entire application process.

Because of the large variety of dyed materials with significantly different properties, many dyes are needed. On a global basis, it is believed that thousands of different dyes have reached commercial importance. In general, dyes are classified into groups in two ways. One method of classification is by chemical structure grouped by chromophore and colored molecular units. The second classification method is based on the application classification of the end-use of the dye. Two classification systems used for color index (CI) are used internationally throughout the dye manufacturing and dye-use industries. In this system, dyes are chemically classified by CI number according to their respective chemical mixtures and uses, or grouped according to their application classification by the CI name of each dye. Disperse dyes are typically water soluble nonionic dyes, which dye an aqueous dispersed hydrophilic fiber. Disperse dyes are used in polyester, nylon, and acetate fibers.

Before stretching, the fibers may be subjected to some spin finish. This finish is water-based. Spin finish can be anionic or nonionic, as is well known in the art. In addition, the fibers can be finished before dyeing, by weaving through mechanical pleating or shaping, as is well known in the art.

In addition, additives mainly used in the art may optionally be mixed into the coloring composition and / or fibers. Representative examples of such materials are hydrophilic modifiers such as monoglycerides such as glycerol monostearate, long chain hydrocarbons with attached hydrophilic groups such as potassium or sodium salts of linear alkyl phosphates, or combinations thereof. Hydrophilic groups include quaternary ammonium salts and polyether groups, as well as carboxyl salts, sulfates, sulfone salts, phosphates and phosphone salts. In addition, swelling agents may be used during the dyeing with wetting agents, dyeing compatibility agents, thickening agents such as various gums and the like. Polyolefin fibers are often used in outdoor products such as outdoor carpets with the addition of ultraviolet stabilizers. In addition, antioxidants may be added to the composition.

In addition to the structural elements of the PP / functionalized-PP / polyetheramines of the present invention, the resin composition will contain impact modifiers, such as impact-modifying elastomers, which are advantageous in applications such as bumper strips to improve impact strength. Potentially useful impact-modifying elastomers of the present invention are well known to those skilled in the art. For example, there are rubbers based on ethylene, propylene, butadiene, and acrylic salts such as methacryl salts, or mixtures thereof. Another example consists of ethylene propylene rubber, EP and EPDM rubber, which are preferred for applications in the manufacture of automotive bodies. A representative example of recently commercialized EP rubber is the trade name VISTALON 878 of Exxon Chemical.

Shock-modified elastomers are described in Methoden der organischen Chemie (houben-Wely), Volume 14/1, Markromolekulare Chemie (Georg-Thieme-Verlag, Stuttgart, 1961). For example, see pages 390 to 406, and a monograph by C.B. Bucknal, Toughened Plastics (Applide publishers, London, 1977).

Compositions containing polypropylene and elastomers, such as EP rubbers, are commonly referred to as "TPOs" which represent thermoplastic polyolefins. TPOs are commonly used in the manufacture of molded vehicle bodies, such as bumper strips. Such molded parts will also contain other compositions, such as fillers, as described below. TPO-based compositions can be prepared in the same manner as inelastic-containing compositions. Representative examples of TPO are commercialized under the trade name HIMONT C53A by Hitmont and under the trade name DEXFLEX D-161 by D & S Plastic International.

Compositions comprising polypropylene consisting of thermoplastic polyolefin vulcanizates and vulcanized elastomers (vulcanized rubber) are commonly referred to as "TPV". TPV is commonly used to manufacture molded automotive body parts such as grips and handles. Such molded parts will contain other components, such as fillers, as described below. TPV-based compositions are prepared in the same manner as non-elastic compositions.

The polypropylene functionalized with polyetheramine, and optionally a small amount of PP, TPV, or TPO, reacts to form a reaction product concentrate, after which the reaction product concentrate is mixed with polypropylene or TPO or TPV. Thus, in the present invention, polyetheramine accounts for 10 to 50% by weight of the concentrate. When the reaction product of polyetheramine and maleated PP is made pure, the reaction product can be mixed or compounded with other components to the desired level using a mixing device such as polyethylene or TPO and an extruder. I think it is. PP is known to be commonly used to dilute the reaction. Depending on the type of mixer, the reaction product, polypropylene and other components are sufficiently mixed into solids prior to introducing the mixture into the mixing apparatus. Optionally, the mixer is adapted to mix the components during the process. In another case, during the mixing process, the components are mixed to form the final composition and heated with the molten components to melt the solid.

In addition to the polyolefins, functionalized polyolefins, and structural elements of polyetheramines and other impact modifiers contained in the resin compositions of the present invention, the resins also include reinforcing agents and / or additives. Reinforcing agents include, for example, carbon, or carbon fibers; Mud, whistle, talc, and mica to control shrinkage and to adjust the coefficient of thermal expansion; Glass (mats such as beads, fibers or woven fibers) to increase the stiffness; And to strengthen fillers such as pigments. In addition, the filler may be finished with an adhesion promoter and / or a grass feed agent. In addition, phosphites or masked phenols, or both, are added as stabilizers (radical scavengers).

If the composition is glass beads or fibers, the composition may contain up to about 40% glass filler if a very rigid composition is desired. If the composition contains a glass mat, the composition will contain up to about 80% glass. More generally, about 2% to 10% glass fillers may be contained. Advantageously, compositions containing the glass fillers of the present invention are generally sufficiently tight to develop into compositions containing polypropylene and glass. While not wishing to be bound by theory, it is believed that the reaction product of polyetheramine and maleated polypropylene causes the glass to “wet” in order to make the glass and polypropylene more bondable (more miscible). In this regard, it is preferred to use maleated polypropylene having an average molecular weight of about 40,000 to 60,000 as specified above. In general, the glass filler and the polypropylene are not miscible, and the compounds typically create gaps in the resulting composition. Materials having a relatively high molecular weight reduce the amount of gaps in the resulting composition of glass filler particles and polypropylene, thereby "wetting" the glass to bond even better.

Suitable thermoplastic resin compositions for use in applications such as automotive bumper strips include from about 66% to 80% by weight of TPO or TPV, from about 5% to 30% by weight of maleated PP and from about 2% to about 10% by weight of polyetheramine. Contains% If the composition contains an elastomer, such as a TPO-based composition used to make automotive body parts, the composition generally contains maleated TPO or TPV as a percentage of the weight of these components of the composition, about 5-40. Weight percent, about 2 to 10 weight percent polyetheramine, and about 50 to 93 weight percent PP. Preferred compositions containing elastomers, or TPV-based, consist of about 15 to 30 weight percent of maleized PP, about 2 to 8 weight percent of polyetheramines, and about 62 to 83 weight percent of TPO or TPV.

Preferred conventional mixing apparatuses are extrusion apparatuses for grafting polyetheramine functionalized fillers at about 175 to 300 ° C. during a residence time of 25 to 300 seconds. For the general composition of the present invention, it starts to decompose above the above temperature range and below the above range the composition generally does not melt. Polypropylene is a component that is non-reactive during mixing. Preferred temperature ranges are about 190 to 260 ° C. Excess moisture in the blended composition creates defects on the surface of the casting, but the moisture can be removed by the usual drying process using heated dry air.

Molded articles made from the compositions of the present invention are generally capable of direct coloring, with the exception of the coloring composition and the fibers. Examples of representative coloring are generally used for the purpose of using urethane-based and melamine-based paints. Such paints apply to using typical techniques. Usefully, the compositions of the present invention can be colored directly, without the solvent produced in the pretreatment of chlorinated polyethylene, and optionally without pretreatment, although a pretreatment is used.

For example, continuous mixing has nine barrel structures, three kneaders and one outlet, and all ingredients are in the same place (the hopper of the extruder), so that the Werner & Pfleiderer 30 It is carried out in a screw extrusion machine (ZSK30) in pairs of mm.

Although this invention is demonstrated to the following example, the scope of the present invention and a claim is not limited to this. In an embodiment, the stoichiometric amount of maleated functionality of maleated polypropylene and maleated polyethylene uses a relative amount of the amount of amine functionality in the polyetheramine.

Example 1-26

In Examples 1 to 26, polyolefins, maleized polypropylenes, and polyetheramines were blended to produce melt spun polyolefin mixtures from which polyolefin fibers were made, with improved, above-expected products with improved colorability. will be. Table 1 shows the amounts and types of polyolefins and the amounts of mixed and melt spun polyetheramines and maleized polypropylenes.

number Polyolefin Type Polyolefin Weight% Polyetheramine weight% Maleized PP Weight% One PP 98.7 0.5 0.8 2 PP 97.5 One 1.5 3 PP 96.2 1.5 2.3 4 PP 95 2 3 5 PP 93.7 2.5 3.8 6 PP 92.5 3 4.5 7 PP 91.2 3.5 5.3 8 PP 90 4 6 9 PP 88.7 4.5 6.8 10 PP 87.5 5 7.5 11 PP 85 6 9 12 PP 82.5 7 10.5 13 PP 80 8 12 14 PE 98.7 0.5 0.8 15 PE 97.5 One 1.5 16 PE 96.2 1.5 2.3 17 PE 95 2 3 18 PE 93.7 2.5 3.8 19 PE 92.5 3 4.5 20 PE 91.2 3.5 5.3 21 PE 90 4 6 22 PE 88.7 4.5 6.8 23 PE 87.5 5 7.5 24 PE 85 6 9 25 PE 82.5 7 10.5 26 PE 80 8 12

Example 27-52

In Examples 27-52, polyolefins, maleated polyethylenes, and polyetheramines were blended to produce a melt spun polyolefin mixture from which polyolefin fibers were made, with an improved, higher-than-expected product with improved colorability. . Table 2 shows the amounts and types of polyolefins and the amounts of mixed and melt spun polyetheramines and maleized polypropylenes.

number Polyolefin Type Polyolefin Weight% Polyetheramine weight% Maleized PE Weight% 27 PP 98.7 0.5 0.8 28 PP 97.5 One 1.5 29 PP 96.2 1.5 2.3 30 PP 95 2 3 31 PP 93.7 2.5 3.8 32 PP 92.5 3 4.5 33 PP 91.2 3.5 5.3 34 PP 90 4 6 35 PP 88.7 4.5 6.8 36 PP 87.5 5 7.5 37 PP 85 6 9 38 PP 82.5 7 10.5 39 PP 80 8 12 40 PE 98.7 0.5 0.8 41 PE 97.5 One 1.5 42 PE 96.2 1.5 2.3 43 PE 95 2 3 44 PE 93.7 2.5 3.8 45 PE 92.5 3 4.5 46 PE 91.2 3.5 5.3 47 PE 90 4 6 48 PE 88.7 4.5 6.8 49 PE 87.5 5 7.5 50 PE 85 6 9 51 PE 82.5 7 10.5 52 PE 80 8 12

Examples 53-78

In Examples 53 to 78, polyethylene, maleated polyethylene, and polyetheramine are blended to produce a melt spun polyolefin mixture from which polyethylene fibers are made, with an improved, higher-than-expected product with improved colorability. . Table 3 shows the amounts and types of polyolefins and the amounts of mixed polyetheramines and maleized polypropylenes.

number Flexible Polyolefin Weight% Polyetheramine weight% Maleized PE Weight% 53 98.7 0.5 0.8 54 97.5 One 1.5 55 96.2 1.5 2.3 56 95 2 3 57 93.7 2.5 3.8 58 92.5 3 4.5 59 91.2 3.5 5.3 60 90 4 6 61 88.7 4.5 6.8 62 87.5 5 7.5 63 85 6 9 64 82.5 7 10.5 65 80 8 12 66 98.7 0.5 0.8 67 97.5 One 1.5 68 96.2 1.5 2.3 69 95 2 3 70 93.7 2.5 3.8 71 92.5 3 4.5 72 91.2 3.5 5.3 73 90 4 6 74 88.7 4.5 6.8 75 87.5 5 7.5 76 85 6 9 77 82.5 7 10.5 78 80 8 12

Term Dictionary

JEFFAMINE M-1000 ^TM

JEFFAMINE ^TM M-2070 and JEFFAMINE ^TM M-2005

Wherein R = H or CH ₃ , m is about 3 to 32 and n is about 10 to 32.

^{JEFFAMINE TM D-2000, JEFFAMINE TM} D-4000 and JEFFAMINE D-400 ^TM

Where x is about 33 for the D-2000, x is about 68 for the D-4000, and x is about 5.6 for the D-400.

^{JEFFAMINE TM ED-600, JEFFAMINE TM} ED-900, JEFFAMINE TM ED-2001,

JEFFAMINE ^TM ED-4000, and JEFFAMINE ^TM ED-6000

Where for b ED-600 b is about 8.5 and a + c is about 15.5, for ED-900 b is about 15.5 and a + c is about 2.5, for ED-2001 b is about 40.5 and a + c Is about 2.5, for ED-4000 b is about 86.0 and a + c is about 2.5, for ED-6000 b is about 132.0 and a + c is about 3.0.

JEFFAMINE ^TM T-3000 and JEFFAMINE ^TM T-5000

Here x + y + z = 50 for T-3000 and x + y + z = 83 for T-5000.

JEFFAMINE ^TM ET-3000

Where x + y + z = 57 and a + b + c = 4.

Claims (49)

A compound consisting of polypropylene and a reaction product of functionalized polypropylene and polyetheramine. A colorable composition comprising the reaction product of a polyolefin and a polyetheramine in an amount sufficient to enhance the colorability of the composition as compared to the colorability of the polyolefin alone. The coloring composition of claim 2, wherein the polyolefin is polypropylene or polyethylene. The coloring composition of claim 2, wherein the polyolefin is polypropylene. The coloring composition of claim 2, wherein the polyetheramine is a monoamine or diamine and has a molecular weight of about 1,000 to about 3,000. 3. The coloring composition of claim 2, wherein said functionalized polyolefin consists of maleated polypropylene. 3. The colorable composition of claim 2, wherein the functionalized polyolefin consists of maleated polypropylene having an average molecular weight of about 20,000 or less. The coloring composition according to claim 2, wherein the functionalized polyolefin is present in an amount of 0.1 wt% to 15 wt% and the polyetheramine is present in an amount of about 0.5 wt% to 25 wt%. The coloring composition of claim 2, wherein the composition is in the form of fibers. The coloring composition of Claim 2 which further contains a dye. The coloring composition of Claim 9 which further contains a dye. Colored fibers consisting of polyolefins and reaction products of functionalized polyolefins and polyetheramines. 13. The colored fiber of claim 12, wherein the functionalized polyolefin is maleated polypropylene. The colored fiber according to claim 12, wherein the functionalized polyolefin is maleated polypropylene containing 1 to 8% anhydride as measured by proton nuclear magnetic resonance spectroscopy (nmr). The colored fiber of claim 12, wherein the functionalized polyolefin is present in an amount from about 0.1 wt% to about 15 wt% and the polyetheramine is present in an amount from about 0.5 wt% to about 25 wt%. The colored fiber of claim 12, wherein the functionalized polyolefin has an average molecular weight of about 20,000 or less. 13. The colored fiber of claim 12, further comprising a dye. 13. The colored fiber of claim 12, wherein the fiber is from about 1 to about 1,500 denier. 13. The colored fiber of claim 12, wherein the fiber is from about 1 to about 60 denier. Woven fibers consisting of polyolefins and reaction products of functionalized polyolefins and polyetheramines. The textile fiber of claim 20 wherein the functionalized polyolefin is maleated polypropylene. 21. The colored textile fiber of claim 20, further comprising a dye. 21. The colored textile fiber of claim 20, wherein the functionalized polyolefin is maleated polypropylene containing 1 to 8% anhydride as measured by proton nuclear magnetic resonance spectroscopy. The textile fiber of claim 20 wherein the functionalized polyolefin is present in an amount from about 0.1 wt% to about 15 wt% and the polyetheramine is present in an amount from about 0.5 wt% to about 25 wt%. The textile fiber of claim 20 wherein the functionalized polyolefin has an average molecular weight of about 20,000 or less. Nonwoven fibers consisting of polyolefins and reaction products of functionalized polyolefins and polyetheramines. 27. The nonwoven fiber of claim 26, wherein said functionalized polyolefin is maleated polypropylene. 27. The colored nonwoven fiber of claim 26, wherein the functionalized polyolefin is maleated polypropylene containing 1 to 8% anhydride as measured by proton nuclear magnetic resonance spectroscopy. The nonwoven fiber of claim 26, wherein the functionalized polyolefin is present in an amount from about 0.1 wt% to about 15 wt% and the polyetheramine is present in an amount from about 0.5 wt% to about 25 wt%. 27. The nonwoven fiber of claim 26, wherein the functionalized polyolefin has an average molecular weight of 20,000 or less. 27. The nonwoven fiber of claim 26, further comprising a dye. Forming a coloring composition consisting of a polyolefin and a reaction product of a functionalized polyolefin with a polyetheramine; And Method for producing a colored fiber comprising the step of extruding the coloring composition into a fiber. 33. The method of claim 32, wherein the functionalized polyolefin is maleated polypropylene. 33. The method of claim 32, wherein the functionalized polypropylene is maleated polypropylene containing 1 to 8% anhydride as measured by proton nuclear magnetic resonance spectroscopy. 33. The method of claim 32, wherein the functionalized polyolefin is present in an amount from about 0.1% to about 15% by weight and the polyetheramine is present in an amount from about 0.5% to about 25% by weight. 33. The method of claim 32, wherein the functionalized polyolefin has an average molecular weight of 20,000 or less. 33. The method of claim 32, further comprising contacting the dye with the fiber in a state sufficient to color the fiber. The method of claim 32, wherein the fiber is about 1 to 1,500 denier. 33. The method of claim 32, wherein the fiber is between 1 and 100 denier. 33. The method of claim 32, further comprising forming the fibers into a nonwoven article. 33. The method of claim 32, further comprising forming the fibers into a textile article. The compound of claim 1, further comprising a flexible polyolefin. The compound of claim 1, wherein said polypropylene is a flexible polyolefin. The coloring composition of claim 2, wherein the polyolefin is a flexible polyolefin. 13. The colored fiber of claim 12, wherein said polyolefin is a flexible polyolefin. 27. The nonwoven fiber of claim 26, wherein said polyolefin is a flexible polyolefin. 33. The method of claim 32, wherein the polyolefin is a flexible polyolefin. A printing and flexible composition consisting of the reaction product of a flexible polyolefin and a polyetheramine and a functionalized polyolefin. Preparation of the printable and flexible compositions comprising mixing the flexible polyolefin, the polyetheramine and the functionalized polyolefin to form a printable composition consisting of the reaction product of the flexible polyolefin and the polyetheramine with the functionalized polyolefin. Way.