WO2012138493A1 - Molded articles having a swirl-like or marble-like appearance and compositions for producing same - Google Patents
Molded articles having a swirl-like or marble-like appearance and compositions for producing same Download PDFInfo
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- WO2012138493A1 WO2012138493A1 PCT/US2012/030500 US2012030500W WO2012138493A1 WO 2012138493 A1 WO2012138493 A1 WO 2012138493A1 US 2012030500 W US2012030500 W US 2012030500W WO 2012138493 A1 WO2012138493 A1 WO 2012138493A1
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- WIPO (PCT)
- Prior art keywords
- polymer
- phase
- melting point
- thermoplastic
- article
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 99
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 60
- 238000002844 melting Methods 0.000 claims abstract description 57
- 230000008018 melting Effects 0.000 claims abstract description 57
- 239000003086 colorant Substances 0.000 claims abstract description 26
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 17
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims abstract description 4
- 229920002647 polyamide Polymers 0.000 claims abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 23
- 239000004416 thermosoftening plastic Substances 0.000 claims description 23
- 229920006126 semicrystalline polymer Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 10
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 150000004292 cyclic ethers Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920013683 Celanese Polymers 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000004579 marble Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- STENYDAIMALDKF-UHFFFAOYSA-N cyclobutane-1,3-diol Chemical compound OC1CC(O)C1 STENYDAIMALDKF-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- NGCMLEQSKQCTAK-UHFFFAOYSA-N tetraoxane Chemical compound C1COOOO1 NGCMLEQSKQCTAK-UHFFFAOYSA-N 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
Definitions
- Structural polymers such as plastic materials are used in numerous and diverse applications. In fact, those skilled in the art continue to strive to replace parts conventionally made from metal and wood with those made from polymers.
- the polymers, for Instance may offer various advantages with respect to strength properties, chemical resistance, and/or cost.
- polyoxymethylene polymers One particular type of structural polymer that has good rigidity and strength properties are polyoxymethylene polymers.
- Polyoxymethylene (which is also referred to as "POM") is a high-performance polymer having good mechanical properties. Due to its properties, polyoxymethylene polymers are commonly used as a direct replacement for metals due to its stiffness, dimensional stability, and corrosion resistance.
- Polyoxymethylene polymers exist in the form of
- polyoxymethylene polymers have a desirable combination of physical properties
- various problems have been encountered in attempting to produce multi-colored articles containing a polyoxymethylene polymer.
- the problems described above have been particularly problematic when processing polyoxymethylene polymers.
- the present disclosure is directed to the production of molded polymeric articles that can have a multi-colored appearance and predominately contain a polyoxymethylene polymer.
- the present disclosure is directed to the production of molded polymeric articles that can have a multi-colored appearance and predominately contain a polyoxymethylene polymer.
- polyoxymethylene polymer articles can be produced with contrasting colors without any substantial adverse impacts upon the strength of the resulting material.
- the present disclosure is directed to a molded polymer article that is made from a two-phase polymer composition.
- the first phase of the composition is immiscible with a second phase.
- the first phase remains distinct from the second phase when the composition is molded into the article.
- the first phase comprises a
- the second phase comprises a thermoplastic, semi-crystalline polymer.
- the thermoplastic, semi-crystalline polymer has a melting point that is at least 5° higher or lower, such as from about 10°C to about 30°C higher or lower than the melting point of the polyoxymethylene polymer. In one particular embodiment, for instance, the thermoplastic, semi-crystalline polymer has a melting point that is higher than the melting point of the polyoxymethylene polymer.
- the first phase may have a different color than the second phase.
- the resulting molded polymer article can have a swirl-like appearance or a marble-like appearance depending upon the relative amounts and the manner in which the phases are combined.
- the thermoplastic, semi-crystalline polymer comprises a thermoplastic elastomer, a glycol-modified polyethylene terephthalate copolymer, or a polyamide.
- the second phase may contain a thermoplastic polyester elastomer.
- the polyoxymethylene polymer contained in the first phase may have a melting point that is lower than the melting point of the polymer contained in the second phase.
- the polyoxymethylene polymer for instance, may have a melting point of from about 150°C to about 200°C.
- the thermoplastic, semi-crystalline polymer contained in the second phase may have a melting point of from about 170°C to about 210°C, such as from about 185°C to about 200°C.
- the second phase may contain a colorant such as a pigment if desired.
- a colorant such as a pigment if desired.
- at least one colorant may be present in the second phase in an amount from about 1% to about 60% by weight of the second phase.
- the relative amount of the first phase in comparison to the second phase can vary depending upon the particular application and the desired result.
- the polymer composition may contain the second phase in an amount of from about 0.5% to about 10% by weight, such as from about 1% to about 5% by weight.
- the relative amount of the phases may have an impact on the resulting appearance of the molded article.
- the molded article may have a swirl-like design.
- the molded article may have a marble-like appearance.
- the first phase and the second phase may have different but complementary colors such that the first and second phases produce a camouflage pattern in the final product.
- the polymer composition can be used in any suitable molding process to produce articles.
- the composition can be used in a blow molding process or in an injection molding process.
- the present disclosure is directed to polymer compositions and molded articles that include at least two distinct phases.
- the first phase comprises one or more polyoxymethylene polymers.
- the second phase comprises a thermoplastic, semi-crystalline polymer that is immiscible with the first phase.
- the polymer composition has many different uses and applications.
- one or more colorants can be incorporated into the second phase and/or the first phase so that the phases have different colors. In this manner, a multi-colored article can be produced.
- a molded article can be produced that has a swirl-like appearance, a marble-like appearance, or the like. In this manner, products can be produced having a very decorative appearance.
- products can be produced having a camouflage-like pattern or can be produced that imitate natural materials, such as wood, marble or granite.
- multi-phase molded articles can be made according to the present disclosure without significantly adversely affecting the strength of the polyoxymethylene polymer.
- a higher melting point polymer is used as the color concentrate resin that is combined with the polyoxymethylene polymer.
- the higher melting point polymer may contain relatively high amounts of colorant while being combined with the polyoxymethylene polymer in relatively low amounts.
- the impact strength resistance of the resulting product may actually be increased in relation to a similar product made exclusively from the
- the polyoxymethylene polymer that comprises the first phase of the polymer composition may comprise any suitable homopolymer or copolymer of polyoxymethylene.
- Po I yoxym ethylenes are generally unbranched linear polymers that may contain at least 80%, such as at least 90% oxymethylene units (-CH 2 -O-).
- the homopolymers are generally obtained by polymerizing
- Copolymers of polyoxymethylenes may contain not only oxymethyiene units but also oxyalkylene units, where the alkyiene groups may contain from about 2 to about 8 carbon units, linear or branched.
- the term polyoxymethylenes as used herein encompasses homopolymers of formaldehyde or its cyclic oligomers, such as trioxane or tetroxane, and also corresponding copolymers.
- Homopolymers of formaldehyde or of trioxane are polymers whose hydroxy end groups have been chemically stabilized in a known manner with respect to degradation, e.g. via esterification or via etherifi cation.
- Copolymers are polymers composed of formaldehyde or of its cyclic oiigomers, in particular trioxane, and of cyclic ethers, of cyclic acetals, and/or of linear polyacetals.
- these polymers have at least 50 mol % of
- the homopolymers are generally prepared via polymerization of formaldehyde or trioxane, preferably in the presence of suitable catalysts.
- POM copolymers are preferred in the inventive molding compositions, particularly those which also contain, besides the— CH2— O— repeat units, up to 50 mol %, preferably from 0.1 to 20 mo! %, and in particular from 0.5 to 10 mol %, of— o— R 1 — repeat units, where R is a saturated or ethylenically unsaturated alkyiene group having at least two carbon atoms, or a cycloalkylene group, which, if appropriate, has sulfur atoms or preferably oxygen atoms in the chain, and which, if appropriate, bears one or more substituents selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, halogen, or alkoxy.
- R 1 is preferably a C 2 -C -alkylene group which, if appropriate, has one or more substituents which are C C 4 -alkyl groups, or are Ci-C -a!koxy groups, and/or are halogen atoms, preferably chlorine atoms, or a group of the formula - ((C n H 2 n)"0-) m , in which n is a whole number from 2 to 4 and m is 1 or2.
- cyclic ethers or acetals are those of the formula
- R 2 is a C 2 -C4-alkylene group or an alkyleneoxyalkylene unit which, if appropriate, have one or more substituents which are CrC 4 -alkyi groups, or which are CrC 4 -alkoxy groups, and/or which 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 oligo- or polyformals, such as polydioxolane or polydioxepan, as comonomers.
- copolymers composed of from 99.5 to 95 mo! % of trioxane and of from 0.5 to 5 mol % of one of the above-mentioned comonomers.
- polyoxymethylenes likewise suitable are oxymethylene terpolymers which by way of example are prepared via reaction of trioxane and of one of the cyclic ethers or acetals described above, and using a third monomer, preferably a bifunctlonal compound of the formula
- Z is a chemical bond, or C 2 -C 8 -cycloalkylene).
- Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diethers composed of glycidyl compounds and formaldehyde in a molar ratio of 2:1, and also diethers composed of 2 mol of glycidyl compound and 1 mol of an aliphatic diol having from 2 to 8 carbon atoms, examples being the diglycidyl ether of ethylene glycol, 1 ,4-butanediol, ,3-butanediol, 1 ,3-cyclobutanediol, 1 ,2- propanediol, and 1 ,4-cyclohexanediol, and also diglycerol diformal, to mention just a few examples.
- Processes for preparation of the POM homo- and copolymers described above are known to the person skilled in the art and are described in the literature.
- the preparation of the polyoxymethylene can be carried out by polymerization of polyoxymethylene-forming monomers, such as trioxane or a mixture of trioxane and dioxolane, in the presence of ethylene glycol as a molecular weight regulator.
- the polymerization can be effected as precipitation polymerization or in the melt.
- Initiators which may be used are the compounds known per se, such as trifluoromethane sulfonic acid, these preferably being added as solution in ethylene glycol to the monomer.
- the procedure and termination of the polymerization and working-up of the product obtained can be effected according to processes known per se.
- the molecular weight and hence the MVR value of the resulting polymer can be adjusted.
- the criteria for choice in this respect are known to the person skilled in the art.
- the melting point of the polyoxymethylene polymer can vary depending upon how the polymer is made, its molecular weight, and various other factors. In one embodiment, for instance, the melting point can be from about 150°C to about 200°C.
- the weight average molecular weight of the polymer can vary from about 5000 to about 200,000, such as from about 7000 to about 150,000.
- the polyoxymethylene polymer present in the composition can generally have a melt volume rate (MVR) of less than 50 cm 3 /10 min, such as from about 0.5 to about 20 cm 3 /10 min, such as from about 2 to about 15 cm 3 /10 min.
- MVR melt volume rate
- the MVR may be from about 6 to about 12 cm 3 /10 min, determined according to ISO 1133 at 190°C and 2.16 kg.
- the polyoxymethylene polymer selected for use in the first phase of the polymer composition generally comprises a polymer having a desired melting point and physical properties.
- the polymer should also not chemically react or otherwise couple to the immiscible polymer contained in the second phase.
- the polymer composition generally does not contain any
- composition of the present disclosure can vary depending upon the particular application. In one embodiment, for instance, the composition contains
- polyoxymethylene polymer in an amount of at least 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 90% by weight, such as in an amount greater than about 95% by weight.
- the polyoxymethylene polymer is present in an amount less than about 99% by weight, such as in an amount less than about 98% by weight, such as in an amount less than about 97% by weight.
- the polymer composition also includes a second phase containing a thermoplastic, semi-crystalline polymer.
- the thermoplastic, semi-crystailine polymer contained in the second phase comprises a polymer that is immiscible with the
- the polymer in the second phase has a melting point that is higher or lower than the melting point of the polyoxymethylene polymer.
- the melting point of the thermoplastic, semi-crystalline polymer can be at least 5°C greater or less than the melting point of the
- the thermoplastic, semi-crystalline polymer has a melting point that is higher than the melting point of the polyoxymethylene polymer.
- the polymer contained in the second phase comprises a thermoplastic elastomer.
- thermoplastic elastomers are polyester elastomers (TPE-E), thermoplastic polyamide elastomers (TPE-A) and thermoplastic polyurethane elastomers (TPE-U).
- TPE-E polyester elastomers
- TPE-A thermoplastic polyamide elastomers
- TPE-U thermoplastic polyurethane elastomers
- a thermoplastic elastomer is selected that has a desired melting point in comparison to the melting point of the polymers contained in the first phase.
- the thermoplastic elastomer should be immiscible with respect to the
- thermoplastic elastomer can be selected that does not chemically react or otherwise couple to the polyoxymethylene polymer.
- one or more thermoplastic elastomers are blended to form the second phase of the polymer composition that have an overall melting temperature that is higher than the melting temperature of the first phase polymers.
- a thermoplastic polyester elastomer having a melting point of about 170°C may be blended with a thermoplastic polyester elastomer having a melting point of about 200°C in order to form the second phase that overall has a melting point that is from about 10°C to about 30°C higher than the melting point of the poiyoxymethylene polymers present in the first phase.
- the second phase can also contain various other thermoplastic, semi-crystalline polymers.
- the second phase may contain a polyethylene terephthaiate copolymer having the desired melting point with respect to the first phase polymers.
- the second phase may contain a glycol-modified polyethylene terephthaiate copolymer.
- the copolyester may contain polyethylene terephthaiate copolymerized with
- Such polymers can have a melting point of from about 170°C to about 215°C, such as from about 170°C to about 210°C.
- the second phase may contain a poiyamide polymer.
- Poiyamide polymers are generally immiscible with poiyoxymethylene polymers and can have a melting point higher than many poiyoxymethylene polymers.
- the poiyamide polymer comprises nylon 11.
- Nylon 11 for instance, can have a melting point of from about 175°C to about 200°C, such as from about 180°C to about 190°C.
- the poiyamide polymer may comprise nylon 12.
- the second phase of the polymer composition may also contain one or more colorants. Colorants can be included in the second phase depending upon the desired color and the final application for the polymer.
- the colorants used may be any desired inorganic pigments, such as titanium dioxide, ultramarine blue, cobalt blue, etc., or organic pigments or colors, such as phthaiocyanines, anthraquinones, etc., or special effects pigments such as pearlescent pigments, aluminum based pigments, fluorescent pigments and the like, or carbon black, either individually or as a mixture, or together with polymer- soluble dyes.
- inorganic pigments such as titanium dioxide, ultramarine blue, cobalt blue, etc.
- organic pigments or colors such as phthaiocyanines, anthraquinones, etc.
- special effects pigments such as pearlescent pigments, aluminum based pigments, fluorescent pigments and the like, or carbon black, either individually or as a mixture, or together with polymer- soluble dyes.
- the amount of colorants present in the second phase of the polymer composition can depend upon the particular application. In general, colorants may be present in the second phase in an amount from about 1 % to about 60% by weight, based upon the weight of the second phase. In certain embodiments, in order to have significant color differences between the first phase and the second phase, the second phase may contain colorants in amounts greater than 10% by weight, such as in amounts greater than 20% by weight, such as in amounts greater than 30% by weight, such as in amounts greater than 40% by weight, such as even in amounts greater than 50% by weight, based upon the weight of the second phase. It was discovered that significant amounts of colorant can be included in the second phase in order to improve the overall appearance of the resulting product without significantly decreasing the strength, such as the impact strength of the product.
- colorants may also be added to the first phase if desired.
- colorants may be combined with the polyoxym ethylene polymers in amounts up to about 10% by weight, such as from about 0.1 % to about 5% by weight.
- the polymer composition predominately comprises the first phase.
- the second phase may be present in the polymer
- composition in an amount less than 10% by weight, such as in an amount from about 1 % to about 5% by weight.
- the polymer composition of the present disclosure can optionally contain a stabilizer and/or various other known additives.
- additives can include, for example, antioxidants, acid scavengers, formaldehyde scavengers, UV stabilizers or heat stabilizers
- the molding material or the molding may contain processing auxiliaries, for example adhesion promoters, lubricants, nucleating agents, demolding agents, fillers, reinforcing materials or antistatic agents and additives which impart a desired property to the molding material or to the molding, such as dyes and/or pigments and/or further impact modifiers and/or additives imparting electrical conductivity; and mixtures of these additives, but without limiting the scope to said examples.
- molded articles can be made in accordance with the present disclosure using various methods and techniques. In particular, articles can be made using any suitable extrusion process. In one embodiment, for instance, molded articles can be produced using injection molding.
- barrel temperatures, compression ratio of the screw, residence time of the material through the barrel, and degree of mixing in the barrel can be controlled so as to produce a product having the desired properties and appearance.
- the stock temperature of the material as controlled by barrel temperatures and shear heating can be kept close to the minimum recommended temperature for the first phase polymer. Elevated tem eratures effectively reduce the delta temperature (melting point of second phase minus actual material temperature of first phase) between the two phases and may yield a less desirable appearance, particularly if the delta temperature approaches 5°C or less,
- Compression ratio of the screw used in the barrel of the injection molding machine may range up to 3:1 , and preferably 2.5:1 or less. Compression ratios of less than 2.5:1 will yield desirable molded part appearance at lower the lower range of melting point differences.
- Shot size refers to the amount of polymer it takes to fill the mold for producing a part. Shot size can vary dramatically between processes and systems. Barrel capacity of 6 shots or less, and preferably 3 shots or less, is desirable. Higher barrel capacity leads to longer residence times and less differentiated swirl patterns.
- degree of mixing in the barrel of the injection molding machine is also controlled by the screw speed and back pressure. It is common practice and knowledge that if less mixing is desired, a slower screw rotation along with low back pressure should be employed. However, when attempting to produce swirllike patterns, fast screw rotation is preferred to minimize screw rotation time, which minimizes mixing and maximizes the swirl pattern. Low back pressure is desirabie. For example, if the mold closed time is 20 seconds, it is common practice to utilize most of the 20 seconds with screw rotation at the slowest speed possible to reduce mixing. In contrast, the preferred method is fast screw rotation (less than 5 second screw rotation time) to maximize the swirl-like pattern.
- a polymer composition was formulated in accordance with the present disclosure.
- the polymer composition included a first phase and a second phase.
- the first phase contained a polyoxymethyiene copolymer.
- polyoxym ethylene copolymer had a melting point of about 170°C and is
- the second phase on the other hand, contained one or more thermoplastic polyester elastomer polymers, which are also commercially available from the Celanese Corporation having different melting points.
- the colorants used were inorganic pigments.
- compositions were formulated and the following results were obtained with respect to swirl effect and part integrity.
- a proto-type automotive grab handle was then molded using injection moiding into a two-cavity tool. Material temperature of 185°C was used in molding. The machine was equipped with a 2.5:1 compression ratio screw. The residence time in the barrel was controlled by a capacity of approximately 6 shots in the barrel. Fast screw rotation ( ⁇ 1 ,5 seconds) was utilized to maximize the swirl effect. Example 2 above showed the best balance of degree of swirl and part integrity for the particular application.
- Example 2 The embodiment of Example 2 was molded into a gun rest part under a commercial process. Material temperature was 185°C, the compression ratio of the screw was 2.5:1 , and the barrel capacity was approximately at 3.5 shots. Again fast screw rotation was employed. Example 2 produced parts that had a swirled appearance due to the manner in which the second phase was combined with the first phase. Overall, the gun rest parts exhibited a camouflage pattern.
- examples 4, 5 and 6 were included using a different polymer system.
- the first phase contained a
- thermoplastic polyester elastomer commercially available from the Celanese Corporation, with a melting point of about 187°C.
- the second phase contained one or more thermoplastic polyester elastomer polymers, which are also commercially available from the Celanese Corporation having different melting points.
- the colorants used were again inorganic pigments.
- Examples 4, 5 and 6 were injection molded into 100mm x 150mm x 3mm plaques using a material temperature of 193°C, the compression ratio of the screw was 2.5: , and the barrel capacity was approximately at 4 shots. Again fast screw rotation was employed.
- Example 5 produced parts that had optimum swirled appearance due to the manner in which the second phase was combined with the first phase.
- Example 4 exhibited insufficient swirl effect.
- Example 6 exhibited a pattern that was too discreet. Overall, the molded plaques of Example 5 exhibited a camouflage pattern.
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Abstract
Polymer compositions are described that contain at least two different immiscible phases for producing molded articles having a swirl-like or marble-like appearance. The first phase, for instance, may contain one or more polyoxymethylene polymers. The second phase, on the other hand, contains one or more polymers that together have a melting point that is from about 5° to about 30° different than the melting point of the polyoxymethylene polymer. In one embodiment, the second phase may contain a thermoplastic elastomer, a glycol-modified polyethylene terephthalate, or a polyamide and may have a melting point that is higher than the melting point of the polyoxymethylene polymer. The second phase is present in the polymer composition in relatively low amounts, such as in amounts less than about 5% by weight. The second phase can contain a high concentration of colorants that creates a contrast of colors when the molded article is produced.
Description
MOLDED ARTICLES HAVING A SWIRL-LIKE OR MARBLE-LIKE
APPEARANCE AND COMPOSITIONS FOR PRODUCING SAME
BACKGROUND
Structural polymers such as plastic materials are used in numerous and diverse applications. In fact, those skilled in the art continue to strive to replace parts conventionally made from metal and wood with those made from polymers. The polymers, for Instance, may offer various advantages with respect to strength properties, chemical resistance, and/or cost.
One problem that has been encountered in producing molded polymer articles, however, is the ability to produce articles with a distinctive look or appearance. For instance, molded polymer articles are generally uniform in color. In certain applications, however, multi-coiored parts are desired. Thus, in the past, non-dispersing pigments or pigment particles have been incorporated into polymers in order to produce articles having contrasting colors. Such non- dispersing pigments, for instance, have been used to produce speckled surfaces or parts having a tortoise-like appearance. Processes for producing molded articles having contrasting color properties are disclosed, for instance, in European Patent Application No. EP 0931807, International PCT Application Publication No. WO 97/37825, U.S. Patent No. 4,125,582, U.S. Patent No. 4,183,673, U.S. Patent No. 5,053,176, U.S. Patent No. 5,489,656, and U.S. Patent Application Publication No. 2001/0045680, which are all incorporated herein by reference.
When attempting to produce molded polymer articles having multiple colors, however, problems have been experienced in producing articles with the desired effect without adversely impacting other properties of the polymer. For instance, producing polymer articles with multiple colors can adversely impact upon the strength of the resulting material depending upon the mixture of materials that are used to produce the part.
One particular type of structural polymer that has good rigidity and strength properties are polyoxymethylene polymers. Polyoxymethylene (which is also referred to as "POM") is a high-performance polymer having good mechanical properties. Due to its properties, polyoxymethylene polymers are commonly used as a direct replacement for metals due to its stiffness, dimensional stability, and
corrosion resistance. Polyoxymethylene polymers exist in the form of
homopolymers and copolymers.
Although polyoxymethylene polymers have a desirable combination of physical properties, various problems have been encountered in attempting to produce multi-colored articles containing a polyoxymethylene polymer. In particular, the problems described above have been particularly problematic when processing polyoxymethylene polymers. Thus, a need currently exists for a polymer composition and method capable of producing multi-colored articles from polyoxymethylene polymers.
SUMMARY
in general, the present disclosure is directed to the production of molded polymeric articles that can have a multi-colored appearance and predominately contain a polyoxymethylene polymer. Of particular advantage, the
polyoxymethylene polymer articles can be produced with contrasting colors without any substantial adverse impacts upon the strength of the resulting material.
In one embodiment, for instance, the present disclosure is directed to a molded polymer article that is made from a two-phase polymer composition. The first phase of the composition is immiscible with a second phase. In this regard, the first phase remains distinct from the second phase when the composition is molded into the article. In one embodiment, the first phase comprises a
polyoxymethylene polymer. The second phase, on the other hand, comprises a thermoplastic, semi-crystalline polymer. In accordance with the present
disclosure, the thermoplastic, semi-crystalline polymer has a melting point that is at least 5° higher or lower, such as from about 10°C to about 30°C higher or lower than the melting point of the polyoxymethylene polymer. In one particular embodiment, for instance, the thermoplastic, semi-crystalline polymer has a melting point that is higher than the melting point of the polyoxymethylene polymer.
In one embodiment, the first phase may have a different color than the second phase. In this manner, when the two phases are combined together, the resulting molded polymer article can have a swirl-like appearance or a marble-like appearance depending upon the relative amounts and the manner in which the phases are combined.
In one embodiment, the thermoplastic, semi-crystalline polymer comprises a thermoplastic elastomer, a glycol-modified polyethylene terephthalate copolymer, or a polyamide. For example, in one particular embodiment, the second phase may contain a thermoplastic polyester elastomer.
The polyoxymethylene polymer contained in the first phase may have a melting point that is lower than the melting point of the polymer contained in the second phase. The polyoxymethylene polymer, for instance, may have a melting point of from about 150°C to about 200°C. The thermoplastic, semi-crystalline polymer contained in the second phase, on the other hand, may have a melting point of from about 170°C to about 210°C, such as from about 185°C to about 200°C.
In order for the second phase to have a desired color and contrast with the first phase, the second phase may contain a colorant such as a pigment if desired. For instance, at least one colorant may be present in the second phase in an amount from about 1% to about 60% by weight of the second phase.
The relative amount of the first phase in comparison to the second phase can vary depending upon the particular application and the desired result. In general, the polymer composition may contain the second phase in an amount of from about 0.5% to about 10% by weight, such as from about 1% to about 5% by weight. The relative amount of the phases may have an impact on the resulting appearance of the molded article. In one embodiment, for instance, the molded article may have a swirl-like design. Alternatively, the molded article may have a marble-like appearance. In one particular embodiment, the first phase and the second phase may have different but complementary colors such that the first and second phases produce a camouflage pattern in the final product.
The polymer composition can be used in any suitable molding process to produce articles. For instance, the composition can be used in a blow molding process or in an injection molding process.
Other features and aspects of the present disclosure are discussed in greater detail below.
DETAILED DESCRIPTION
It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present disclosure.
In general, the present disclosure is directed to polymer compositions and molded articles that include at least two distinct phases. The first phase comprises one or more polyoxymethylene polymers. The second phase, on the other hand, comprises a thermoplastic, semi-crystalline polymer that is immiscible with the first phase. The polymer composition has many different uses and applications. In one particular embodiment, one or more colorants can be incorporated into the second phase and/or the first phase so that the phases have different colors. In this manner, a multi-colored article can be produced. Depending upon the relative amounts of the phases and the manner in which the phases are mixed, for instance, a molded article can be produced that has a swirl-like appearance, a marble-like appearance, or the like. In this manner, products can be produced having a very decorative appearance. In addition, products can be produced having a camouflage-like pattern or can be produced that imitate natural materials, such as wood, marble or granite.
Of particular advantage, multi-phase molded articles can be made according to the present disclosure without significantly adversely affecting the strength of the polyoxymethylene polymer. In one embodiment, for instance, a higher melting point polymer is used as the color concentrate resin that is combined with the polyoxymethylene polymer. The higher melting point polymer, for instance, may contain relatively high amounts of colorant while being combined with the polyoxymethylene polymer in relatively low amounts. In some
applications, the impact strength resistance of the resulting product may actually be increased in relation to a similar product made exclusively from the
polyoxymethylene polymer.
The polyoxymethylene polymer that comprises the first phase of the polymer composition may comprise any suitable homopolymer or copolymer of polyoxymethylene. Po I yoxym ethylenes are generally unbranched linear polymers that may contain at least 80%, such as at least 90% oxymethylene units
(-CH2-O-). The homopolymers are generally obtained by polymerizing
formaldehyde or trioxane, wherein the polymerization is initiated cationical!y or anionically. Copolymers of polyoxymethylenes may contain not only oxymethyiene units but also oxyalkylene units, where the alkyiene groups may contain from about 2 to about 8 carbon units, linear or branched. The term polyoxymethylenes as used herein encompasses homopolymers of formaldehyde or its cyclic oligomers, such as trioxane or tetroxane, and also corresponding copolymers.
Homopolymers of formaldehyde or of trioxane are polymers whose hydroxy end groups have been chemically stabilized in a known manner with respect to degradation, e.g. via esterification or via etherifi cation. Copolymers are polymers composed of formaldehyde or of its cyclic oiigomers, in particular trioxane, and of cyclic ethers, of cyclic acetals, and/or of linear polyacetals.
These POM homo- or copolymers are known per se to the person skilled in the art and are described in the literature.
Very generally, these polymers have at least 50 mol % of
— CH2— O— repeat units in the main polymer chain. The homopolymers are generally prepared via polymerization of formaldehyde or trioxane, preferably in the presence of suitable catalysts.
POM copolymers are preferred in the inventive molding compositions, particularly those which also contain, besides the— CH2— O— repeat units, up to 50 mol %, preferably from 0.1 to 20 mo! %, and in particular from 0.5 to 10 mol %, of— o— R1— repeat units, where R is a saturated or ethylenically unsaturated alkyiene group having at least two carbon atoms, or a cycloalkylene group, which, if appropriate, has sulfur atoms or preferably oxygen atoms in the chain, and which, if appropriate, bears one or more substituents selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, halogen, or alkoxy.
R1 is preferably a C2-C -alkylene group which, if appropriate, has one or more substituents which are C C4-alkyl groups, or are Ci-C -a!koxy groups, and/or are halogen atoms, preferably chlorine atoms, or a group of the formula - ((CnH2n)"0-)m, in which n is a whole number from 2 to 4 and m is 1 or2.
These groups can advantageously be introduced into the copolymers via ring-opening of cyclic ethers and/or acetals.
Preferred cyclic ethers or acetals are those of the formula
R2— O
[0 I.— C I¾], in which x is 0 or 1 and R2 is a C2-C4-alkylene group or an alkyleneoxyalkylene unit which, if appropriate, have one or more substituents which are CrC4-alkyi groups, or which are CrC4-alkoxy groups, and/or which are halogen atoms, preferably chlorine atoms.
Merely by way of example, mention may be made of 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 oligo- or polyformals, such as polydioxolane or polydioxepan, as comonomers.
It is particularly advantageous to use copolymers composed of from 99.5 to 95 mo! % of trioxane and of from 0.5 to 5 mol % of one of the above-mentioned comonomers.
Other polyoxymethylenes likewise suitable are oxymethylene terpolymers which by way of example are prepared via reaction of trioxane and of one of the cyclic ethers or acetals described above, and using a third monomer, preferably a bifunctlonal compound of the formula
Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diethers composed of glycidyl compounds and formaldehyde in a molar ratio of 2:1, and also diethers composed of 2 mol of glycidyl compound and 1 mol of an aliphatic diol having from 2 to 8 carbon atoms, examples being the diglycidyl ether of ethylene glycol, 1 ,4-butanediol, ,3-butanediol, 1 ,3-cyclobutanediol, 1 ,2- propanediol, and 1 ,4-cyclohexanediol, and also diglycerol diformal, to mention just a few examples.
Processes for preparation of the POM homo- and copolymers described above are known to the person skilled in the art and are described in the literature.
In one embodiment, the preparation of the polyoxymethylene can be carried out by polymerization of polyoxymethylene-forming monomers, such as trioxane or a mixture of trioxane and dioxolane, in the presence of ethylene glycol as a molecular weight regulator. The polymerization can be effected as precipitation polymerization or in the melt. Initiators which may be used are the compounds known per se, such as trifluoromethane sulfonic acid, these preferably being added as solution in ethylene glycol to the monomer. The procedure and termination of the polymerization and working-up of the product obtained can be effected according to processes known per se. By a suitable choice of the polymerization parameters, such as duration of polymerization or amount of molecular weight regulator, the molecular weight and hence the MVR value of the resulting polymer can be adjusted. The criteria for choice in this respect are known to the person skilled in the art.
The melting point of the polyoxymethylene polymer (or blend of polymers) can vary depending upon how the polymer is made, its molecular weight, and various other factors. In one embodiment, for instance, the melting point can be from about 150°C to about 200°C. The weight average molecular weight of the polymer can vary from about 5000 to about 200,000, such as from about 7000 to about 150,000.
The polyoxymethylene polymer present in the composition can generally have a melt volume rate (MVR) of less than 50 cm3/10 min, such as from about 0.5 to about 20 cm3/10 min, such as from about 2 to about 15 cm3/10 min. In one particular embodiment, for instance, the MVR may be from about 6 to about 12 cm3/10 min, determined according to ISO 1133 at 190°C and 2.16 kg.
The polyoxymethylene polymer selected for use in the first phase of the polymer composition generally comprises a polymer having a desired melting point and physical properties. In addition, the polymer should also not chemically react or otherwise couple to the immiscible polymer contained in the second phase. In this regard, the polymer composition generally does not contain any
compatibilizers or coupling agents, i.e. non-compatibilized.
The amount of polyoxymethylene polymer present in the polymer
composition of the present disclosure can vary depending upon the particular application. In one embodiment, for instance, the composition contains
polyoxymethylene polymer in an amount of at least 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 90% by weight, such as in an amount greater than about 95% by weight. In general, the polyoxymethylene polymer is present in an amount less than about 99% by weight, such as in an amount less than about 98% by weight, such as in an amount less than about 97% by weight.
In addition to a polyoxymethylene polymer contained in the first phase, the polymer composition also includes a second phase containing a thermoplastic, semi-crystalline polymer. The thermoplastic, semi-crystailine polymer contained in the second phase comprises a polymer that is immiscible with the
polyoxymethylene polymer. In addition, the polymer in the second phase has a melting point that is higher or lower than the melting point of the polyoxymethylene polymer. For instance, the melting point of the thermoplastic, semi-crystalline polymer can be at least 5°C greater or less than the melting point of the
polyoxymethylene poiymer, such as from about 10°C to about 30°C higher or lower than the melting point of the polyoxymethylene polymer. In one particular embodiment, the thermoplastic, semi-crystalline polymer has a melting point that is higher than the melting point of the polyoxymethylene polymer.
For instance, in one embodiment, the polymer contained in the second phase comprises a thermoplastic elastomer. Examples of thermoplastic elastomers are polyester elastomers (TPE-E), thermoplastic polyamide elastomers (TPE-A) and thermoplastic polyurethane elastomers (TPE-U). In general, a thermoplastic elastomer is selected that has a desired melting point in comparison to the melting point of the polymers contained in the first phase. In addition, the thermoplastic elastomer should be immiscible with respect to the
polyoxymethylene polymer. Thus, a thermoplastic elastomer can be selected that does not chemically react or otherwise couple to the polyoxymethylene polymer.
In one particular embodiment, one or more thermoplastic elastomers are blended to form the second phase of the polymer composition that have an overall melting temperature that is higher than the melting temperature of the first phase
polymers. For instance, in one embodiment, a thermoplastic polyester elastomer having a melting point of about 170°C may be blended with a thermoplastic polyester elastomer having a melting point of about 200°C in order to form the second phase that overall has a melting point that is from about 10°C to about 30°C higher than the melting point of the poiyoxymethylene polymers present in the first phase.
In addition to or instead of a thermoplastic elastomer, the second phase can also contain various other thermoplastic, semi-crystalline polymers. For instance, in an alternative embodiment, the second phase may contain a polyethylene terephthaiate copolymer having the desired melting point with respect to the first phase polymers. For instance, in one embodiment, the second phase may contain a glycol-modified polyethylene terephthaiate copolymer. For instance, the copolyester may contain polyethylene terephthaiate copolymerized with
cyclohexane dimethanol. Such polymers can have a melting point of from about 170°C to about 215°C, such as from about 170°C to about 210°C.
In yet another embodiment, the second phase may contain a poiyamide polymer. Poiyamide polymers are generally immiscible with poiyoxymethylene polymers and can have a melting point higher than many poiyoxymethylene polymers. For instance, in one embodiment, the poiyamide polymer comprises nylon 11. Nylon 11 , for instance, can have a melting point of from about 175°C to about 200°C, such as from about 180°C to about 190°C.
In another embodiment, the poiyamide polymer may comprise nylon 12. In addition to a thermoplastic, semi-crystalline polymer, the second phase of the polymer composition may also contain one or more colorants. Colorants can be included in the second phase depending upon the desired color and the final application for the polymer.
The colorants used may be any desired inorganic pigments, such as titanium dioxide, ultramarine blue, cobalt blue, etc., or organic pigments or colors, such as phthaiocyanines, anthraquinones, etc., or special effects pigments such as pearlescent pigments, aluminum based pigments, fluorescent pigments and the like, or carbon black, either individually or as a mixture, or together with polymer- soluble dyes.
The amount of colorants present in the second phase of the polymer
composition can depend upon the particular application. In general, colorants may be present in the second phase in an amount from about 1 % to about 60% by weight, based upon the weight of the second phase. In certain embodiments, in order to have significant color differences between the first phase and the second phase, the second phase may contain colorants in amounts greater than 10% by weight, such as in amounts greater than 20% by weight, such as in amounts greater than 30% by weight, such as in amounts greater than 40% by weight, such as even in amounts greater than 50% by weight, based upon the weight of the second phase. It was discovered that significant amounts of colorant can be included in the second phase in order to improve the overall appearance of the resulting product without significantly decreasing the strength, such as the impact strength of the product.
In addition to being contained in the second phase, the above colorants may also be added to the first phase if desired. For instance, colorants may be combined with the polyoxym ethylene polymers in amounts up to about 10% by weight, such as from about 0.1 % to about 5% by weight.
In general, the polymer composition predominately comprises the first phase. For instance, the second phase may be present in the polymer
composition in an amount less than 10% by weight, such as in an amount from about 1 % to about 5% by weight.
The polymer composition of the present disclosure can optionally contain a stabilizer and/or various other known additives. Such additives can include, for example, antioxidants, acid scavengers, formaldehyde scavengers, UV stabilizers or heat stabilizers, in addition, the molding material or the molding may contain processing auxiliaries, for example adhesion promoters, lubricants, nucleating agents, demolding agents, fillers, reinforcing materials or antistatic agents and additives which impart a desired property to the molding material or to the molding, such as dyes and/or pigments and/or further impact modifiers and/or additives imparting electrical conductivity; and mixtures of these additives, but without limiting the scope to said examples.
In general, other additives can be present in the polymer composition in an amount up to about 10% by weight, such as from about 0.1% to about 5% by weight, such as from about 0.1 to about 2% by weight.
Molded articles can be made in accordance with the present disclosure using various methods and techniques. In particular, articles can be made using any suitable extrusion process. In one embodiment, for instance, molded articles can be produced using injection molding.
During injection molding, barrel temperatures, compression ratio of the screw, residence time of the material through the barrel, and degree of mixing in the barrel can be controlled so as to produce a product having the desired properties and appearance.
For example, the stock temperature of the material as controlled by barrel temperatures and shear heating can be kept close to the minimum recommended temperature for the first phase polymer. Elevated tem eratures effectively reduce the delta temperature (melting point of second phase minus actual material temperature of first phase) between the two phases and may yield a less desirable appearance, particularly if the delta temperature approaches 5°C or less,
Compression ratio of the screw used in the barrel of the injection molding machine may range up to 3:1 , and preferably 2.5:1 or less. Compression ratios of less than 2.5:1 will yield desirable molded part appearance at lower the lower range of melting point differences.
Sizing of the barrel to the shot size of the molded article may be used to control the desired appearance. Shot size refers to the amount of polymer it takes to fill the mold for producing a part. Shot size can vary dramatically between processes and systems. Barrel capacity of 6 shots or less, and preferably 3 shots or less, is desirable. Higher barrel capacity leads to longer residence times and less differentiated swirl patterns.
Finally, degree of mixing in the barrel of the injection molding machine is also controlled by the screw speed and back pressure. It is common practice and knowledge that if less mixing is desired, a slower screw rotation along with low back pressure should be employed. However, when attempting to produce swirllike patterns, fast screw rotation is preferred to minimize screw rotation time, which minimizes mixing and maximizes the swirl pattern. Low back pressure is desirabie. For example, if the mold closed time is 20 seconds, it is common practice to utilize most of the 20 seconds with screw rotation at the slowest speed
possible to reduce mixing. In contrast, the preferred method is fast screw rotation (less than 5 second screw rotation time) to maximize the swirl-like pattern.
Changing the above factors, for instance, can create the difference between little to no swirl or marble effect, to a highly desirable swirl or marble pattern.
The present disclosure may be better understood with reference to the following example.
EXAMPLE
The following experiment was conducted in order to show some of the benefits and advantages of the present invention.
In this example, a polymer composition was formulated in accordance with the present disclosure. The polymer composition included a first phase and a second phase.
The first phase contained a polyoxymethyiene copolymer. The
polyoxym ethylene copolymer had a melting point of about 170°C and is
commercially available from the Celanese Corporation.
The second phase, on the other hand, contained one or more thermoplastic polyester elastomer polymers, which are also commercially available from the Celanese Corporation having different melting points.
The colorants used were inorganic pigments.
More particularly, the following compositions were formulated and the following results were obtained with respect to swirl effect and part integrity.
A proto-type automotive grab handle was then molded using injection moiding into a two-cavity tool. Material temperature of 185°C was used in molding. The machine was equipped with a 2.5:1 compression ratio screw. The residence
time in the barrel was controlled by a capacity of approximately 6 shots in the barrel. Fast screw rotation (< 1 ,5 seconds) was utilized to maximize the swirl effect. Example 2 above showed the best balance of degree of swirl and part integrity for the particular application.
The embodiment of Example 2 was molded into a gun rest part under a commercial process. Material temperature was 185°C, the compression ratio of the screw was 2.5:1 , and the barrel capacity was approximately at 3.5 shots. Again fast screw rotation was employed. Example 2 produced parts that had a swirled appearance due to the manner in which the second phase was combined with the first phase. Overall, the gun rest parts exhibited a camouflage pattern.
To further illustrate the present disclosure, examples 4, 5 and 6 were included using a different polymer system. The first phase contained a
thermoplastic polyester elastomer, commercially available from the Celanese Corporation, with a melting point of about 187°C.
The second phase contained one or more thermoplastic polyester elastomer polymers, which are also commercially available from the Celanese Corporation having different melting points.
The colorants used were again inorganic pigments.
Examples 4, 5 and 6 were injection molded into 100mm x 150mm x 3mm plaques using a material temperature of 193°C, the compression ratio of the screw was 2.5: , and the barrel capacity was approximately at 4 shots. Again fast screw rotation was employed. Example 5 produced parts that had optimum swirled appearance due to the manner in which the second phase was combined with the first phase. Example 4 exhibited insufficient swirl effect. Example 6 exhibited a
pattern that was too discreet. Overall, the molded plaques of Example 5 exhibited a camouflage pattern.
These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.
Claims
What Is Claimed:
. A molded polymer article comprising:
a multi-phase polymer composition comprising a first phase that is immiscible with a second phase, the first phase remaining distinct from the second phase in the molded article, the first phase comprising a polyoxymethylene polymer having a melting point, the second phase comprising a thermoplastic, semi-crystalline polymer having a melting point that is at least 5°C higher or lower than the melting point of the polyoxymethylene polymer.
2. A molded polymer article as defined in claim 1 , wherein the first phase has a first color and the second phase has a second color that is different than the first color.
3. A molded polymer article as defined in claim 1 , wherein the immiscible phases create a swirl-like or marble-like appearance.
4. A molded polymer article as defined in claim 1 , wherein the second phase comprises discrete domains within a matrix formed by the first phase.
5. A molded polymer article as defined in claim 1 , wherein the thermoplastic, semi-crystalline polymer contained in the second phase comprises a thermoplastic elastomer, a polyamide, or a glycol-modified polyethylene terephthalate.
6. A molded polymer article as defined in claim 1 , wherein the melting point of the thermoplastic, semi-crystalline polymer is from about 10°C to about 30°C higher or lower than the melting point of the polyoxymethylene polymer.
7. A molded polymer article as defined in claim 5, wherein the polyoxymethylene polymer has a melting point that is lower than the thermoplastic, semi-crystalline polymer.
8. A molded polymer article as defined in claim 1 , wherein the polyoxymethylene polymer has a melting point of from about 150°C to about 200°C and wherein the thermoplastic, semi-crystalline polymer has a melting point of from about 170°C to about 210°C.
9. A molded polymer article as defined in claim 1 , wherein the thermoplastic, semi-crystalline polymer comprises a thermoplastic polyester elastomer.
10. A molded polymer article as defined in claim 1 , wherein the first phase and the second phase create a camouflage pattern on a surface of the article.
11 . A molded polymer article as defined in claim 1 , wherein the article has been formed by injection molding.
12. A molded polymer article as defined in claim 1 , wherein the second phase contains at least one color pigment, the at least one colorant being present in the second phase in an amount from about 1% to about 60% by weight, based upon the weight of the second phase.
13. A molded polymer article as defined in claim 1 , wherein the second phase is present in the polymer composition in an amount from about 1% to about 5% by weight.
14. A polymer composition comprising:
a first phase comprising a polyoxymethylene polymer, the polyoxymethylene polymer having a melting point, the polyoxymethylene polymer being present in the polymer composition in an amount of at least about 70% by weight; and
a second phase that is immiscible with the first phase, the second phase comprising a thermoplastic, semi-crystailine polymer comprising a thermoplastic elastomer, a polyamide, or a glyco!-modified polyethylene terephthalate copolymer, the thermoplastic, semi-crystalline polymer having a melting point that is from about 5°C to about 30°C higher than the melting point of the polyoxymethylene polymer, the second phase further comprising at least one colorant such that the second phase has a different color than the first phase.
5. A polymer composition as defined in claim 14, wherein the thermoplastic, semi-crystalline polymer comprises a thermoplastic polyester elastomer.
16. A polymer composition as defined in claim 14, wherein the second phase is present in the polymer composition in an amount from about 1% to about 5% by weight.
17. A polymer composition as defined in claim 14, wherein the polyoxymethylene polymer has a melting point of from about 150°C to about 200°C
and wherein the thermoplastic, semi-crystalline polymer has a melting point of from about 170°C to about 210°C.
18. A polymer composition as defined in claim 15, wherein the polyoxym ethylene polymer has a melting point of from about 160°C to about 180°C and wherein the thermoplastic, semi-crystalline polymer has a melting point of from about 190°C to about 200°C.
19. A process for producing a molded polymer article comprising injection molding the polymer composition defined in claim 14 to form a polymer article, the first phase remaining distinct from the second phase in the polymer article such that the second phase comprises discrete domains within a matrix formed by the first phase.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280023117.0A CN103534311B (en) | 2011-04-05 | 2012-03-26 | Have swirling or marbled appearance molded products and for the manufacture of its composition |
EP12711546.7A EP2694585B1 (en) | 2011-04-05 | 2012-03-26 | Molded articles having a swirl-like or marble-like appearance and compositions for producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US13/080,364 | 2011-04-05 | ||
US13/080,364 US9090769B2 (en) | 2011-04-05 | 2011-04-05 | Molded articles having a swirl-like or marble-like appearance and compositions for producing same |
Publications (1)
Publication Number | Publication Date |
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WO2012138493A1 true WO2012138493A1 (en) | 2012-10-11 |
Family
ID=45922855
Family Applications (1)
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PCT/US2012/030500 WO2012138493A1 (en) | 2011-04-05 | 2012-03-26 | Molded articles having a swirl-like or marble-like appearance and compositions for producing same |
Country Status (4)
Country | Link |
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US (2) | US9090769B2 (en) |
EP (1) | EP2694585B1 (en) |
CN (1) | CN103534311B (en) |
WO (1) | WO2012138493A1 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20160236385A1 (en) * | 2015-02-12 | 2016-08-18 | T.F.H Publications, Inc. | Injection molded pet chew article |
CN105286221A (en) * | 2015-11-24 | 2016-02-03 | 浙江伟星实业发展股份有限公司 | Injection molding zipper and production process thereof |
EP3228737B1 (en) * | 2016-04-04 | 2018-12-12 | Polytex Sportbeläge Produktions-GmbH | Artificial turf with marbled monofilament |
JP2022547632A (en) * | 2019-09-30 | 2022-11-14 | ザ プロクター アンド ギャンブル カンパニー | Molded article with grain-like appearance |
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Also Published As
Publication number | Publication date |
---|---|
US20120259059A1 (en) | 2012-10-11 |
EP2694585B1 (en) | 2016-08-03 |
US9090769B2 (en) | 2015-07-28 |
US9745469B2 (en) | 2017-08-29 |
EP2694585A1 (en) | 2014-02-12 |
US20150329720A1 (en) | 2015-11-19 |
CN103534311B (en) | 2016-04-20 |
CN103534311A (en) | 2014-01-22 |
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