WO2015059599A1 - Systèmes à base de polyoxyméthylène à deux composants - Google Patents

Systèmes à base de polyoxyméthylène à deux composants Download PDF

Info

Publication number
WO2015059599A1
WO2015059599A1 PCT/IB2014/065223 IB2014065223W WO2015059599A1 WO 2015059599 A1 WO2015059599 A1 WO 2015059599A1 IB 2014065223 W IB2014065223 W IB 2014065223W WO 2015059599 A1 WO2015059599 A1 WO 2015059599A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
article according
polymer layer
layer
less
Prior art date
Application number
PCT/IB2014/065223
Other languages
English (en)
Inventor
Qamer Zia
Oliver Juenger
Jos Bastiaens
Original Assignee
Ticona Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ticona Gmbh filed Critical Ticona Gmbh
Publication of WO2015059599A1 publication Critical patent/WO2015059599A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/746—Slipping, anti-blocking, low friction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone

Definitions

  • polyoxymethylene polymers have become established as exceptionally useful engineering materials in a variety of applications. For instance, because polyoxymethylene polymers have excellent mechanical properties, fatigue resistance, abrasion resistance, chemical resistance, and moldability, they are widely used in constructing polymer articles, such as articles for use in the automotive industry and the electrical industry.
  • Polyoxymethylene polymers are often provided with additives to adapt the properties for a specific application, for example by using reinforcing fibers or tribological modifiers.
  • polyoxymethylene polymers have been combined with a tribological modifier for producing polymer compositions well suited for use in tribological applications where the polymer article is in moving contact with other articles, such as metal articles, plastic articles, and the like.
  • tribological applications can include embodiments where the polymer composition is formed into gear wheels, pulleys, sliding elements, and the like.
  • the addition of a tribological modifier can provide a composition with a reduced coefficient of friction, little frictional noise, and low wear.
  • modified poiyoxymethylene compositions have been found to be well suited in tribological applications, further improvements are still necessary. For instance, a need exists for providing a poiyoxymethylene based system with improved tribological properties. In particular, a need exists for providing a poiyoxymethylene based system with a reduced coefficient of friction when in contact with other moving articles such as metal articles or plastic articles such as polyethylene terephthalate. In addition, a need exists for providing a
  • the present disclosure is directed to a polymer article comprising a first polymer layer and a second polymer layer.
  • the first polymer layer is comprised of a poiyoxymethylene polymer composition comprising a poiyoxymethylene polymer and optionally, at least one tribological modifier.
  • the second polymer layer is comprised of a second polymer composition comprising a liquid crystalline polymer, a polyarylene sulfide polymer, or a combination thereof.
  • the second polymer composition further comprises at least one tribological modifier.
  • the tribological modifier in the second polymer composition may comprise a polytetrafluoroethylene.
  • the second polymer composition may further comprise a reinforcing fiber.
  • the second polymer layer may be connected to the first polymer layer.
  • the second polymer layer may be connected to the first polymer layer via overmolding.
  • the second polymer layer may be connected to the first polymer layer using an interlocking mechanism.
  • the second polymer layer may be connected to the first polymer layer using a fastener.
  • Figure 1 is a conveyor belt assembly comprising conveyor components according to one embodiment of the present disclosure
  • Figure 2 is a two-component conveyor component according to one embodiment of the present disciosure
  • Figure 3a is a two-component conveyor component demonstrating an interlocking mechanism according to one embodiment of the present disciosure
  • Figure 3b is a two-component conveyor component demonstrating an interlocking mechanism according to another embodiment of the present disclosure
  • Figure 4 is a two-component conveyor component demonstrating a fastening mechanism according to one embodiment of the present disclosure
  • Figure 5a is a two-component conveyor component produced using an overmoiding process according to one embodiment of the present disclosure
  • Figure 5b is a two-component conveyor component produced using an overmoiding process according to another embodiment of the present disclosure.
  • the present disclosure is directed to a polyoxymethyiene based system with improved tribological properties such as a reduced coefficient of friction.
  • the triboiogicaS properties of the polyoxymethyiene based system can be improved by utilizing tribological modifiers.
  • the polyoxymethyiene based system may comprise a two-component system.
  • a two-component system is comprised of a first polymer layer and a second polymer layer wherein the second polymer layer may be connected to the first polymer layer.
  • the first polymer layer is comprised of a
  • polyoxymethyiene polymer composition comprising a polyoxymethyiene polymer and optionally, at least one tribological modifier.
  • the second polymer layer is comprised of a second polymer composition comprising a liquid crystalline polymer, a polyaryiene sulfide polymer, or a combination thereof.
  • the second polymer composition may further comprise at least one tribological modifier, a reinforcing fiber, or a combination thereof.
  • polyoxymethyiene based system of the present invention improved sliding properties and a reduced coefficient of friction against other surfaces can be obtained.
  • the system can exhibit a reduced coefficient of friction against other surfaces, such as a polyethylene terephthalate surface, while still exhibiting desirable mechanical properties.
  • these systems also generate little frictional noise and experience low wear.
  • the polyoxymethyiene polymer composition of the two-component system is comprised of a polyoxymethyiene polymer.
  • the preparation of the polyoxymethyiene polymer can be carried out by polymerization of polyoxymethylene-forming monomers, such as trioxane or a mixture of trioxane and a cyclic acetal such as dioxolane in the presence of ethylene glycol as a molecular weight regulator.
  • the polyoxymethyiene polymer used in the polymer composition may comprise a homopolymer or a copolymer.
  • the polyoxymethyiene is a homo- or copolymer which comprises at least 50 mo!.%, such as at least 75 mol.%, such as at least 90 moi.% and such as even at least 97 mol.% of -CHjO-repeat units.
  • a polyoxymethyiene copolymer is used.
  • the copolymer can contain from about 0.1 moi.% to about 20 mol.% and in particular from about 0.5 mol.% to about 10 mol.% of repeat units that comprise a saturated or ethylenicaily unsaturated alkylene group having at least 2 carbon atoms, or a cycioa!kylene group, which has sulfur atoms or oxygen atoms in the chain and may include one or more substituents selected from the group consisting of alkyl cycloalkyl, aryi, aralkyl, heteroaryl, halogen or alkoxy.
  • a cyclic ether or acetal is used that can be introduced into the copolymer via a ring-opening reaction.
  • Preferred cyclic ethers or acetals are those of the formula:
  • R 2 is a C 2 -C 4 -alkylene group which, if appropriate, has one or more substituents which are CrC 4 ⁇ akyi groups, or are CrC 4 -alkoxy groups, and/or are halogen atoms, preferably chlorine atoms.
  • ethylene oxide propylene 1 ,2-oxide, butylene 1 ,2-oxide, butylene 1 ,3-oxide, 1 ,3-dioxane, 1 ,3-dioxolane, and 1 ,3-dioxepan as cyclic ethers, and also of linear o!igo- or polyformals, such as polydioxo!ane or polydioxepan, as comonomers.
  • copolymers composed of from 99.5 to 95 mol.% of trioxane and of from 0.5 to 5 mol.% of one of the above-mentioned comonomers.
  • the polymerization can be effected as precipitation polymerization or in the melt.
  • the polymerization parameters such as duration of polymerization or amount of molecular weight regulator, the molecular weight and hence the VR value of the resulting polymer can be adjusted.
  • a polyoxymethyiene polymer with hydroxy! terminal groups can be produced using a cationic polymerization process followed by solution hydrolysis to remove any unstable end groups.
  • a cationic polymerization process followed by solution hydrolysis to remove any unstable end groups.
  • a glycol such as ethylene glycol can be used as a chain
  • the cationic polymerization results in a bimodal molecular weight distribution containing low molecular weight constituents.
  • the low molecular weight constituents can be significantly reduced by conducting the polymerization using a heteropoly acid such as phosphotungstic acid as the catalyst.
  • a heteropoly acid such as phosphotungstic acid
  • the amount of low molecular weight constituents can be less than about 2 wt.%.
  • a heteropoly acid refers to polyacids formed by the condensation of different kinds of oxo acids through dehydration and contains a mono- or poly- nuclear complex ion wherein a hetero element is present in the center and the oxo acid residues are condensed through oxygen atoms.
  • Such a heteropoly acid is represented by the formula:
  • M 1 represents an element selected from the group consisting of W, Mo, V or
  • n 1 to 10
  • n 6 to 40
  • z 10 to 100
  • x is an integer of 1 or above
  • y is 0 to 50.
  • the central element (M) in the formula described above may be composed of one or more kinds of elements selected from P and Si and the coordinate element (!W) is composed of at least one element selected from W, Mo and V, particularly W or Mo.
  • heteropoly acids are phosphomo!ybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomoiybdotungstovanadic acid, phosphotungstovanadic acid, siiicotungstic acid, silicomolybdic acid, si!icomolybdotungstic acid,
  • siiicomolybdotungstovanadic acid and acid salts thereof excellent results have been achieved with heteropoly acids selected from 12 ⁇ molybdophosphoric acid (H3PM012O40) and 12 ⁇ tungstophosphoric acid (H3PW12O40) and mixtures thereof.
  • the heteropoly acid may be dissolved in an alky! ester of a polybasic carboxyiic acid. It has been found that alkyl esters of polybasic carboxyiic acid are effective to dissolve the heteropoly acids or salts thereof at room temperature (25°C).
  • the alkyl ester of the polybasic carboxyiic acid can easily be separated from the production stream since no azeotropic mixtures are formed. Additionally, the alkyl ester of the polybasic carboxyiic acid used to dissolve the heteropoly acid or an acid salt thereof fulfills the safety aspects and environmental aspects and, moreover, is inert under the conditions for the manufacturing of oxymethylene polymers,
  • the alky! ester of a polybasic carboxyiic acid is an alkyl ester of an aliphatic dicarboxylic acid of the formula:
  • n is an integer from 2 to 12, preferably 3 to 6 and
  • R and R' represent independently from each other an alkyl group having 1 to 4 carbon atoms, preferably selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyi, iso-butyl and tert-butyl.
  • the polybasic carboxyiic acid comprises the dimethyl or diethyl ester of the above-mentioned formula, such as a dimethyl adipate (DMA).
  • DMA dimethyl adipate
  • alkyl ester of the polybasic carboxyiic acid may also be represented by the following formula:
  • n is an integer from 0 to 10, preferably from 2 to 4 and
  • R and R' are independently from each other alkyi groups having 1 to 4 carbon atoms, preferably selected from the group consisting of methyl, ethyl, n- propy!, iso-propyS, n-butyl, iso-butyi and tert.-butyi.
  • heteropoly acid Particularly preferred components which can be used to dissolve the heteropoly acid according to the above formula are butantetracarboxylic acid tetratethyl ester or butantetracarboxylic acid tetramethyl ester,
  • alky! ester of a polybasic carboxyiic acid are dimethyl giutaric acid, dimethyl adipic acid, dimethyi pimelic acid, dimethyl suberic acid, diethyl giutaric acid, diethyl adipic acid, diethyl pimelic acid, diethyl sube ic acid, diemethyl phthalic acid, dimethyl isophthaiic acid, dimethyl terephthalic acid, diethyl phthalic acid, diethyl isophthaiic acid, diethyl terephthalic acid,
  • dimethylisophthalate diethylisophthalate, dimethyiterephthalate or
  • the heteropoly acid is dissolved in the alkyi ester of the po!ybasic carboxyiic acid in an amount lower than 5 wt.%, preferably in an amount ranging from 0.01 to 5 wt.%, wherein the weight is based on the entire solution.
  • the polymer composition of the present disclosure may contain other polyoxymethylene homopolymers and/or
  • polystyrene resin polystyrene resin
  • polystyrene resin polystyrene resin
  • Such polymers are generally unbranched linear polymers which contain at least 80%, such as at least 90%, oxymethylene units.
  • the polyoxymethylene polymer can have any suitable molecular weight.
  • the molecular weight of the polymer for instance, can be from about 4,000 grams per mole to about 20,000 g/mo!. In other embodiments, however, the molecular weight can be well above 20,000 g/mol, such as from about 20,000 g/mol to about 100,000 g/mol.
  • the poiyoxymethyiene polymer present in the composition can generally melt flow index (MF!) ranging from about 1 to about 50 g/10 min, as determined according to ISO 1133 at 190 °C and 2.16 kg, though polyoxymethyienes having a higher or lower melt flow index are also encompassed herein.
  • the poiyoxymethyiene polymer may be a low or mid-molecular weight
  • poiyoxymethyiene that has a melt flow index of greater than about 5 g/10 min, greater than about 10 g/10 min. or greater than about 15 g/10 min.
  • the melt flow index of the poiyoxymethyiene polymer can be less than about 25 g/10 min, less than about 20 g/10 min, less than about 18 g/10 min, less than about 15 g/10 min, less than about 13 g/10 min, or less than about 12 g/10 min.
  • poiyoxymethyiene polymer may for instance be a high molecular weight
  • poiyoxymethyiene that has a melt flow index of less than about 5 g/10min, less than about 3 g/10min s or less than about 2 g/10min.
  • the poiyoxymethyiene polymer may contain a relatively high amount of functional groups, such as hydroxy! groups in the terminal positions. More particularly, the poiyoxymethyiene polymer can have terminal hydroxy! groups, for example hydroxyethylene groups and/or hydroxyl side groups, in at least more than about 50% of all the terminal sites on the polymer. It should be understood that the total number of terminai groups present includes ail side terminal groups. In addition to the terminal hydroxyl groups, the poiyoxymethyiene polymer may also have other terminal groups usual for these polymers such as alkoxy groups, formate groups, acetate groups or hemiacetal groups.
  • the poiyoxymethyiene polymer may also optionally have a relatively low amount of low molecular weight constituents.
  • low molecular weight constituents or fractions refer to constituents having molecular weights below 10,000 dalton.
  • the poiyoxymethyiene polymer can contain low molecular weight constituents in an amount less than about 10 wt.%, based on the total weight of the poiyoxymethyiene.
  • the poiyoxymethyiene polymer may contain low molecular weight constituents in an amount iess than about 5 wt.%, such as in an amount less than about 3 wt.%, such as even in an amount iess than about 2 wt.%.
  • the polyoxymethyiene polymer may be present in the polyoxymethyiene polymer composition in an amount of at least 60 wt.%, such as at least 70 wt.%, such as at least 80 wt.%, such as at least 90 wt.%, such as at least 95 wt.%.
  • the polyoxymethyiene polymer is present in an amount of less than about 100 wt.%, such as less than about 99 wt.%, such as less than about 97 wt.%, wherein the weight is based on the total weight of the polyoxymethyiene polymer composition.
  • the second po!ymer composition of the two-component system may comprise a liquid crystalline polymer.
  • Suitable thermotropic liquid crystalline polymers may include aromatic polyesters, aromatic poly(esteramides), aromatic poly(estercarbonates), aromatic polyamides, etc., and may likewise contain repeating units formed from one or more aromatic hydroxycarboxylic acids, aromatic dicarboxyiic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic amines, aromatic diamines, etc., as well as combinations thereof.
  • Liquid crystalline polymers are generally classified as "thermotropic” to the extent that they can possess a rod-like structure and exhibit a crystalline behavior in its molten state (e.g., thermotropic nematic state).
  • Such polymers may be formed from one or more types of repeating units as is known in the art.
  • the liquid crystalline polymer may, for example, contain one or more aromatic ester repeating units, typically in an amount of from about 60 mo!.% to about 99.9 mo!.%, in some embodiments from about 70 mol.% to about 99.5 moi.%, and in some embodiments, from about 80 mol.% to about 99 mol.% of the polymer.
  • the aromatic ester repeating units may be generally represented by the following Formula (I):
  • ring B is a substituted or unsubstituted ⁇ -membered aryi group (e.g., 1 ,4- pheny!ene or 1 ,3-phenylene), a substituted or unsubstituted 6-membered ary! group fused to a substituted or unsubstituted 5- or 6-membered aryi group (e.g., 2,6-naphthalene), or a substituted or unsubstituted 6-membered aryi group linked to a substituted or unsubstituted 5- or 6-membered aryi group (e.g., 4,4- biphenyiene); and
  • Yi and Y 2 are independently O, C(O), NH, C(0)HN, or NHC(O).
  • Y-i and Y2 are C(O).
  • aromatic ester repeating units may include, for instance, aromatic dicarboxylic repeating units (Yi and Y2 in Formula I are C(O)), aromatic hydroxycarboxylic repeating units (Y-i is O and Y 2 is C(O) in Formula I), as weli as various
  • Aromatic dicarboxylic repeating units may be employed that are derived from aromatic dicarboxylic acids, such as terephthalic acid, isophtha!ic acid, 2,6-naphthalenedicarboxylic acid, diphenyi efher-4,4'-dicarboxylic acid, 1 ,6-naphthalenedicarboxy!ic acid, 2,7-naphthalenedicarboxylic acid, 4,4 - dicarboxybiphenyl, bis(4-carboxyphenyl)ether, bis(4-carboxyphenyl)butane i bis (4- carboxyphenyl)ethane, bis(3-carboxyphenyl)ether, bis(3-carboxypheny!ethane, etc., as well as alkyl, alkoxy, aryi and halogen substituents thereof, and
  • aromatic dicarboxylic acids may include, for instance, terephthalic acid (“TA”), isophthalic acid (“IA”), and 2,6- naphthalenedicarboxylic acid (“NDA”).
  • TA terephthalic acid
  • IA isophthalic acid
  • NDA 2,6- naphthalenedicarboxylic acid
  • repeating units derived from aromatic dicarboxylic acids typically constitute from about 5 moi.% to about 60 moi.%, in some embodiments from about 10 mol.% to about 55 mol.%, and in some embodiments, from about 15 mol.% to about 50 mol.% of the polymer.
  • Aromatic hydroxycarboxylic repeating units may also be employed that are derived from aromatic hydroxycarboxylic acids, such as, 4-hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2 ⁇ hydroxy-6-naphthoic acid; 2-hydroxy- 5-naphthoic acid; 3-hydroxy-2 ⁇ naphthoic acid; 2-hydroxy-3-naphthoic acid; 4'- hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl-4-benzoic acid; 4'-hydroxyphenyl- 3-benzoic acid, etc., as well as alkyl, alkoxy, aryi and halogen substituents thereof, and combination thereof.
  • Particularly suitable aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid (“HBA”) and 8-hydroxy-2-naphthoic acid (“HNA").
  • repeating units derived from hydroxycarboxylic acids typically constitute from about 10 mol.% to about 85 mol.%, in some embodiments from about 20 mol.% to about 80 moi.%, and in some embodiments, from about 25 mol.% to about 75 moi.% of the polymer.
  • repeating units may also be employed in the polymer.
  • repeating units may be employed that are derived from aromatic diols, such as hydroquinone, resorcinol, 2,6-dihydroxynaphthaiene, 2,7- dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (or 4,4'- biphenol), 3,3'-dihydroxybtphenyi, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4 ⁇ hydroxypheny!ethane, etc., as well as alkyl, alkoxy.
  • aromatic diols such as hydroquinone, resorcinol, 2,6-dihydroxynaphthaiene, 2,7- dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (or 4,4'- biphenol), 3,
  • aromatic diols may include, for instance, hydroquinone (“HQ”) and 4,4'-biphenol (“BP").
  • HQ hydroquinone
  • BP 4,4'-biphenol
  • repeating units derived from aromatic diols typically constitute from about 1 mol.% to about 30 mol.%, in some embodiments from about 2 mol.% to about 25 mol.%, and in some embodiments, from about 5 mol.% to about 20% of the polymer.
  • Repeating units may also be employed, such as those derived from aromatic amides (e.g., acetaminophen (“APAP”)) and/or aromatic amines (e.g., 4-aminophenol (“AP”), 3-aminophenol, 1 ,4- phenylenediamine, 1 ,3-phenylenediamine, etc.).
  • aromatic amides e.g., acetaminophen (“APAP)
  • aromatic amines e.g., 4-aminophenol (“AP”), 3-aminophenol, 1 ,4- phenylenediamine, 1 ,3-phenylenediamine, etc.
  • repeating units derived from aromatic amides (e.g., APAP) and/or aromatic amines (e.g., AP) typically constitute from about 0.1 moi.% to about 20 mol.%, in some embodiments from about 0.5 mol.% to about 15 mol.%, and in some embodiments, from about 1 mol.% to about 10 mol.% of the polymer. It should also be understood that various other monomeric repeating units may be incorporated into the polymer.
  • the polymer may contain one or more repeating units derived from non-aromatic monomers, such as aliphatic or cycioa!iphatsc hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.
  • non-aromatic monomers such as aliphatic or cycioa!iphatsc hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.
  • the polymer may be "wholly aromatic" in that it lacks repeating units derived from non-aromatic (e.g., aliphatic or cycloaliphatic) monomers.
  • the liquid crystalline polymer may be a 'low naphthenic" polymer to the extent that it contains a minimal content of repeating units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as naphthalene-2,6-dicarboxylic acid (“NDA”), 6 ⁇ hydroxy- 2-naphthoic acid (“HNA”), or combinations thereof.
  • NDA naphthalene-2,6-dicarboxylic acid
  • HNA 6 ⁇ hydroxy- 2-naphthoic acid
  • the total amount of repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids may typically be no more than 30 mol.%, in some embodiments no more than about 15 mol.%, in some embodiments no more than about 10 mo!.%, in some embodiments no more than about 8 mol.%, and in some embodiments, from 0 mol.% to about 5 mo!.% of the polymer (e.g., 0 mol.%).
  • the resulting "low naphthenic" polymers are still capable of exhibiting good thermal and mechanical properties.
  • the liquid crystalline polymer may be formed from repeating units derived from 4 ⁇ hydroxybenzoic acid (“HBA”) and terephthalic acid (“TA”) and/or isophthalic acid (“IA”), as well as various other optional constituents.
  • HBA 4 ⁇ hydroxybenzoic acid
  • TA terephthalic acid
  • IA isophthalic acid
  • the repeating units derived from 4-hydroxybenzoic acid (“HBA”) may constitute from about 10 mol.% to about 80 mol.%, in some
  • the repeating units derived from terephthalic acid (“TA”) and/or isophthalic acid (“IA " ) may likewise constitute from about 5 mol.% to about 40 mol.%, in some embodiments from about 10 mol.% to about 35 mol.%, and in some embodiments, from about 15 mol.% to about 35 mol.% of the polymer.
  • Repeating units may also be employed that are derived from 4,4'-biphenol (“BP”) and/or hydroquinone (“HQ”) in an amount from about 1 mol.% to about 30 mol.%, in some embodiments from about 2 mol.% to about 25 mol.%, and in some embodiments, from about 5 mol.% to about 20 mol.% of the polymer.
  • Other possible repeating units may include those derived from 6-hydroxy-2-naphthoic acid (“HNA”), 2,6-naphthaienedicarboxylic acid (“NDA”), and/or acetaminophen (“APAP”).
  • repeating units derived from HNA, NDA, and/or APAP may each constitute from about 1 mol.% to about 35 mol.%, in some embodiments from about 2 mol.% to about 30 mol.%, and in some embodiments, from about 3 rno!.% to about 25 mol.% when employed.
  • the liquid crystalline polymer may be prepared by initially introducing the aromatic monomer ⁇ s) used to form ester repeating units (e.g., aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, etc.) and/or other repeating units (e.g., aromatic diol, aromatic amide, aromatic amine, etc.) into a reactor vessel to initiate a polycondensation reaction.
  • ester repeating units e.g., aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, etc.
  • other repeating units e.g., aromatic diol, aromatic amide, aromatic amine, etc.
  • the vessel employed for the reaction is not especially limited, although it is typically desired to employ one that is commonly used in reactions of high viscosity fluids.
  • a reaction vessel may include a stirring tank-type apparatus that has an agitator with a variably-shaped stirring blade, such as an anchor type, multistage type, spiral- ribbon type, screw shaft type, etc., or a modified shape thereof.
  • Further examples of such a reaction vessel may include a mixing apparatus commonly used in resin kneading, such as a kneader, a roil mill, a Banbury mixer, etc.
  • the reaction may proceed through the acetyiation of the monomers as known the art. This may be accomplished by adding an acetylating agent (e.g., acetic anhydride) to the monomers.
  • acetyiation is generally initiated at temperatures of about 90°C. During the initial stage of the acetyiation, reflux may be employed to maintain vapor phase temperature below the point at which acetic acid byproduct and anhydride begin to distill. Temperatures during acetyiation typically range from between 90°C to 150°C, and in some
  • the vapor phase temperature typically exceeds the boiling point of acetic acid, but remains low enough to retain residual acetic anhydride.
  • acetic anhydride vaporizes at temperatures of about 140°C.
  • providing the reactor with a vapor phase reflux at a temperature of from about 1 10°C to about 130°C is particularly desirable.
  • an excess amount of acetic anhydride may be employed.
  • the amount of excess anhydride wili vary depending upon the particular acety!ation conditions employed, including the presence or absence of reflux.
  • the use of an excess of from about 1 to about 10 mole percent of acetic anhydride, based on the total moles of reactant hydroxy! groups present is not uncommon.
  • Aceiylaiion may occur in in a separate reactor vessel, or it may occur in situ within the polymerization reactor vessel.
  • one or more of the monomers may be introduced to the acetyiation reactor and subsequently transferred to the polymerization reactor.
  • one or more of the monomers may also be directly introduced to the reactor vessel without undergoing pre-acetylation.
  • a catalyst may be optionally employed, such as metal salt catalysts (e.g., magnesium acetate, tin(l) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, etc.) and organic compound catalysts (e.g., N-methyiimidazole).
  • metal salt catalysts e.g., magnesium acetate, tin(l) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, etc.
  • organic compound catalysts e.g., N-methyiimidazole
  • the reaction mixture is generally heated to an elevated temperature within the polymerization reactor vessel to initiate melt polycondensatson of the reactants.
  • Polycondensatson may occur, for instance, within a temperature range of from about 250°C to about 400°C, in some embodiments from about 280°C to about 395°C, and in some embodiments, from about 300°C to about 38Q°C.
  • one suitable technique for forming the liquid crystalline polymer may include charging precursor monomers and acetic anhydride into the reactor, heating the mixture to a temperature of from about 90°C to about 150°C to acetylize a hydroxy!
  • the reaction mixture is generally subjected to agitation during polymerization to ensure good heat and mass transfer, and in turn, good material homogeneity.
  • the rotational velocity of the agitator may vary during the course of the reaction, but typically ranges from about 10 to about 100 revolutions per minute (“rpm"), and in some embodiments, from about 20 to about 80 rpm.
  • the polymerization reaction may also be conducted under vacuum, the application of which facilitates the removal of volatiies formed during the final stages of polycondensation.
  • the vacuum may be created by the application of a suctional pressure, such as within the range of from about 5 to about 30 pounds per square inch (“psi"), and in some embodiments, from about 10 to about 20 psi.
  • the molten polymer may be discharged from the reactor, typically through an extrusion orifice fitted with a die of desired configuration, cooled, and collected. Commonly, the melt is discharged through a perforated die to form strands that are taken up in a water bath, pelletized and dried. In some embodiments, the melt polymerized polymer may also be subjected to a subsequent solid-state polymerization method to further increase its molecular weight. Solid-state polymerization may be conducted in the presence of a gas (e.g., air, inert gas, etc.). Suitable inert gases may include, for instance, include nitrogen, helium, argon, neon, krypton, xenon, etc., as well as
  • a gas e.g., air, inert gas, etc.
  • Suitable inert gases may include, for instance, include nitrogen, helium, argon, neon, krypton, xenon, etc., as well as
  • the solid-state polymerization reactor vessel can be of virtually any design that will allow the polymer to be maintained at the desired solid-state polymerization temperature for the desired residence time. Examples of such vessels can be those that have a fixed bed, static bed, moving bed, fiuidized bed, etc.
  • the temperature at which solid-state polymerization is performed may vary, but is typically within a range of from about 250°C to about 350°C.
  • the polymerization time will of course vary based on the temperature and target molecular weight. In most cases, however, the solid-state polymerization time will be from about 2 to about 12 hours, and in some embodiments, from about 4 to about 10 hours.
  • the liquid crystalline polymer may be present in the second polymer composition in an amount of at least 40 wt.%, such as at least 50 wt.%, such as at least 80 wt.%, such as at least 70 wt.%. such as at least 80 wt.%, such as at least 90 wt.%.
  • the liquid crystalline polymer is present in an amount of less than about 100 wt.%, such as less than about 90 wt.%, such as less than about 80 wt.%, such as less than about 70 wt.%, such as less than about 60 wt.%, wherein the weight is based on the total weight of the second polymer composition.
  • the second polymer composition of the two-component system may comprise a poiyaryiene sulfide polymer.
  • Poiyaryiene sulfide polymers are generally able to withstand relatively high temperatures without melting.
  • Poiyaryiene sulfide polymers generally have repeating units of the formula:
  • Ar 1 , Ar 2 , Ar 3 , and Ar 4 are independently arylene units of 8 to 18 carbon atoms;
  • W, X, Y, and Z are independently bivalent linking groups selected from -S0 2 -, -S-, -SO-, -CO-, -0-, -C(0)0- or alky!ene or alkylidene groups of 1 to 6 carbon atoms, wherein at least one of the linking groups is -S-; and n, m, i, j, k, I, o, and p are independently 0, 1 , 2, 3, or 4, subject to the proviso that their sum total is not less than 2.
  • the arylene units Ar 1 , Ar ⁇ , Ar°, and Ar 4 may be selectively substituted or unsubstituted.
  • Advantageous arylene units are phenylene, biphenylene, naphthylene, anthracene and phenanthrene.
  • the poiyaryiene sulfide typically includes more than about 30 mol.%, more than about 50 mol.%, or more than about 70 mol. % arylene sulfide (-S-) units.
  • the poiyaryiene sulfide may include at least 85 mol.% sulfide linkages attached directly to two aromatic rings, in one particular embodiment, the poiyaryiene sulfide is a polyphenylene sulfide, defined herein as containing the phenylene sulfide structure -(CeH 4 --S) n - (wherein n is an integer of 1 or more) as a component thereof.
  • Synthesis techniques that may be used in making a poSyary!ene sulfide are generally known in the art.
  • a process for producing a polyarylene sulfide can include reacting a material that provides a hydrosu!fide son (e.g., an alkali metal sulfide) with a dihaloaromatic compound in an organic amide solvent.
  • the alkali metal sulfide can be, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide or a mixture thereof.
  • the alkali metal sulfide is a hydrate or an aqueous mixture, the alkali metal sulfide can be processed according to a dehydrating operation in advance of the polymerization reaction.
  • An alkali metal sulfide can also be generated in situ.
  • a small amount of an alkali metal hydroxide can be included in the reaction to remove or react impurities (e.g., to change such impurities to harmless materials) such as an alkali metal polysuifide or an alkali metal thiosulfate, which may be present in a very small amount with the alkali metal sulfide.
  • the dihaloaromatic compound can be, without limitation, an o- dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene,
  • dihaiodiphenyl ketone Dihaloaromatic compounds may be used either singly or in any combination thereof.
  • Specific exemplary dihaloaromatic compounds can include, without limitation, p-dichiorobenzene; m-dichlorobenzene; o- dichlorobenzene; 2,5-dich!orotoluene; 1 .4-dibromobenzene; 1 ,4- dichioronaphthalene; 1 -methoxy-2,5-dichlorobenzene; 4,4 i -dichSorobiphenyi; 3,5- dichlorobenzoic acid; 4,4' ⁇ dichlorodiphenyl ether; 4,4'-dichlorodiphenylsuifone; 4,4'-dichlorodiphenylsulfoxide; and 4,4'-dichlorodiphenyi ketone.
  • the halogen atom can be fluorine, chlorine, bromine or iodine, and two halogen atoms in the same dihalo-aromatic compound may be the same or different from each other.
  • o-dichiorobenzene, m-dichlorobenzene, p-dichlorobenzene or a mixture of two or more compounds thereof is used as the dihalo-aromatic compound.
  • a monohalo compound not necessarily an aromatic compound
  • the dihaloaromatic compound it is also possible to use a monohalo compound (not necessarily an aromatic compound) in combination with the dihaloaromatic compound in order to form end groups of the polyarylene sulfide or to regulate the polymerization reaction and/or the molecular weight of the polyarylene sulfide.
  • the polyarylene sulfide(s) may be homopoiymers or copolymers.
  • selective combination of dshaloaromatic compounds can result in a polyarylene sulfide copolymer containing not less than two different units.
  • a polyarylene sulfide copolymer can be formed containing segments havin the structure of formula:
  • a polyarylene sulfide copolymer may be formed that includes a first segment with a number-average molar mass Mn of from 1000 to 20,000 g/moS.
  • the first segment may include first units that have been derived from structures of the formula:
  • radicals R 1 and R 2 independently of one another, are a hydrogen, fluorine, chlorine or bromine atom or a branched or unbranched alkyl or aikoxy radical having from 1 to 6 carbon atoms; and/or second units that are derived from structures of the formula:
  • the first unit may be p-hydroxybenzoic acid or one of its derivatives
  • the second unit may be composed of 2-hydroxynaphthalene-8-carboxylsc acid.
  • the second segment may be derived from a poiyarylene sulfide structure of the formula:
  • Ar is an aromatic radical or more than one condensed aromatic radical, and q is a number from 2 to 100, in particular from 5 to 20.
  • the radical Ar may be a phenylene or naphthyiene radical.
  • the second segment may be derived from poiy(m-thiophenyiene), from poly ⁇ o- thiophenyiene), or from po!y(p-tbiophenylene).
  • the poiyarylene su!fide(s) may be linear, semi-linear, branched or crosslinked.
  • Linear poiyarylene sulfides typically contain 80 mol.% or more of the repeating unit -(Ar-S)-.
  • Such linear polymers may also include a small amount of a branching unit or a cross-linking unit, but the amount of branching or cross- linking units is typically less than about 1 mol.% of the total monomer units of the poiyarylene sulfide.
  • a linear poiyarylene sulfide polymer may be a random copolymer or a block copolymer containing the above-mentioned repeating unit.
  • Semi-linear poiyarylene sulfides may likewise have a cross-linking structure or a branched structure introduced into the polymer a small amount of one or more monomers having three or more reactive functional groups.
  • monomer components used in forming a semi-linear poiyarylene sulfide can include an amount of polyhaloaromatic compounds having two or more halogen substituents per molecule which can be utilized in preparing branched polymers.
  • Such monomers can be represented by the formula R'X n , where each X is selected from chlorine, bromine, and iodine, n is an integer of 3 to 8, and R' is a polyvalent aromatic radical of valence n which can have up to about 4 methyl substituents, the total number of carbon atoms in R' being within the range of 6 to about 16,
  • R'X n is an integer of 3 to 8
  • R' is a polyvalent aromatic radical of valence n which can have up to about 4 methyl substituents, the total number of carbon atoms in R' being within the range of 6 to about 16
  • examples of some polyhaloaromatic compounds having more than two halogens substituted per molecufe that can be empfoyed in forming a semi-linear polyarylene sulfide include 1 ,2,3-trichlorobenzene, 1 ,2,4-trichlorobenzene, 1 ,3- dichloro-5-bromobenzen
  • the number average molecular weight of the polyarylene sulfide is typically about 15,000 g/mol or more, and in some embodiments, about 30,000 g/mol or more.
  • a small amount of chlorine may be employed during formation of the polyarylene sulfide.
  • the polyarylene sulfide will still have a low chlorine content, such as about 1000 ppm or less, in some embodiments about 900 ppm or less, in some embodiments from about 1 to about 800 ppm, and in some embodiments, from about 2 to about 700 ppm. In certain embodiments, however, the
  • polyarylene sulfide is generally free of chlorine or other halogens.
  • the polyarylene sulfide polymer may be present in the second polymer composition in an amount of at least 40 wt.%, such as at least 50 wt.%, such as at least 60 wt.%, such as at least 70 wt.%, such as at least 80 wt.%, such as at least 90 wt.%.
  • the polyarylene sulfide polymer is present in an amount of less than about 100 wt.%, such as less than about 90 wt.%, such as less than about 80 wt.%, such as less than about 70 wt.%, such as less than about 60 wt.%, wherein the weight is based on the total weight of the second polymer
  • the poiyoxymethylene polymer composition of the two-component system may further comprise at least one tribological modifier. Additionally, according to the present disclosure, the second polymer composition of the two-component system may further comprise at least one tribological modifier. [00078] According to the present disclosure, the poiyoxymethyiene poiymer composition of the two-component system may comprise boron nitride, ultra-high molecular weight silicone, or a combination thereof,
  • boron nitride may be used to modify the
  • Boron nitride can be particularly beneficial in improving the tribological properties and reducing the coefficient of friction of poiyoxymethyiene.
  • Boron nitride exists in a variety of different crystalline forms (e.g., n-BN - hexagonal, c-BN - cubic or spharlerite, and w-BN - wurtzite).
  • hexagonal boron nitride may be used in the composition.
  • the h-BN may promote lubricity due to its layered structure and weak secondary forces between adjacent layers allowing or easy sliding of the layers.
  • the boron nitride may have an average particle size ranging from about 0.5 pm to about 10 ⁇ , such as from about 1 ⁇ to about 6 ⁇ , such as about 1.5 pm or 5 pm.
  • the boron nitride may be present in the polyoxymethyiene poiymer composition in an amount of at least about 0.1 wt.%, such as at feast about 0.5 wt.%, such as at least about 0.75 wt.%, such as at least about 1 wt.%, such as at least about 2 wt.% and generally less than about 10 wt.%, such as less than about 5 wt.%, such as less than about 2.5 wt.%, such as less than about 2 wt.%, wherein the weight is based on the total weight of the polyoxymethyiene polymer composition.
  • the composition may be substantially free of the boron nitride such that it is present in an amount of 0 wt.%.
  • ultra-high molecular weight silicone may be used to modify the polyoxymethyiene polymer.
  • the UHMW-Si can have an average molecular weight of greater than 100,000 g/mol, such as greater than about 200,000 g/mol, such as greater than about 300,000 g/mol, such as greater than about 500,000 g/mol and less than about 3,000,000 g/mol, such as less than about 2,000,000 g/mol, such as less than about 1 ,000,000 g/mol, such as less than about 500,000 g/mol, such as less than about 300,000 g/mol.
  • the UHMW-Si can have a kinematic viscosity at 40°C measured according to DIN 51562 of greater than 100,000 mm 2 s '1 , such as greater than about 200,000 mmV, such as greater than about 1 ,000,000 mm 2 s "1 , such as greater than about 5,000,000 mm 2 s "1 , such as greater than about 10,000,000 mm 2 s “1 , such as greater than about 15,000,000 mmV 1 and less than about 50,000,000 mmV ⁇ such as less than about 25,000,000 mm 1 , such as less than about 10,000,000 mm 2 s "1 , such as less than about 1 ,000,000 mm 2 s " ⁇ such as less than about 500,000 mm 2 s "1 , such as less than about 200,000 mm 2 s "1 ,
  • the UH W-Si may comprise a siloxane such as a polysiloxane or polyorganosiloxane.
  • the UHMW-Si may comprise a
  • dialkylpolysiloxane such as a dimethylsiloxane, an alkylaryisi!oxane such as a phenyimethylsilaoxane, or a diarylsiioxane such as a diphenylsiloxane, or a homopolymer thereof such as a polydimethylsiloxane or a
  • polymethyiphenylsiioxane or a copolymer thereof with the above molecular weight and/or kinematic viscosity requirements.
  • the polysiloxane or polyorganosiloxane may also be modified with a substituent such as an epoxy group, a hydroxy! group, a carboxyl group, an amino group or a substituted amino group, an ether group, or a meth(acryloy!) group in the end or main chain of the molecule.
  • the UHMW-Si compounds may be used singly or in combination. Any of the above UHMW-Si compounds may be used with the above molecular weight and/or kinematic viscosity requirements.
  • the UHMW-Si may be added to the poiyoxymethyiene polymer composition as a masterbatch wherein the UHMW-Si is dispersed in a
  • the masterbatch may comprise from about 10 wt.% to about 50 wt.%, such as from about 25 wt.% to about 50 wt.%, such as from about 35 wt.% to about 45 wt.% of an UHMW-Si.
  • the UHMW-Si may be present in the poiyoxymethyiene polymer composition in an amount of at least about 0.1 wt.%, such as at least about 0.5 wt.%, such as at least about 0.75 wt.%, such as at least about 1 wt.%, such as at least about 2 wt.% and generally less than about 10 wt.%, such as less than about 6 wt.%, such as less than about 5 wt.%, such as less than about 4 wt.%, such as less than about 3.5 wt.%, such as less than about 3 wt.%, wherein the weight is based on the total weight of the poiyoxymethyiene polymer composition.
  • the composition may be substantially free of the UHMW ⁇ Ss such that it is present in an amount of 0 wt.%.
  • boron nitride such as hexagonal- boron nitride
  • UH W-Si may be utilized in combination to modify the poiyoxymethy!ene polymer.
  • the present inventors have discovered that when both tribological modifiers are used simultaneously, the combination provides a synergistic effect with a resulting polymer composition that exhibits improved tribological properties while maintaining or even improving the mechanical properties.
  • the boron nitride and UHMW-Si may be utilized in the polyoxymethylene polymer composition in the amounts disclosed above.
  • the second polymer composition of the two-component system may comprise a polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the PTFE may be in the form of a powder.
  • the PTFE may be in the form of a fiber.
  • the PTFE may be present in an amount of at least 0.1 wt.%, such as at feast 1 wt.%, such as at least 5 wt.%, such as at least 10 wt.%, such as at least 15 wt.% and generally less than about 50 wt.%, such as less than about 40 wt.%, such as less than about 30 wt.%, such as less than about 25 wt.%, such as less than about 15 wt.%.
  • the polyoxymethylene polymer composition of the two-component system may also comprise PTFE as described above.
  • the second polymer composition may also comprise boron nitride, UHMW-Si, or a combination thereof as described above.
  • tribological modifiers may be incorporated into the polyoxymethylene polymer composition or the second polymer composition.
  • These tribological modifiers may include, for instance, calcium carbonate particles, ultrahigh-moSecular weight polyethylene (UHMW-PE) particles, stearyl stearate particles, silicone oil, a polyethylene wax, an amide wax, wax particles comprising an aliphatic ester wax comprised of a fatty acid and a monohydric alcohol, a graft copolymer with an olefin polymer as a graft base, or a combination thereof.
  • UHMW-PE ultrahigh-moSecular weight polyethylene
  • stearyl stearate particles silicone oil
  • a polyethylene wax an amide wax
  • wax particles comprising an aliphatic ester wax comprised of a fatty acid and a monohydric alcohol
  • graft copolymer with an olefin polymer as a graft base or a combination thereof.
  • UHMW-PE uitrahigh-moiecular weight polyethylene
  • the UHMW-PE can have an average molecular weight of higher than 1.0-10 6 g/moi, such as higher than 2.0- 10 6 g/mol, such as higher than 4.0 0 6 g/moi, such as ranging from 1 ,0-1 Q 6 g/moi to 15.0-10 6 g/mol, such as from 3.0- 10 6 g/mol to 12.0-10 6 g/moi, determined by viscosimetry.
  • the viscosity number of the UHMW-PE is higher than 1000 ml/g, such as higher than 1500 m!/g, such as ranging from 1800 ml/g to 5000 ml/g, such as ranging from 2000 ml/g to 4300 ml/g (determined according to ISO 1828, part 3; concentration in
  • decahydronaphthalin 0.0002 g/ml
  • the composition may be substantially free of silicone oil, such as less than about 0.2 wt.%, such as less than about 0.1 wt.%, such as less than about 0.05 wt.%, such as less than about 0.01 wt.%, such as about 0 wt.%. . in another embodiment, the composition may not comprise a combination of silicone oil and UHMW-Si alone. In such
  • the composition may comprise UHMW-Si, silicone oil, and another triboiogical modifier, such as hexagonal boron nitride or PTFE.
  • the silicone oil can have an average molecular weight of at least about 5,000 g/mol, such as at least about 20,000 g/mol, such as at least about 50,000 g/mol and generally less than 100,000 g/mol, such as less than about 75,000 g/mol, such as less than about 50,000 g/mol.
  • the silicone oil can have a kinematic viscosity at 40°C measured according to DIN 51582 of greater than about 100 mm 2 s "1 , such as greater than about 5,000 mmV 1 , such as greater than about 15,000 mrnV and generally less than
  • the silicone oil may be a silicone oil, such as less than about 50,000 mm 2 s " ! , such as less than about 25,000 mm 2 s 1 , such as less than about 15,000 mmV 1 .
  • the silicone oil may be a silicone oil, such as less than about 50,000 mm 2 s " ! , such as less than about 25,000 mm 2 s 1 , such as less than about 15,000 mmV 1 .
  • the silicone oil may be a silicone oil, such as less than about 50,000 mm 2 s " ! , such as less than about 25,000 mm 2 s 1 , such as less than about 15,000 mmV 1 .
  • liquid polysiloxane such as a poiydimethyisiioxane at a room
  • a graft copolymer which has an olefin polymer as a graft base and, grafted on this, at least one vinyl polymer or one ether polymer, and/or a graft copolymer which has an elastomeric core based on polydienes and a hard graft envelope composed of (meth)acrylates and/or of ⁇ meth)acrylonitriles.
  • a suitable graft base can be any olefin homopo!ymer (e.g., polyethylene or polypropylene) or copolymer or copolymers derived from copolymerizable eihyienicaiiy unsaturated monomers (e.g, ethylenepropylene copolymers, ethylene-1-butene copolymers, ethylene/glycidyi (meth)acrylate copolymers).
  • Suitable graft monomers are any of the ethylenicaily unsaturated monomers having a polar group or other graftabie monomers having polar groups that modify the polarity of the essentially non-polar graft base (e.g.
  • the graft copolymer may comprise a
  • the tribological modifiers improve the triboiogical properties of the poiyoxymethylene polymer composition and second polymer composition of the poiyoxymethylene based system such as by reducing the coefficient of friction and wear when contacted with another surface, such as a polyethylene
  • tribological modifiers may even improve upon the mechanical properties of the poiyoxymethylene poiymer composition and/or the second polymer composition.
  • tribologicai modifiers improve the tribologicai properties of the compositions and the polyoxymethylene based systems without the need for an external lubricant, such as water-based or PTFE- based external lubricants, when utilized in tribologicai applications.
  • An external lubricant may be a lubricant that is applied to a polymer article or
  • an external lubricant may not be associated with the polyoxymethylene based system or polymer article such that the external lubricant is not present on a surface of the polyoxymethylene based system or polymer article.
  • an external lubricant may be utilized with the polyoxymethylene based system and polymer article of the present disclosure.
  • the polyoxymethylene poiymer composition of the two-component system may further comprise at least one reinforcing fiber. Additionally, according to the present disclosure, the second polymer composition of the two-component system may further comprise at least one reinforcing fiber.
  • the reinforcing fibers which may be used according to the present invention include mineral fibers, glass fibers, polymer fibers such as aramid fibers, metal fibers such as steel fibers, carbon fibers, or natural fibers. These fibers may be unmodified or modified, e.g. provided with a sizing or chemically treated, in order to improve adhesion to the polymer.
  • the reinforcing fibers comprise glass fibers.
  • Glass fibers may be provided with a sizing to protect the glass fiber, to smooth the glass fiber, and to improve the adhesion between the glass fiber and the poiymer matrix material.
  • a sizing usually comprises silanes, film forming agents, lubricants, wetting agents, adhesives, optionally antistatic agents and p!asticizers, emulsifiers and optionally further additives.
  • silanes are aminosiianes.
  • Film forming agents are. for example, polyvinylacetates, polyesters, and poiyurethanes.
  • glass fibers are E-glass, A- g!ass, C-giass, D-glass, AR-glass, R-glass, S1 -glass, S2-giass, etc., and mixtures thereof.
  • the glass fibers may be chopped glass fibers or glass fiber rovings (tows).
  • the reinforcing fibers may be compounded into the polymer matrix, for example in an extruder or kneader.
  • the reinforcing fibers may also advantageously take the form of continuous-filament fibers sheathed or
  • Fiber diameters can vary depending upon the particular fiber used and whether the fiber is in either a chopped or a continuous form.
  • the fibers can have a diameter of less than about 100 pm, such as less than about 50 pm.
  • the fibers can be chopped or continuous fibers and can have a fiber diameter of from about 5 pm to about 100 pm, such as from about 5 pm to about 50 pm, such as from about 5 ⁇ to about 15 pm.
  • the fibers may also have a relatively high aspect ratio (average length divided by nominal diameter) to help improve the mechanical properties of the resulting polymer composition.
  • the fibers may have an aspect ratio of from about 2 to about 50, in some embodiments from about 4 to about 40, and in some embodiments, from about 5 to about 20.
  • the reinforcing fibers may also help improve the strength.
  • the relative amount of the reinforcing fiber in the polymer compositions may also be selectively controlled to help achieve the desired mechanical properties without adversely impacting other properties of the composition, such as its flowability.
  • the respective composition may contain reinforcing fibers in an amount of at least 1 wt.%, such as at least 5 wt.%, such as at least 7 wt.%, such as at least 10 wt.%, such as at least 15 wt.% and generally less than about 50 wt.%, such as less than about 45 wt.%, such as less than about 40 wt.%, such as less than about 30 wt.%, such as less than about 20 wt.%, wherein the weight is based on the total weight of the respective poiyoxymethylene or second polymer composition.
  • polymer compositions of the present disclosure may also contain other known additives such as, for exampie, antioxidants, formaldehyde
  • compositions can contain processing auxiliaries, for example adhesion promoters, lubricants, nucleants, demolding agents, fillers, or antistatic agents and additives which impart a desired property to the compositions and articles or parts produced therefrom.
  • processing auxiliaries for example adhesion promoters, lubricants, nucleants, demolding agents, fillers, or antistatic agents and additives which impart a desired property to the compositions and articles or parts produced therefrom.
  • an ultraviolet light stabilizer may be present.
  • the ultraviolet light stabilizer may comprise a benzophenone. a benzotriazole, or a benzoate.
  • the UV light absorber when present, may be present in the polymer composition in an amount of at least about 0.01 wt.%, such as at least about 0.05 wt.%, such as at least about 0.075 wt.% and less than about 1 wt.%, such as less than about 0.75 wt.%, such as less than about 0.5 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • a formaldehyde scavenger such as a nitrogen- containing compound
  • a formaldehyde scavenger such as a nitrogen- containing compound
  • these are heterocyclic compounds having at least one nitrogen atom as hetero atom which is either adjacent to an amino-substituted carbon atom or to a carbonyi group, for example pyridine, pyrimidine, pyrazine, pyrroiidone, aminopyridine and compounds derived therefrom.
  • Other particularly advantageous compounds are friamino-1 ,3,5-triazine (melamine) and its derivatives, such as melamine-formaldehyde condensates and methyloi melamine.
  • Oligomeric poiyamides are also suitable in principle for use as formaldehyde scavengers.
  • the formaldehyde scavenger may be used individually or in combination,
  • the formaldehyde scavenger can be a guanamine compound which can include an aliphatic guanamine-based compound, an alicyclic guanamine-based compound, an aromatic guanamine-based compound, a hetero atom-containing guanamine-based compound, or the like.
  • the formaldehyde scavenger may be present in the polymer composition in an amount of at least about 0.01 wt.%, such as at least about 0.05 wt.%, such as at least about 0.075 wt.% and less than about 1 wt.%, such as less than about 0.75 wt.%, such as less than about 0.5 wt.%, wherein the weight is based on the total weight of the respective poiymer composition.
  • an acid scavenger may be present.
  • the acid scavenger may comprise, for instance, an alkaline earth metal salt.
  • the acid scavenger may comprise a calcium salt, such as a calcium citrate.
  • the acid scavenger may be present in an amount of at least about 0.001 wt.%, such as at Ieast about 0.005 wt.%, such as at Ieast about 0.0075 wt.% and less than about 1 wt.%, such as less than about 0,75 wt.%, such as less than about 0.5 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • a nucleant may be present.
  • the nucieant may increase crystallinity and may comprise an oxymethylene terpolymer.
  • the nucieant may comprise a terpolymer of butanediol diglycidyl ether, ethylene oxide, and trioxane.
  • the nucieant may be present in the composition in an amount of at Ieast about 0.01 wt.%, such as at Ieast about 0.05 wt.%, such as at least about 0.1 wt.% and less than about 2 wt.%, such as less than about 1.5 wt.%, such as less than about 1 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • an antioxidant such as a sterlcally hindered phenol
  • examples which are available commercially, are pentaerythrityl tetrakis[3-(3,5-di-tert ⁇ butyl-4-hydroxyphenyl)propionate], Methylene glycol bis[3-(3- tert-butyS-4-hydroxy-5-methylphenyl)propionate], 3,3 !
  • the antioxidant may be present in the polymer composition in an amount of at least about 0.01 wt.%, such as at least about 0.05 wt.%, such as at Ieast about 0.075 wt.% and less than about 1 wt.%, such as less than about 0.75 wt.%, such as less than about 0.5 wt.%, wherein the weight is based on the total weight of the respective poiymer composition.
  • a light stabilizer such as a sterlcally hindered amine
  • a light stabilizer may be present in addition to the ultraviolet light stabilizer.
  • Hindered amine light stabilizers that may be used include oligomeric hindered amine compounds that are N-methylated.
  • hindered amine light stabilizer may comprise a high molecular weight hindered amine stabilizer.
  • the Sight stabilizers when present, may be present in the polymer composition in an amount of at least about 0.01 wt.%, such as at least about 0.05 wt.%, such as at least about 0.075 wt.% and less than about 1 wt.%, such as less than about 0.75 wt.%, such as iess than about 0.5 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • a lubricant not including the triboiogica! modifiers mentioned above, may be present.
  • the lubricant may comprise a polymer wax composition. Further, in one embodiment, a polyethylene glycol polymer
  • the polyethylene glycol may have a molecular weight of from about 1000 to about 5000, such as from about 3000 to about 4000. !n one embodiment, for instance, PEG-75 may be present.
  • Lubricants may generally be present in the polymer composition in an amount of at least about 0.01 wt.%, such as at least about 0,05 wt.%, such as at least about 0.075 wt.% and less than about 1 wt.%, such as less than about 0.75 wt.%, such a than about 0.5 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • a compafibilizer such as a phenoxy resin
  • the phenoxy resin may be present in the composition in an amount of at least about 0.01 wt.%, such as at least about 0.05 wt.%, such as at least about 0.075 wt.% and iess than about 1 wt.%, such as less than about 0,75 wt.%, such as iess than about 0.5 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • a colorant may be present.
  • Colorants that may be used include any desired inorganic pigments, such as titanium dioxide, ultramarine blue, cobalt blue, and other organic pigments and dyes, such as phthaiocyanines, anthraquinnones, and the like.
  • Other colorants include carbon black or various other polymer-soluble dyes.
  • the coiorant may be present in the composition in an amount of at least about 0.01 wt.%, such as at least about 0.05 wt.%, such as at least about 0.1 wt.% and less than about 5 wt.%, such as less than about 2.5 wt.%, such as less than about 1 wt.%, wherein the weight is based on the total weight of the respective polymer composition.
  • compositions of the present disclosure can be compounded and formed into a polymer article using any technique known in the art.
  • the respective composition can be intensively mixed to form a substantially homogeneous blend.
  • the blend can be melt kneaded at an elevated temperature, such as a temperature that is higher than the melting point of the polymer utilized in the polymer composition but lower than the degradation temperature.
  • the respective composition can be melted and mixed together in a conventional single or twin screw extruder.
  • the melt mixing is carried out at a temperature ranging from 100 to 280°C, such as from 120 to 260°C, such as from 140 to 240°C or 180 to 220°C.
  • processing should be conducted for each respective composition at a desired temperature to minimize any polymer degradation.
  • the compositions may be formed into pellets.
  • the pellets can be molded into polymer articles by techniques known in the art such as injection molding, thermoforming, blow molding, rotational molding and the like. According to the present disclosure, the polymer articles demonstrate excellent tribological behavior and mechanical properties. Consequently, the polymer articles can be used for several applications where low wear and excellent gliding properties are desired.
  • Polymer articles include any moving articles or moldings that are in contact with another surface and may require high tribological requirements
  • polymer articles include articles for the automotive industry, especially housings, latches such as rotary latches, window winding systems, wiper systems, pulleys, sun roof systems, seat adjustments, levers, bushes, gears, gear boxes, claws, pivot housings, wiper arms, brackets or seat rail bearings, zippers, switches, cams, rollers or roiling guides, sliding elements or glides such as sliding plates, conveyor belt parts such as chain elements and links, castors, fasteners, levers, conveyor system wear strips and guard rails.
  • An almost limitless variety of polymer articles may be formed from the polymer compositions of the present disclosure.
  • the polyoxymethylene based system can be used to produce a polymer article comprising two layers to provide at least a two-component system. In such system, the second polymer layer is connected to the first polymer layer.
  • the first polymer layer is comprised of a polyoxymethylene polymer composition comprising a polyoxymethylene polymer and optionally at least one triboiogical modifier.
  • the first polymer layer provides a support or base for the second polymer layer.
  • the second polymer layer is comprised of a second polymer composition comprising a liquid crystalline polymer, a poiyarylene sulfide polymer, or a combination thereof and at least one triboiogical modifier.
  • the second polymer layer provides a surface for contacting and/or conveying against another body to provide a triboiogical effect.
  • the second polymer layer may contact a sliding body such as a bottle or a container.
  • the first polymer layer and/or the second polymer layer may contain engaging mechanisms allowing one article to be connected to an adjacent article.
  • Such mechanisms include but are not limited to a pin or the like. It should be noted that any engaging mechanisms in the art may be utilized to engage adjacent articles.
  • the first polymer layer can be connected to the second polymer layer using any method known in the art.
  • the polymer layers may be connected to one another such that they are directly or indirectly connected or linked.
  • the layers may be fixedly or removably attached to one another and/or an intermediate layer.
  • the layers may be connected using any method known in the art.
  • the polymer layers may be connected by interlocking mechanisms, fasteners, co-molding, overmolding, intermediate layers, adhesives, etc.
  • the interlocking mechanism may include a male member and a female member for accepting the male member, such as grooves and plugs,
  • the male member or groove and/or female member or plug may be located on either the first or second polymer layer, it should also be understood that the these members may be of any shape or configuration as long as they provide an interlocking mechanism. It should also be understood that more than one interlocking mechanism may be utilized.
  • the members may be formed into the respective layers and subsequently combined to form the polymer article. On the other hand, a member may be created in one layer and the other layer may be injection molded to provide the corresponding interlocking part comprising a member.
  • the first polymer layer can be connected to the second polymer layer during a two-component injection molding process.
  • the first polymer layer may be connected to the second polymer layer using a fastener, such as a mechanical fastener.
  • a fastener such as a mechanical fastener.
  • Fasteners include screws, nails, rivets, snaps, and the like and others generally known in the art.
  • the fastener can be inserted through either the first polymer layer or the second poiymer !ayer in order to attach or connect the polymer layers together, it should also be understood that any number of fasteners may be utilized for connecting the poiymer layers.
  • the first poiymer layer is in direct contact and connected to the second poiymer layer.
  • the first polymer layer is in indirect contact and connected to the second polymer layer.
  • an intermediate layer may also be utilized to connect the polymer layers.
  • an intermediate layer may be utilized individually or in conjunction with an interlocking mechanism or a fastener as described above.
  • the second poiymer layer may be overmolded onto the first poiymer layer.
  • the second polymer layer may entirely overmold or partially overmold the first polymer layer.
  • any overmoiding configuration may be utilized as long as the second polymer layer generally provides a surface for contacting and conveying against another body to provide a triboiogical effect, in addition, when overmoiding, if should be
  • first polymer layer or second polymer layer may employ engaging mechanisms.
  • St should be understood that any method of overmoiding known in the art may be utilized to connect the second polymer layer with the first poiymer layer.
  • the second poiymer layer overlays or covers at least 50%, such as at least 75%, such as least 85%, such as at least 90%, such as at least 95% of at least one surface of the first polymer layer. In one embodiment, the second polymer overlays or covers 100% of at least one surface of the first polymer layer.
  • the second polymer may have a thickness of at least about 0.01 mm, such as at least about 0.02 mm, such as at least about 0.1 mm, such as at least about 0.5 mm, such as at least about 0.75 mm, such as at least about 1 mm and generally less than about 10 mm, such as less than about 7,5 mm, such as less than about 5 mm, such as less than about 3 mm.
  • the polymer article can be a conveyor component, such as a conveyor chain component.
  • conveyor chains are made from a series of links having generally flat surfaces wherein the links may be connected to each other by pins.
  • General examples of such conveyor components are disclosed in U.S. Patent No.
  • the conveyor component may be a conveyor chain link.
  • a conveying system 10 is comprised of a conveyor belt 12.
  • the conveyor belt 12 is comprised of conveyor components 14.
  • the conveyor belt 12 and conveyor components 14 are used to transport items 18 such as packages, containers, and the like.
  • the conveyor components 14 may exist as a two-component system.
  • the poiymer article may be a conveyor component 14 that exists as a two-component system 34.
  • Figure 2 exhibits a general characterization of a two-component system.
  • the second polymer layer 22 is connected to the first polymer layer 24.
  • a second polymer layer 22 overlays a first poiymer layer 24 such that the second polymer layer 22 covers an entire surface of the first poiymer layer 24.
  • the second polymer layer 22 may partiaiiy overlay the first poiymer layer 24 such that the second polymer layer 22 only partially covers a surface of the first polymer layer 24.
  • the first poiymer layer 24 is comprised of a polyoxymethyiene poiymer composition comprising a polyoxymethyiene polymer and optionally at least one tribological modifier.
  • the first polymer layer 24 provides a support or base for the second poiymer layer 22.
  • the second polymer layer 22 is comprised of a second polymer composition comprising a liquid crystalline poiymer or a polyarylene sulfide polymer and at least one tribologica! modifier.
  • the second polymer layer 22 provides a surface for contacting and conveying a sliding body or container such as a plastic or glass bottle.
  • engaging mechanisms 18 and 20 are located on the first polymer layer 24. However, it should be understood that engaging mechanisms 18 and 20 may be located on second polymer layer 22 or on both poiymer layers 22 and 24. Engaging mechanisms 18 and 20 of adjacent components 14 can be connected using a pin (not shown) or the like to create a conveyor belt as shown in Figure 1. It should be understood that any engaging mechanisms 18 and 20 known in the art can be utilized to engage adjacent conveyor components 14.
  • first polymer layer 24 can be connected to the second polymer layer 22 using an interlocking mechanism 26 such as a male member 28 or a groove 28 and a female member 30 or a plug 30.
  • the first polymer layer 24 may comprise a mate member/groove 28 while the second polymer layer comprises a female member 30.
  • the first polymer layer 24 may comprise a female member 30 while the second polymer layer 22 comprises a male member 28.
  • the male member and female member may be of any shape or configuration as long as they provide an interlocking mechanism 26. It should also be understood that more than one interlocking mechanism may be utilized.
  • the male member 28 or female member 30 may be formed into the respective layers and subsequently combined to form a conveyor component 14.
  • a male member 28 or female member 30 may be created in one layer and the other layer may be injection molded to provide the corresponding interlocking part comprising a male member 28 or female member 30.
  • the first poiymer layer 24 can be connected to the second poiymer layer 22 during a two-component injection molding process.
  • the first polymer layer 24 may be connected to the second polymer layer 22 using a fastener 36.
  • Fasteners include screws, nails, snaps, and the like.
  • the fastener 36 is inserted through the second polymer layer 22 and into the first polymer layer 24.
  • the fastener 36 may also be inserted through the first polymer layer 24 and into the second polymer layer 22. It should also be understood that any number of fasteners 36 may be utilized for connecting the polymer layers.
  • the second polymer layer 22 may be overmoided onto the first polymer layer 24, As shown in Figure 5a, the second polymer layer 22 entirely overmolds the first poiymer layer 24. As shown in Figure 5b, the second polymer layer 22 partially overmolds the first polymer layer 24.
  • any overmolding configuration may be utilized as long as the second polymer layer 24 generally provides a surface for contacting and conveying a sliding body or container such as a plastic or glass bottle.
  • first polymer layer 24 or second polymer layer 22 may employ engaging mechanisms 18 and 20. St should be understood that any method of overmolding known in the art may be utilized to connect the second polymer layer 22 with the first polymer layer 24,
  • Utilizing the polyoxymethylene based system according to the present disclosure provides compositions and articles with improved triboSogicai properties.
  • the tribologicai properties are generally measured by the coefficient of friction.
  • static friction is the friction between two or more surfaces that are not moving relative to each other (ie. , both objects are stationary)
  • dynamic friction occurs when two objects are moving relative to each other (ie., at least one object is in motion).
  • stick-slip is generally known as a phenomenon caused by continuous alternating between static and dynamic friction.
  • the poiymer article of the two- component system may exhibit a static coefficient of friction against another surface, as determined according to VDA 230-206, of greater than about 0.01 , such as greater than about 0.03, such as greater than about 0.05, such as greater than about 0.08, such as greater than about 0.1 but generally !ess than about 0.18, such as less than about 0.15, such as less than about 0.12, such as less than about 0.1.
  • the second polymer layer of the poiymer article may exhibit the aforementioned static coefficient of friction.
  • the poiymer article of the two- component system may exhibit a dynamic coefficient of friction against another surface, as determined according to VDA 230-206, of greater than about 0.01 , such as greater than about 0.03, such as greater than about 0.05, such as greater than about 0.08, such as greater than about 0.1 but generally less than about 0.18, such as less than about 0.15, such as less than about 0.12, such as less than about 0.1.
  • the second polymer layer of the polymer article may exhibit the aforementioned dynamic coefficient of friction.
  • the above static coefficient of friction and dynamic coefficient of friction values are exhibited between the polymer article, such as the second polymer layer, of the two-component system and various counter- materials.
  • the above values can be exhibited between the polymer article, such as the second polymer layer, of the two-component system and a polyester surface such as a polyethylene terephthalate surface.
  • the above values are exhibited between the polymer article, such as the second polymer layer, of the two-component system and a poiyacetai surface, a metal surface such as a steel surface, or a polyoSefin surface such as a polypropylene surface or a polyethylene surface such as an ultra-high molecular weight polyethylene surface.
  • compositions comprise either a liquid crystalline polymer or a polyphenylene sulfide polymer and at least one tribological modifier such as poiytetrafluoroethylene.
  • tribological modifier such as poiytetrafluoroethylene.
  • glass fibers were also utilized in the compositions. The formulations are disclosed in the table below.
  • each respective polymer composition was substantially and homogeneously blended and compounded using a co-rotating intermeshing twin screw extruder. When glass fibers were utilized, they were added to the twin-screw extruder at a suitable downstream feeding position. The respective compositions were extruded, peiletized, and then molded using an injection molding machine.
  • New polymer layers or molds were tested after injection molding. Used polymer layers or molds were produced by abrading a new polymer mold with

Abstract

La présente invention concerne un système à base de polyoxyméthylène à deux composants. Le système à deux composants se compose d'une première couche polymère et d'une seconde couche polymère. La première couche polymère se compose d'une composition polymère de polyoxyméthylène comprenant un polymère de polyoxyméthylène et éventuellement un agent de modification tribologique. La seconde couche polymère se compose d'une seconde composition polymère comprenant un polymère cristallin liquide, un polymère de polysulfure d'arylène, ou une combinaison de ceux-ci, et au moins un agent de modification tribologique. Les compositions confèrent à des articles polymères, tels que des composants d'acheminement, des propriétés tribologiques améliorées.
PCT/IB2014/065223 2013-10-21 2014-10-10 Systèmes à base de polyoxyméthylène à deux composants WO2015059599A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361893480P 2013-10-21 2013-10-21
US61/893,480 2013-10-21

Publications (1)

Publication Number Publication Date
WO2015059599A1 true WO2015059599A1 (fr) 2015-04-30

Family

ID=51903962

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2014/065223 WO2015059599A1 (fr) 2013-10-21 2014-10-10 Systèmes à base de polyoxyméthylène à deux composants

Country Status (2)

Country Link
US (1) US20150111794A1 (fr)
WO (1) WO2015059599A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9718225B2 (en) * 2013-08-27 2017-08-01 Ticona Llc Heat resistant toughened thermoplastic composition for injection molding
KR102300453B1 (ko) * 2015-05-14 2021-09-09 에스케이케미칼 주식회사 금속과의 접착성이 우수한 폴리아릴렌 설파이드 조성물
CN108368325A (zh) 2015-09-30 2018-08-03 塞拉尼斯销售德国有限公司 低摩擦无刺耳音的组合件
CN110392715A (zh) 2017-03-10 2019-10-29 塞拉尼斯销售德国有限公司 聚酯聚合物组合物
US20220127221A1 (en) * 2019-02-08 2022-04-28 Basf Se Crystal composition (cc) comprising 4,4'-dichlorodiphenylsulfoxide crystals (c)
KR20230050439A (ko) * 2020-08-14 2023-04-14 셀라니즈 인터내셔날 코포레이션 폴리옥시메틸렌 공중합체를 생산하기 위한 바이오매스의 사용

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161470A (en) 1977-10-20 1979-07-17 Celanese Corporation Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing
US4436200A (en) 1972-02-14 1984-03-13 Rexnord Inc. Low friction flat-top article carrying chain
DE4311634A1 (de) * 1992-04-09 1993-10-14 Rabe Thore Verfahren zur Herstellung eines hülsenförmigen Gleitlagers und nach diesem Verfahren hergestelltes Gleitlager
US5309705A (en) 1993-07-06 1994-05-10 Tsubakimoto Chain Co. Flat top conveyor chain
US5559180A (en) 1993-03-22 1996-09-24 E. I. Du Pont De Nemours And Company Polyacetal compositions for use in wear applications
US5616680A (en) 1994-10-04 1997-04-01 Hoechst Celanese Corporation Process for producing liquid crystal polymer
EP0831038A1 (fr) 1996-03-29 1998-03-25 Toray Industries, Inc. Chaine transporteuse
US6114492A (en) 2000-01-14 2000-09-05 Ticona Llc Process for producing liquid crystal polymer
US6161685A (en) 1999-03-26 2000-12-19 Rexnord Corporation Thermoplastic chain link for a modular conveyor chain
US6485794B1 (en) 1999-07-09 2002-11-26 Ecolab Inc. Beverage container and beverage conveyor lubricated with a coating that is thermally or radiation cured
US6514611B1 (en) 2001-08-21 2003-02-04 Ticona Llc Anisotropic melt-forming polymers having a high degree of stretchability
WO2004058866A1 (fr) * 2002-12-18 2004-07-15 E.I. Du Pont De Nemours And Company Composition thermoplastique a faible coefficient de frottement contenant des charges
WO2004058851A1 (fr) 2002-12-18 2004-07-15 E.I. Du Pont De Nemours And Company Procede de production d'un polymere cristallin liquide
DE102004057190A1 (de) * 2004-11-26 2006-06-01 Frenzelit-Werke Gmbh & Co Kg Tribologische Schicht

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19606948A1 (de) * 1996-02-23 1997-08-28 Hoechst Ag Kunststoff-Formmassen mit geringerem Verschleiß
KR20060022685A (ko) * 2003-06-11 2006-03-10 이 아이 듀폰 디 네모아 앤드 캄파니 상이한 열가소성 중합체의 연결

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4436200A (en) 1972-02-14 1984-03-13 Rexnord Inc. Low friction flat-top article carrying chain
US4161470A (en) 1977-10-20 1979-07-17 Celanese Corporation Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing
DE4311634A1 (de) * 1992-04-09 1993-10-14 Rabe Thore Verfahren zur Herstellung eines hülsenförmigen Gleitlagers und nach diesem Verfahren hergestelltes Gleitlager
US5559180A (en) 1993-03-22 1996-09-24 E. I. Du Pont De Nemours And Company Polyacetal compositions for use in wear applications
US5309705A (en) 1993-07-06 1994-05-10 Tsubakimoto Chain Co. Flat top conveyor chain
US5616680A (en) 1994-10-04 1997-04-01 Hoechst Celanese Corporation Process for producing liquid crystal polymer
EP0831038A1 (fr) 1996-03-29 1998-03-25 Toray Industries, Inc. Chaine transporteuse
US6161685A (en) 1999-03-26 2000-12-19 Rexnord Corporation Thermoplastic chain link for a modular conveyor chain
US6485794B1 (en) 1999-07-09 2002-11-26 Ecolab Inc. Beverage container and beverage conveyor lubricated with a coating that is thermally or radiation cured
US7067182B2 (en) 1999-07-09 2006-06-27 Ecolab Inc. Lubricant coated beverage container or conveyor therefor
US6114492A (en) 2000-01-14 2000-09-05 Ticona Llc Process for producing liquid crystal polymer
US6514611B1 (en) 2001-08-21 2003-02-04 Ticona Llc Anisotropic melt-forming polymers having a high degree of stretchability
WO2004058866A1 (fr) * 2002-12-18 2004-07-15 E.I. Du Pont De Nemours And Company Composition thermoplastique a faible coefficient de frottement contenant des charges
WO2004058851A1 (fr) 2002-12-18 2004-07-15 E.I. Du Pont De Nemours And Company Procede de production d'un polymere cristallin liquide
DE102004057190A1 (de) * 2004-11-26 2006-06-01 Frenzelit-Werke Gmbh & Co Kg Tribologische Schicht

Also Published As

Publication number Publication date
US20150111794A1 (en) 2015-04-23

Similar Documents

Publication Publication Date Title
WO2015059599A1 (fr) Systèmes à base de polyoxyméthylène à deux composants
JP6936278B2 (ja) 本質的に低摩擦のポリオキシメチレン
EP3029107B1 (fr) Composition de polyester à cristaux liquides
KR20120060216A (ko) 폴리아미드 수지 조성물
WO2003044088A1 (fr) Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition
WO2016098026A1 (fr) Composition polymère de polyoxyméthylène à faible friction
JP7051021B1 (ja) 組成物、ペレット、成形品および組成物の製造方法
KR100601770B1 (ko) 폴리옥시메틸렌 수지 조성물 및 그의 성형품
JP5752986B2 (ja) ポリアセタール樹脂組成物及びそれからなる成形品
JP2012233131A (ja) ポリアセタール樹脂組成物及びそれからなる成形品
KR102473791B1 (ko) 열가소성 수지 조성물 및 그것을 이용한 성형체
WO2019008539A1 (fr) Composition polymère à faible bruit
EP3341439A1 (fr) Ensemble sans grincement à faible frottement
JP3187372B2 (ja) 摺動部材用樹脂組成物及び摺動部材
JPS5910700B2 (ja) ポリエステル樹脂組成物
EP3872114A1 (fr) Polyester cristallin entièrement aromatique et composition de résine polyester
JP3238737U (ja) 摺動部材用樹脂組成物からなる樹脂製歯車
US5194506A (en) Polyethylene terephthalate compositions with arylene sulfide random copolymers
WO2018229678A1 (fr) Composition de polyoxyméthylène renforcée présentant de faibles émissions
JPWO2018230389A1 (ja) ポリアセタール樹脂組成物、成形品およびポリアセタール樹脂組成物の製造方法
WO2023276902A1 (fr) Composition de résine et corps moulé
EP3974469A1 (fr) Composition de résine à base de polyamide pour moulage par injection et composant coulissant formé à partir de celle-ci
WO2005113636A1 (fr) Procédé pour réduire la viscosité de fonte des polyesters
JPH042622B2 (fr)
WO2023238790A1 (fr) Composition de résine et article moulé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14799544

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14799544

Country of ref document: EP

Kind code of ref document: A1