WO2014020570A2 - A method for producing fiber reinforced rubber comprising unsaturated bonds - Google Patents

A method for producing fiber reinforced rubber comprising unsaturated bonds Download PDF

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Publication number
WO2014020570A2
WO2014020570A2 PCT/IB2013/056335 IB2013056335W WO2014020570A2 WO 2014020570 A2 WO2014020570 A2 WO 2014020570A2 IB 2013056335 W IB2013056335 W IB 2013056335W WO 2014020570 A2 WO2014020570 A2 WO 2014020570A2
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Prior art keywords
reinforced rubber
fiber reinforced
unsaturated bonds
producing
fiber
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PCT/IB2013/056335
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French (fr)
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WO2014020570A3 (en
Inventor
Serkan BAS
Burak ERGUN
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Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi
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Priority to LU92421A priority Critical patent/LU92421B1/en
Publication of WO2014020570A2 publication Critical patent/WO2014020570A2/en
Publication of WO2014020570A3 publication Critical patent/WO2014020570A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a method for producing rubber reinforced with a fiber comprising unsaturated bonds which eliminates dipping process performed in producing fiber reinforced rubber and the need for the chemicals used during dipping process, and thus decreases the costs of producing fiber reinforced rubber.
  • the first step of this production is producing fibers such as polyester, nylon 6.6, nylon 6, rayon, aramide, dipping this material with an adhesive dipping solution and curing this material in a rubber composition.
  • the fibers are subjected to dipping process in conventional resorcinol-formaldehyde-latex (RFL) solution.
  • RTL resorcinol-formaldehyde-latex
  • Resorcinol-formaldehyde is then blended with latex (styrene- butadiene-vinyl pyridine terpolymer) which forms sulfur crosslinking with the styrene-butadiene rubber present in the rubber compound by means of the unsaturated bonds during vulcanization process.
  • latex styrene- butadiene-vinyl pyridine terpolymer
  • the dipping solution is an emulsion of activating chemicals such as blocked polyisocyanate and epoxy resin and/or the composition of water based resorcinol, formaldehyde and latex (RFL).
  • the polyester fiber treated with the said dipping solutions respectively is cured at high temperature and high tension.
  • the polyester yarns have a smooth surface and low reactivity.
  • polyester yarns cannot be completely adhered to the rubber without using adhesion promoters.
  • the low surface activity of the yarns stems from the low polarity and low reactivity of polyester.
  • polyester yarns have short residence time in the dipping solution. Because of the low surface activity, smoothness, short residence time of yarns in the adhesive dipping solution, it is hard to coat the surface of polyester with the activating solution and RFL. These parameters reduce the adhesion performance of polyester yarns coated with RFL. Since the physical and chemical bonding is too low between the reinforcement material and the rubber, adhesion activators are used in the interface to improve adhesion performance. Adhesion activators are expensive epoxy or blocked polyisocyanate or blocked polyurethane. Additionally, for better adhesion, the adhesive amount in the dipping solution should be increased. All these increase the cost of the dipping solution and thus the dipped reinforcement material.
  • the objective of the present invention is to produce fiber comprising unsaturated bonds.
  • the unsaturated fibers in this invention do not require treatment with RFL solution and activating chemicals in the production of fiber reinforced rubber.
  • Another objective of the present invention is to provide a fiber comprising unsaturated bonds which has lower production, processing and investment costs since the RFL solution and activating chemicals are not used.
  • a further objective of the present invention is to provide a production process which is more environmental friendly since RFL solution and activating chemicals are not needed.
  • a further objective of the present invention is to provide a production process which is improved in terms of worker's health and work safety since RFL solution and activating chemicals are not used.
  • Another objective of the present invention is to provide a method for producing fiber comprising unsaturated bonds which has the required fatigue and elongation properties without needing high twisting levels since the elongation of unsaturated fibers is higher than the saturated fibers.
  • the inventive fiber comprising unsaturated bonds forms the rubber-fiber composite structure by crosslinking with the sulfur during vulcanization by means of the unsaturated bonds therein without need RFL solution and activators.
  • the fibers used for reinforcement are the "nylon fibers" which is synthesized through a condensation reaction between diamines and dicarboxylic acids wherein water is by-product.
  • the fibers used for reinforcement are the "polyester fibers" which is synthesized through a condensation reaction between diamines and dihydroxyl acids wherein water is by-product.
  • dicarboxylic acids comprising unsaturated bonds can be cyclic 4-cyclohexene- 1 ,2-dicarboxylic anhydride; 2-cyclohexene- 1 ,2-dicarboxylic anhydride; l-cyclohexene-l,2-dicarboxylic anhydride; 3,5-cyclohexene-l,2- dicarboxylic anhydride and 2,6-cyclohesene-l,2-dicarboxylic anhydride.
  • the use of cyclic acid makes it possible to produce fibers having higher modulus than the linear dicarboxylic acids.
  • the linear dicarboxylic acids used in production of fibers having unsaturated bonds are selected from a group comprised of unsaturated linear diacids which can be itaconic, citraconic, mesaconic, cis-/trans- glutaconic acid, maleic acid and fumaric acid and/or dianhydrides but not limited with these monomers.
  • the diamines used in the production of nylon fibers can be ethylenediamine, propylenediamine, 2,2-dimethylpropylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decemethylene diamine, dodecamethylene diamine, 4,4'- diaminodicyclohexylmethane, xylene diamine, bis(aminomethyl)cyclohexane, para- and meta-phenylenediamine, oxybis(aniline), thiobis (aniline), sulfonilbis (aniline), diaminobenzophenone, methylenebis(aniline), benzydine, 1,5-diaminonaphtaline, oxybis(2,methylaniline), thiobis(2-methylainiline), 1,6- diamino-2-hexene, l,6-diamino-3-hexene, 2,7-
  • the dihydroxyls used with dicarboxylic acids in the production of polyester fibers can be l-propenediol-2,3, 2-propenediol-l,3, l-butenediol-1,4, 2-butenediol-l,4, 2-butenediol-l,3, l-butenediol-3,4, 2-pentenediol-3,5, 2,4-pentadienediol-3,5, 2,4- heptadienediol-1,4, 2,6-octadienediol-3,5, 3-pentenediol-l,4, 3-pentenediol-2,5, 1- hexenediol-3,6, 2,4-hexadienediol-3,5, ethylene glycol, propylene glycol, glycerol, trimethylolethane but not limited with these monomers.
  • Synthesis and spinning of unsaturated nylon and polyester fiber can be performed similar to the conventional nylon and polyester fiber production process.
  • the polymers disclosed in the said invention have tendency to gelling since they carry double bonds. This may cause the polymers of the invention to become gel at polymerization or processing temperature (150-300 °C). For this reason free radical inhibitors should be used.
  • the said inhibitors can be added to the polymer in the range of 0.001-1% by weight.
  • the said stoppers can be the chemicals selected from p-t-butyl hydroxytoluene, p-t-butyl hydroxyanisol, distearyl tiodipropionate, dilauryl tiodipropionate.
  • the unsaturated functional groups only dicarboxylic or only diamine or only diol
  • two unsaturated monomers is used for unsaturated polyester or nylon fiber.
  • the unsaturation degree of the fiber can be adjusted.
  • the unsaturation degree is important since the unsaturated bonds crosslink with the rubber through sulfur bonds during vulcanization.
  • the unsaturation degree can be adjusted with the mixture of saturated and unsaturated monomers (dicarboxylic acids, diamines or dihydroxyls) in polymer chain as well as the polymers comprising unsaturated bonds can be mixed with the saturated polymers (Nylon 6.6, polyethylene teraphthalate (PET) etc.).
  • the said degree can be in the range of 1-100 wt% of unsaturated polymer.
  • FIG. 1 The cross-sections of the rubbers reinforced with conventional nylon and polyester fiber dipped with RFL are shown below ( Figure 1,2).
  • Conventional nylon 6.6 fiber is used in Figure 1, the said fiber is dipped with RFL and used as a reinforcement material for rubber.
  • the fiber which is a reinforcing material, resorcinol-formaldehyde resin, vinyl pyridine latex and rubber are shown respectively.
  • Sulfur (Sg) is present in a certain concentration in rubber formulation. During the vulcanization of the rubber, the cyclic sulfur opens, and the vinyl pyridine latex in RFL and the styrene-butadiene rubber present in the rubber compound are reacted to each other through sulfur covalent bonds.
  • the said bonds are important to form a stable composite structure.
  • the resorcinol-formaldehyde resin also forms covalent bonds by reacting with the nylon.
  • the bonding mechanism of the conventional polyester fiber to the rubber is shown in figure 2.
  • activators such as epoxy and polyisocyanate are also used.
  • the said components form thermoset polyurethane after reacting.
  • the said activators form covalent bonds with the polyester; they mainly form secondary bonds (such as hydrogen and van der Waals).
  • the vinyl pyridine latex present in the RFL is cured with rubber during the vulcanization.
  • Figures 3 and 4 show the vulcanization of rubber reinforced with novel nylon and polyester fibers with unsaturated bonds through sulfur.
  • the rubber can be reacted with the fiber with sulfur bonds without any interface such as RFL or epoxy and polyisocyanate.
  • the production rate of fiber reinforced rubber material can be accelerated. Therefore, production, processing and investment costs decrease.
  • the RFL solution becomes redundant and the costs of the reinforced rubber materials decrease significantly in the rubber reinforcement. Eliminating RFL dipping process will reduce the factory and business investment costs. Furthermore many expensive chemicals used in conventional methods will not be needed in the present invention, and the rubber materials reinforced with fiber and the production process will be more environmental friendly. Through the inventive fiber with unsaturated bonds, the dipping process will be completely eliminated. The fibers can be twisted and weaved.. Therefore, production efficiency and capacity will increase significantly.
  • Twisting process is performed to improve the fatigue properties of yarn in the fiber reinforced rubber.
  • the increase in twisting level of the fiber to a certain level improves the fatigue resistance and the elongation of the twisted fiber before rupture.
  • the elongation of unsaturated fibers is higher than the saturated fibers.
  • the cost of the twisting process energy, labor etc.
  • the use of RFL is eliminated by using said fibers.
  • RFL is a hard coating which leads to a high heat build-up and therefore poor fatigue properties.
  • the conventional dipping and curing processes will be eliminated by the fibers in the present invention and the product costs of the reinforcement materials decreases. Furthermore the expensive chemicals used in conventional dipping and curing processes will not be used with the present invention, and the rubber materials reinforced with fiber and the production process thereof will be more environmental friendly.
  • the new reinforcement materials in the present invention a similar adhesion performance to the rubber will be acquired as in the conventional dipping solutions. Besides, friction and heat build-up is eliminated and the lifetime of the reinforced rubber material increases since the RFL interface is eliminated.
  • Conventional dipping processes require high investment cost (factory, labor, substructure, energy etc.). By means of the inventive fiber reinforced rubber comprising unsaturated bonds, all substructure, unit and labor required by the dipping process will be eliminated.

Abstract

The present invention relates to a method for producing fiber or fiber compositions comprising unsaturated bonds. These fibers eliminate dipping and curing process in producing fiber reinforced rubber and the need for the chemicals used during dipping process. These novel yarns, thus, decrease the costs of producing fiber reinforced rubber. The objective of the present invention is to produce fiber comprising unsaturated bonds which do not require treatment with RFL solution and activating chemicals in the fiber reinforced rubber materials. Reinforced rubber production will have lower production, processing and investment costs and will be more environmental friendly since RFL solution and activating chemicals are not used. Fibers with good fatigue and elongation properties can be produced without needing high twisting levels since the unsaturated fibers have higher elongation than the saturated fibers.

Description

A METHOD FOR PRODUCING FIBER REINFORCED RUBBER COMPRISING UNSATURATED BONDS
Field of the Invention
The present invention relates to a method for producing rubber reinforced with a fiber comprising unsaturated bonds which eliminates dipping process performed in producing fiber reinforced rubber and the need for the chemicals used during dipping process, and thus decreases the costs of producing fiber reinforced rubber.
Background of the Invention
Reinforced rubber production has been performed with the same methods for almost 70 years. The first step of this production is producing fibers such as polyester, nylon 6.6, nylon 6, rayon, aramide, dipping this material with an adhesive dipping solution and curing this material in a rubber composition. Before the rubber is reinforced with the fibers, the fibers are subjected to dipping process in conventional resorcinol-formaldehyde-latex (RFL) solution. Initially, the synthesis of resorcinol-formaldehyde was performed which provides functional groups to hold onto the surface of the fiber and provide strength to the interface of fiber and rubber. Resorcinol-formaldehyde is then blended with latex (styrene- butadiene-vinyl pyridine terpolymer) which forms sulfur crosslinking with the styrene-butadiene rubber present in the rubber compound by means of the unsaturated bonds during vulcanization process. For this reason the current fibers in the market necessitate dipping with RFL. The dipping solution is an emulsion of activating chemicals such as blocked polyisocyanate and epoxy resin and/or the composition of water based resorcinol, formaldehyde and latex (RFL). The polyester fiber treated with the said dipping solutions respectively is cured at high temperature and high tension. The polyester yarns have a smooth surface and low reactivity. Therefore, polyester yarns cannot be completely adhered to the rubber without using adhesion promoters. The low surface activity of the yarns stems from the low polarity and low reactivity of polyester. In addition, polyester yarns have short residence time in the dipping solution. Because of the low surface activity, smoothness, short residence time of yarns in the adhesive dipping solution, it is hard to coat the surface of polyester with the activating solution and RFL. These parameters reduce the adhesion performance of polyester yarns coated with RFL. Since the physical and chemical bonding is too low between the reinforcement material and the rubber, adhesion activators are used in the interface to improve adhesion performance. Adhesion activators are expensive epoxy or blocked polyisocyanate or blocked polyurethane. Additionally, for better adhesion, the adhesive amount in the dipping solution should be increased. All these increase the cost of the dipping solution and thus the dipped reinforcement material.
In the literature, unsaturated polyesters were formulated with glass fiber, acrylic copolymer and styrene monomer. The said formulation is cured with peroxide and used for applications of composite material (C. H. Kroekel, US Patent 3,701,748, Jul 20, 1966). Another study discloses polyester production with high molecular weight (E. Takiyama, Y. Hatano, US Patent 5,198,529, Nov 18, 1991). In another study, unsaturated nylon 6 and 18 polymers are synthesized by using diacid monomers comprising unsaturated bonds in the center of the molecule (C. Bennett, L. J. Mathias, Macromolecular Chemistry and Physics, 205, 18, 2438- 2442, 2004). However, none of these polymers in the state of the art are used to produce fibers or used as a rubber reinforcement material. With the present invention, by producing unsaturated fibers, the production time and cost of rubber materials reinforced with fiber can be reduced.
Summary of the Invention
The objective of the present invention is to produce fiber comprising unsaturated bonds. The unsaturated fibers in this invention do not require treatment with RFL solution and activating chemicals in the production of fiber reinforced rubber. Another objective of the present invention is to provide a fiber comprising unsaturated bonds which has lower production, processing and investment costs since the RFL solution and activating chemicals are not used. A further objective of the present invention is to provide a production process which is more environmental friendly since RFL solution and activating chemicals are not needed.
A further objective of the present invention is to provide a production process which is improved in terms of worker's health and work safety since RFL solution and activating chemicals are not used.
High twisting of yarns is needed to have high elongation properties. Another objective of the present invention is to provide a method for producing fiber comprising unsaturated bonds which has the required fatigue and elongation properties without needing high twisting levels since the elongation of unsaturated fibers is higher than the saturated fibers.
Detailed Description of the Invention
The inventive fiber comprising unsaturated bonds forms the rubber-fiber composite structure by crosslinking with the sulfur during vulcanization by means of the unsaturated bonds therein without need RFL solution and activators.
In one embodiment of the invention, the fibers used for reinforcement are the "nylon fibers" which is synthesized through a condensation reaction between diamines and dicarboxylic acids wherein water is by-product.
In one embodiment of the invention, the fibers used for reinforcement are the "polyester fibers" which is synthesized through a condensation reaction between diamines and dihydroxyl acids wherein water is by-product. In the novel yarns, dicarboxylic acids comprising unsaturated bonds can be cyclic 4-cyclohexene- 1 ,2-dicarboxylic anhydride; 2-cyclohexene- 1 ,2-dicarboxylic anhydride; l-cyclohexene-l,2-dicarboxylic anhydride; 3,5-cyclohexene-l,2- dicarboxylic anhydride and 2,6-cyclohesene-l,2-dicarboxylic anhydride.. The use of cyclic acid makes it possible to produce fibers having higher modulus than the linear dicarboxylic acids. The linear dicarboxylic acids used in production of fibers having unsaturated bonds are selected from a group comprised of unsaturated linear diacids which can be itaconic, citraconic, mesaconic, cis-/trans- glutaconic acid, maleic acid and fumaric acid and/or dianhydrides but not limited with these monomers.
The diamines used in the production of nylon fibers can be ethylenediamine, propylenediamine, 2,2-dimethylpropylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decemethylene diamine, dodecamethylene diamine, 4,4'- diaminodicyclohexylmethane, xylene diamine, bis(aminomethyl)cyclohexane, para- and meta-phenylenediamine, oxybis(aniline), thiobis (aniline), sulfonilbis (aniline), diaminobenzophenone, methylenebis(aniline), benzydine, 1,5-diaminonaphtaline, oxybis(2,methylaniline), thiobis(2-methylainiline), 1,6- diamino-2-hexene, l,6-diamino-3-hexene, 2,7-diamino-2,7-dimethyl-4-octene, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) methane and 2,2-bis(4-aminocyclohexyl)propane but not limited with these monomers.
The dihydroxyls used with dicarboxylic acids in the production of polyester fibers can be l-propenediol-2,3, 2-propenediol-l,3, l-butenediol-1,4, 2-butenediol-l,4, 2-butenediol-l,3, l-butenediol-3,4, 2-pentenediol-3,5, 2,4-pentadienediol-3,5, 2,4- heptadienediol-1,4, 2,6-octadienediol-3,5, 3-pentenediol-l,4, 3-pentenediol-2,5, 1- hexenediol-3,6, 2,4-hexadienediol-3,5, ethylene glycol, propylene glycol, glycerol, trimethylolethane but not limited with these monomers. Synthesis and spinning of unsaturated nylon and polyester fiber can be performed similar to the conventional nylon and polyester fiber production process. The polymers disclosed in the said invention have tendency to gelling since they carry double bonds. This may cause the polymers of the invention to become gel at polymerization or processing temperature (150-300 °C). For this reason free radical inhibitors should be used. The said inhibitors can be added to the polymer in the range of 0.001-1% by weight. The said stoppers can be the chemicals selected from p-t-butyl hydroxytoluene, p-t-butyl hydroxyanisol, distearyl tiodipropionate, dilauryl tiodipropionate.
In the inventive fiber reinforced rubber comprising unsaturated bonds, at least one of the unsaturated functional groups (only dicarboxylic or only diamine or only diol) or two unsaturated monomers is used for unsaturated polyester or nylon fiber. Thus the unsaturation degree of the fiber can be adjusted. The unsaturation degree is important since the unsaturated bonds crosslink with the rubber through sulfur bonds during vulcanization. The unsaturation degree can be adjusted with the mixture of saturated and unsaturated monomers (dicarboxylic acids, diamines or dihydroxyls) in polymer chain as well as the polymers comprising unsaturated bonds can be mixed with the saturated polymers (Nylon 6.6, polyethylene teraphthalate (PET) etc.). The said degree can be in the range of 1-100 wt% of unsaturated polymer.
The cross-sections of the rubbers reinforced with conventional nylon and polyester fiber dipped with RFL are shown below (Figure 1,2). Conventional nylon 6.6 fiber is used in Figure 1, the said fiber is dipped with RFL and used as a reinforcement material for rubber. Here, the fiber which is a reinforcing material, resorcinol-formaldehyde resin, vinyl pyridine latex and rubber are shown respectively. Sulfur (Sg) is present in a certain concentration in rubber formulation. During the vulcanization of the rubber, the cyclic sulfur opens, and the vinyl pyridine latex in RFL and the styrene-butadiene rubber present in the rubber compound are reacted to each other through sulfur covalent bonds. The said bonds are important to form a stable composite structure. In the said composite structure, the resorcinol-formaldehyde resin also forms covalent bonds by reacting with the nylon. The bonding mechanism of the conventional polyester fiber to the rubber is shown in figure 2. Here, since the surface activity of the polyester is very low, activators such as epoxy and polyisocyanate are also used. The said components form thermoset polyurethane after reacting. Besides, the said activators form covalent bonds with the polyester; they mainly form secondary bonds (such as hydrogen and van der Waals). Here, the vinyl pyridine latex present in the RFL is cured with rubber during the vulcanization.
Figures 3 and 4 show the vulcanization of rubber reinforced with novel nylon and polyester fibers with unsaturated bonds through sulfur. By means of the said fibers having unsaturated bonds, the rubber can be reacted with the fiber with sulfur bonds without any interface such as RFL or epoxy and polyisocyanate. By means of the new fibers in the invention, the production rate of fiber reinforced rubber material can be accelerated. Therefore, production, processing and investment costs decrease.
Through the inventive fiber with unsaturated bonds, the RFL solution becomes redundant and the costs of the reinforced rubber materials decrease significantly in the rubber reinforcement. Eliminating RFL dipping process will reduce the factory and business investment costs. Furthermore many expensive chemicals used in conventional methods will not be needed in the present invention, and the rubber materials reinforced with fiber and the production process will be more environmental friendly. Through the inventive fiber with unsaturated bonds, the dipping process will be completely eliminated. The fibers can be twisted and weaved.. Therefore, production efficiency and capacity will increase significantly.
Twisting process is performed to improve the fatigue properties of yarn in the fiber reinforced rubber. The increase in twisting level of the fiber to a certain level improves the fatigue resistance and the elongation of the twisted fiber before rupture. Besides, it is known that the elongation of unsaturated fibers is higher than the saturated fibers. For this reason, by using the inventive fibers, necessary fatigue and elongation properties can be acquired without needing high twisting levels. By decreasing the twisting levels the cost of the twisting process (energy, labor etc.) decreases. Additionally, the use of RFL is eliminated by using said fibers. RFL is a hard coating which leads to a high heat build-up and therefore poor fatigue properties. Through the use of inventive fibers, heat build-up on the fibers will be eliminated and therefore the lifetime of fibers and fiber-reinforced rubber can be extended.
The conventional dipping and curing processes will be eliminated by the fibers in the present invention and the product costs of the reinforcement materials decreases. Furthermore the expensive chemicals used in conventional dipping and curing processes will not be used with the present invention, and the rubber materials reinforced with fiber and the production process thereof will be more environmental friendly. By means of the new reinforcement materials in the present invention, a similar adhesion performance to the rubber will be acquired as in the conventional dipping solutions. Besides, friction and heat build-up is eliminated and the lifetime of the reinforced rubber material increases since the RFL interface is eliminated. Conventional dipping processes require high investment cost (factory, labor, substructure, energy etc.). By means of the inventive fiber reinforced rubber comprising unsaturated bonds, all substructure, unit and labor required by the dipping process will be eliminated.

Claims
CLAIMS A method for producing nylon fiber reinforced rubber which do not require dipping solutions and activators such as RFL dipping solution and epoxy and/or polyisocyanate, and characterized by the steps of spinning fiber with unsaturated bonds synthesized by the condensation reaction of diamine and dicarboxylic acid and the unsaturated bonds within the fiber crosslinking with styrene -butadiene through the sulfur in the rubber during vulcanization.
A method for producing nylon fiber reinforced rubber, according to claim 1, characterized in that the fiber with unsaturated bonds is spun after synthesizing polymer comprising at least one unsaturated bonds such as the reaction of cyclic dicarboxylic acid with diamine.
A method for producing nylon fiber reinforced rubber according to claim 2, characterized by a cyclic dicarboxylic acid which is selected from a monomer group comprising 4-cyclohexene-l,2-dicarboxylic anhydride; 2- cyclohexene- 1 ,2-dicarboxylic anhydride; 1 -cyclohexene- 1 ,2-dicarboxylic anhydride; 3,5-cyclohexene-l,2-dicarboxylic anhydride and 2,6- cyclohesene- 1 ,2-dicarboxylic anhydride
A method for producing nylon fiber reinforced rubber , according to claim 1, characterized in that the fiber with unsaturated bonds is spun after synthesizing polymer comprising at least one unsaturated bonds such as the reaction of the linear dicarboxylic acids with diamine.
A method for producing nylon fiber reinforced rubber , according to claim 4, characterized by at least one linear dicarboxylic acid selected from a monomer group itaconic, citraconic, mesaconic, cis-/trans-glutonic acid, maleic acid and fumaric acid . A method for producing nylon fiber reinforced rubber , according to any one of the preceding claims, characterized in that at least one diamine monomer selected from a monomer group comprising ethylenediamine, propylenediamine, 2,2-dimethylpropylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decemaethylene diamine, dodecamethylene diamine, 4,4'- diaminodicyclohexylmethane, xylene diamine, bis(aminomethyl)cyclohexane, para- and meta-phenylenediamine, oxybis(aniline), thiobis(aniline), sulfonilbis(aniline), diaminobenzophenone, methylenebis(aniline), benzydine, 1,5- diaminonaphtaline, oxybis(2,methylaniline), thiobis(2-methylainiline), 1,6- diamino-2-hexene, 1 ,6-diamino-3-hexene, 2,7-diamino-2,7-dimethyl-4- octene, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) methane and 2,2-bis(4-aminocyclohexyl)propane is reacted with dicarboxylic acid and spun as a nylon with unsaturated bonds.
A method for producing polyester fiber reinforced rubber without needing dipping solution such as RFL dipping solution and epoxy and/or polyisocyanate on polyester fiber surface, and characterized by the steps of synthesizing fiber with unsaturated bonds as a result of the condensation of dihydroxyl with dicarboxylic acid and crosslinking the unsaturated bonds of rubber through sulfur bonds during vulcanization.
A method for producing polyester fiber reinforced rubber, according to claim 7, characterized in that the fiber with unsaturated bonds is spun after synthesizing polymer comprising at least one unsaturated bonds such as the reaction of the cyclic dicarboxylic acids with dihydroxyls.
A method for producing polyester fiber reinforced rubber according to claim 8, characterized by a cyclic dicarboxylic acid which is selected from a monomer group comprising 4-cyclohexene-l,2-dicarboxylic anhydride; 8-cyclohexene- 1 ,2-dicarboxylic anhydride; 1 -cyclohexene- 1 ,2-dicarboxylic anhydride; 3,5-cyclohexene-l,2-dicarboxylic anhydride and 2,6- cyclohesene- 1 ,2-dicarboxylic anhydride.
10. A method for producing polyester fiber reinforced rubber, according to claim 7, characterized in that the fiber with unsaturated bonds is spun after synthesizing polymer from monomers comprising at least one unsaturated bonds such as the reaction of the linear dicarboxylic acids with dihydroxyls.
11. A method for producing polyester fiber reinforced rubber, according to claim 10, characterized by at least one linear dicarboxylic acid selected from a monomer group comprising itaconic, citraconic, mesaconic, cis- /trans-glutonic acid, maleic acid and fumaric acid.
12. A method for producing polyester fiber reinforced rubber, according to any one of the claims 7-11, characterized in that at least one dihydroxyl monomer selected from a monomer group comprising l-propenediol-2,3, 2- propenediol-1,3, l-butenediol-1,4, 2-butenediol-l,4, 2-butenediol-l,3, 1- butenediol-3,4, 2-pentenediol-3,5, 2,4-pentadienediol-3,5, 2,4- heptadienediol-1,4, 2,6-octadienediol-3,5, 3-pentenediol-l,4, 3- pentenediol-2,5, l-hexenediol-3,6, 2,4-hexadienediol-3,5, ethylene glycol, propylene glycol, glycerol, trimethylolethane is reacted with dicarboxylic acid and the polyester fibers are spun from a material synthesized after the reaction of said hydroxyls and dicarboxylic acids.
13. A method for producing fiber reinforced rubber according to any one of the preceding claims, characterized in that the fiber spinning of the synthesized polyester or nylon fibers is performed by using free radical inhibitors in the range of 0.001-1% by weight and thus gelation during process is prevented.
14. A method for producing fiber reinforced rubber according to any one of the preceding claims, characterized in that the nylon or polyester fibers are the nylon or polyester fibers are placed inside the rubber material.
15. A method for producing fiber reinforced rubber according to any one of the preceding claims, characterized in that produced unsaturated fibers is used to produce fiber reinforced rubber material.
PCT/IB2013/056335 2012-08-03 2013-08-02 A method for producing fiber reinforced rubber comprising unsaturated bonds WO2014020570A2 (en)

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