MXPA97000142A - Compositions of rigidas calandra vinyl polymer - Google Patents
Compositions of rigidas calandra vinyl polymerInfo
- Publication number
- MXPA97000142A MXPA97000142A MXPA/A/1997/000142A MX9700142A MXPA97000142A MX PA97000142 A MXPA97000142 A MX PA97000142A MX 9700142 A MX9700142 A MX 9700142A MX PA97000142 A MXPA97000142 A MX PA97000142A
- Authority
- MX
- Mexico
- Prior art keywords
- vinyl polymer
- polyethylene
- tin
- present
- vinyl
- Prior art date
Links
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- -1 polyethylene Polymers 0.000 claims abstract description 42
- 239000004698 Polyethylene (PE) Substances 0.000 claims abstract description 35
- 229920000573 polyethylene Polymers 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000003490 calendering Methods 0.000 claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims description 21
- 229910052718 tin Inorganic materials 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 12
- 239000004800 polyvinyl chloride Substances 0.000 claims description 12
- 238000004448 titration Methods 0.000 claims description 6
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical group CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 claims description 3
- 229940071127 thioglycolate Drugs 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims description 3
- SPIUEOWNLJQKJK-UHFFFAOYSA-J [Sn+4].[O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS Chemical group [Sn+4].[O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS SPIUEOWNLJQKJK-UHFFFAOYSA-J 0.000 claims 3
- 239000004605 External Lubricant Substances 0.000 abstract description 20
- 230000001050 lubricating Effects 0.000 abstract description 3
- 239000000314 lubricant Substances 0.000 description 14
- AZUZXOSWBOBCJY-UHFFFAOYSA-N 6-hydroxy-5-methyl-4,11-dioxoundecanoic acid Chemical compound OC(=O)CCC(=O)C(C)C(O)CCCCC=O AZUZXOSWBOBCJY-UHFFFAOYSA-N 0.000 description 11
- OMFHQUCUWSMFOJ-FMONCPFKSA-N COMP protocol Chemical compound ClCCN(CCCl)P1(=O)NCCCO1.O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1.C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1.C([C@H](C[C@]1(C(=O)OC)C=2C(=C3C([C@]45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C=O)=CC=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 OMFHQUCUWSMFOJ-FMONCPFKSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 7
- 102200046998 RS1 G70S Human genes 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004610 Internal Lubricant Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000004209 oxidized polyethylene wax Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ZIUHCEIEPOPBCK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;hexanedioic acid;octadecanoic acid Chemical compound OCC(CO)(CO)CO.OC(=O)CCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O ZIUHCEIEPOPBCK-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- CJSGFXKAHVWGMU-ODZAUARKSA-L (Z)-but-2-enedioate;tin(2+) Chemical compound [Sn+2].[O-]C(=O)\C=C/C([O-])=O CJSGFXKAHVWGMU-ODZAUARKSA-L 0.000 description 1
- HCVMXNVIYWNLML-UHFFFAOYSA-N 1-ethenyl-9H-carbazole;styrene Chemical compound C=CC1=CC=CC=C1.N1C2=CC=CC=C2C2=C1C(C=C)=CC=C2 HCVMXNVIYWNLML-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N 2-cyanopropene-1 Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 102100012482 KRT27 Human genes 0.000 description 1
- 101710026188 KRT27 Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N N-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000000111 anti-oxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000001143 conditioned Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical group CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009999 singeing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-M stearate Chemical compound CCCCCCCCCCCCCCCCCC([O-])=O QIQXTHQIDYTFRH-UHFFFAOYSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The present invention relates to: The present invention provides an external lubricating composition for the calendered vinyl polymer. The external lubricant provides rigid vinyl polymer compositions having improved slimming resistance, clarity, detachment and stability. The external lubricant comprises an effective amount for lubricating the polyethylene vinyl polymer having a Brookfield viscosity at a temperature of 150 ° C, greater than about 85,000 centipoises and an acid number as determined by the standardized KOH value of between about 5 and about 9. The sheets of the calendered vinyl polymer are used for blister packs and credit cards.
Description
"COMPOSITIONS OF CALIBRATED RIGID VINYL POLYMERS"
The present invention relates to rigid calendered vinyl polymer compositions.
BACKGROUND OF THE INVENTION
^ __ Rigid vinyl polymer compositions, such as polyvinyl chloride compositions, are used to produce a variety of structural articles, such as plastic tubing, sills, containers and sheets. These rigid compositions are essentially not plasticized. The sheets are typically manufactured by calendering, which involves passing the material between rollers. Because the resulting sheets are typically used for blister packs and credit cards, a very clear end product is highly desirable. In order to stabilize the vinyl polymer against the influence of heat and light decomposition, tin stabilizer vinyl polymers including organotin stabilizers, such as organotin mercaptides and organotin sulfides are used to stabilize.
Lubricants are also added to the vinyl polymers to facilitate extrusion or other melt processing of the structural articles produced. Lubricants are generally classified as external or internal lubricants. An external lubricant provides a lubrication layer between the plastic melt and the metal surfaces of the processing equipment. The external lubricant is used to coat the particles
"^. of the polymer resin and inhibits its adhesion to metal surfaces. In contrast, an internal lubricant reduces the viscosity by effective melting of the vinyl polymer at the processing temperatures in order to improve its flow properties during processing, as well as to activate its melting. An internal lubricant is generally needed only for thin extrusions, such as thin-walled films and pipes. The suitability of the lubricants for the vinyl polymer is determined by the type of stabilizer used in the vinyl polymer. For example, the PLASTICS ADDITIVE HANDBOOK, third edition (Hanser Publishers 1990) discloses that oxidized polyethylene waxes are suitable lubricants for tin-stabilized polyvinyl chloride sheets.
Known stable tin stabilized polyvinyl chloride calendered sheet formulations include compositions such as
Rigid Resin of 4-Cells 100 phr
Organotin Stabilizer 2.0
0 Acrylic Processing Assistant 3.0
to be known by David Hur itz "The Use of Low Molecular Weight Polyethylene in Rigid PVC Lubrication", 5 Society of Plastic Engineers, Annual Technical Conference Trigesimoprimera, 349 (May 1973), and
PVC 100 phr
0, * '*' - Processing Assistant 1.5
Glycerol mono-oleate 1.0
Octyl Stabilizer Sn 1.6 5 Impact or Shock Modifier 5 - 10
A-c'R) 316 (oxidized homopolymer polyethylene wax, number 0 of acid of 16) 0.05-0.3 J which is disclosed in A-C < R) POLYETHYLENES FOR PVC by AlliedSignal Inc. (1986). See also Technical Data on Ac (R) Polyethylenes and Copolymers for Plastics by AlliedSignal Inc. (1973) which gives 5 that -c (R) 392A (high density oxidized polyethylene wax having an acid number of 30). ) is useful for tin-stabilized polyvinyl chloride. See also Technical Data on -c (R) Polyethylenes for c- Plastics by Allied (1984) which discloses that -c (R) 0 316A (high density oxidized polyethylene wax having an acid number of 16) or -c (R) 330 (high density oxidized polyethylene wax having an acid number of 30) is useful for tin-stabilized calendered polyvinyl chloride. US Pat. No. 4,203,880 discloses tin stabilized polyvinyl chloride having a lubricant package comprising oxidized polyethylene wax having an acid number greater than 5., and a melt viscosity of 1,000 to 60,000 centipoise 0 to 140 ° C, and a known external lubricant such as paraffin oils, paraffin waxes, liquid and solid hydrocarbons, non-oxidized polyethylene waxes, ester of montane ester, stearate of lead, mineral oil, 12-hydroxystearic acid, ethylene bis-stearamide and glycol esters of fatty acids containing from 10 to 20 or more carbon atoms. It would be desirable for there to be a calendered vinyl polymer composition having improved resistance to thinning, clarity, detachment, stability and improved slimming strength compared to the calendered vinyl polymer compositions currently used.
COMPENDIUM OF THE INVENTION
A composition has been found that meets the need previously cited in the art. Surprisingly, we have found an external lubricant composition for vinyl polymer, wherein the external lubricant provides resistance to improved electrodeposition, clarity, detachment and stability. In this manner, the present invention provides a composition comprising: (a) vinyl polymer; (b) an amount effective to stabilize the vinyl polymer of the tin stabilizer and (c) an amount effective to lubricate the polyethylene vinyl polymer having a Brookfield viscosity at a temperature of 140 ° C, greater than about 85,000 centipoise and an acid number as determined by the normalized KOH titration of between about 5 and about 9. If measured at a temperature of 150 ° C, the polyethylene has a Brookfield viscosity of about 40,000 to about 60,000 centipoise. The present invention also provides a calendered sheet comprising: (a) vinyl polymer; (b) an amount effective to stabilize the vinyl polymer of the tin stabilizer and (c) an effective amount for lubricating the polyethylene vinyl polymer having a Brookfield viscosity at a temperature of 140 ° C, greater than about 85,000 centipoise, and an acid number as determined by normalized KOH titration of between about 5 and about 9. The present composition and the calendered sheets made of the present composition advantageously have improved resistance to thinning and light transmission compared to the known composition. which has an external lubricant of pentaerythritol adipate stearate. Other advantages of the present invention will become apparent from the following description and the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED MODALITIES
Vinyl polymers useful in the present invention include polyvinyl chloride and polymerized forms of vinyl acetate, vinyl chloride-vinyl acetate copolymers, vinylidene halides such as vinylidene vinyl pyridine, vinyl carbazole styrene, vinylbenzene, acrylic esters such as methyl acrylate, ethyl acrylate or methyl methacrylate as well as acrylonitrile. The preferred vinyl polymer is a polyvinyl chloride which includes both vinyl chloride homopolymers and both copolymers and terpolymers of vinyl chloride with comonomers such as vinyl acetate, vinyl formate, alkylvinyl ethers, ethylene, propylene, butylene, chloride of vinylidene, alkyl acrylates and methacrylates, alkyl maleates and alkyl fumarates. Preferably, at least 80 percent and most preferably 100 percent of the monomer to be polymerized will be a vinyl chloride monomer. The vinyl polymers useful in the present invention can be obtained commercially. Stabilizers useful in the present invention include cadmium, barium, zinc and calcium salts; and tin stabilizers, such as tin maleate and tin thioglycollates. Stabilizers of tin are preferred. A particularly preferred tin stabilizer is ethyl thioglycolate. The tin stabilizers useful in the present invention can be obtained commercially. Other useful tin stabilizers are disclosed in U.S. Patent Number 4,203,880 which is incorporated herein by reference. '-. An effective amount is used to stabilize the vinyl polymer of the tin stabilizer. Typically, the tin stabilizer is present in an amount of about 0.25 to about 5 parts by weight per 100 parts of the vinyl polymer. The polyethylene of the present invention has a Brookfield viscosity at a temperature of 140 ° C greater than about 85, 000 centipoise and an acid number as determined by normalized KOH titration of between about 5 and about 9. If measured at a temperature of 150 ° C, the polyethylene has a Brookfield viscosity of about 40,000 to about 60,000 centipoise. Suitable polyethylenes can be characterized as high density oxidized homopolymers of ethylene, copolymers containing acrylates and ethylene, terpolymers containing acrylates, esters and ethylene. Preferably, oxidized high density ethylene homopolymers are used. These polyethylenes have been oxidized to an acid number as determined by a more preferred normalized KOH titration, of between about 1 and about 12, and especially preferably between about 5 and about 9. The appropriate oxidized polyethylenes can be obtained from AlliedSignal Inc. of Morristown, New Jersey. A preferred oxidized polyethylene is listed in the following Table:
Polyethylene Number of Acid Density Oxidized Viscosity (mgKOH / gram) (gr / cc) Brookfield (cps at 140 ° C)
A-C (R> 307A 5 - 9 0.98> 85,000
These oxidized polyethylenes as well as others which are useful in the practice of the present invention can be obtained by oxidizing the polyethylene with air or oxygen by conventional methods. Appropriate methods are described in U.S. Patent Nos. 3,060,163 and 3,322,711 which are incorporated herein by reference. As is known to those skilled in the art, oxidation results in cleavage of the polymer and formation of acid groups. In addition, from the formation of acid groups in the polymer chain, the esters, aldehydes, ketones, hydroxides and peroxides are also found in different amounts along the polymer chains. If too small a quantity of lubricant is present in the final vinyl polymer composition, the melt viscosity of the vinyl polymer composition may be too high or the melting time may be too short. An extremely short melting time is undesirable for extrudable compositions because this can result in prolonged exposure of the polymer melt at elevated temperatures resulting in premature degradation. If too large a quantity of lubricant is present in the final vinyl polymer composition, a condition referred to as "SLIMMING" may occur. The excess lubricant rises to the surface of the vinyl polymer composition and remains in contact. with the heated wall of the extrusion apparatus, the mill or the calender cylinder for a period of time sufficient to singe. The singeing is carried out either together with the molten polymer, causing discoloration or scorching can form deposits along the inner wall or in the die of the extrusion apparatus thereby altering the shape of the extruded or calendered article. An effective amount is used to lubricate the vinyl polymer of the oxidized polyethylene. Typically, the oxidized polyethylene is present in an amount of about 0.01 to about 10 parts by weight per 100 parts of vinyl polymer. The oxidized polyethylene is preferably present in an amount of about 0.05 to about 5 parts by weight per 100 parts of the vinyl polymer, more preferably in an amount of about 0.05 to about 1 part by weight per 100 parts of the vinyl polymer, and especially preferably in an amount of about 0.1 to about 1 part by weight per 100 parts of the vinyl polymer. In addition to the thermal stabilizer and the external lubricant, the present compositions may contain one or more additives that are conventionally employed in the polymer compositions. These additives include fillers or fillers, such as alkaline earth metal carbonates, pigments such as titanium dioxide, antioxidants such as sterically hindered phenols or bis-phenols, impact or shock modifiers such as methyl methacrylate-butadiene-styrene terpolymers , and adsorbents such as alkaline earth metal silicates and diatomaceous earth, if the composition contains a significant amount of liquid ingredients. The vinyl compositions to which the external lubricants present are added are rigid which means that they contain essentially no plasticizer. These vinyl resins are useful in the production of rigid articles, mainly pipes.
rigid, costaneras, containers and sheets. It is known that the effectiveness of lubricants in resin formulations can be evaluated by measuring the rheological properties of the formulation. These properties are typically studied by means of a torque rheometer of
torsion consisting of a miniature mixer and a torque meter that measures the load on the mixer. The mixing forces developed within a sample of material at a certain temperature, cause a deviation of a record dynamometer. This 0 deviation is recorded in a strip chart. This torque, which is expressed in meter-grams, is directly related to the viscosity of the fusion that is being mixed. When a vinyl-type polymer is degraded, it rapidly cross-links and exhibits a sharp elevation in its melt viscosity. The time for this to occur is a measure of the thermal stability under dynamic shear conditions. A curve of the typical torque rheometer provides a person skilled in the art with information regarding melting, melting, flow and crosslinking in the processing of the tested polymer. This procedure is disclosed in Method D 2538-88 of the American Society for the Testing of Materials "Standard Practice for Fusion of Poly (Vinyl Chioride) (PVC) Compounds Using a Torque Rheometer". The most general used rheometer is the "Plasticorder Brabender" which essentially consists of an oil-heated roller mixing head driven by a variable speed motor equipped with means to measure the torque developed in the head. The machine is conditioned with a mixing head equipped with a thermoelectric melting tank. To determine the melting time of the vinyl chloride powder mixture, for example, an exactly weighed quantity of the mixture is charged to the mixing head with the aid of a fast-charging chute. A graph of the torque versus time is produced and the point where the fusion is completed is shown by an initial maximum in torque. The dynamic thermal stability is measured in minutes from the beginning of the graph to the point of decomposition that is marked by an elevation in the torque. The present invention is illustrated more fully by the following non-limiting Examples. Unless otherwise stated, all parts are by weight.
EXAMPLES OF COMPARISON AND EXAMPLES
For each Example, the effect of the external lubricants present for the calendered polyvinyl chloride sheet composites was determined using a "Plasticorder Brabender" at a temperature of 190 ° C, at 60 revolutions per minute and a sample size of 40xSPG. Each composition was prepared by mixing in a Henschel mixer for 10 minutes at 3,800 revolutions per minute and for an additional 10 minutes at 2,600 revolutions per minute. The light transmission was measured by spectrophotometry using a "Coloreye Macbeth" 3000. The injection molded samples of the clear rigid polyvinyl chloride with the following dimensions were those that were used (3.81 x 2.54 x .381 centimeters). The transmittance was terminated using a light source D65 that is representative of daylight from the northeast end and a standard observer of 10 °. CIELAB was the calculation method for the amount of light transmission through each sample. Glass was used as the norm. The spiral flow was measured using the following equipment. The injection molding machine was Kawaguchi
K25C (28 grams, type of reciprocating screw). The mold was made to measure, with multiple cavities for the thermoplastic products. The cavity was 6.35 millimeters, in a semi-round spiral, four turns, a maximum radius of 3.81 centimeters, five millimeter marks filled from the shore. The injection molding parameters were normal rigid PVC conditions. The procedure was an injection mold of one to two dozen coils, which determine the final lengths and select the median value. The two-row mill tack test determined the time required for the external lubricant system of the composite to disintegrate and thereby cause the compound to adhere to the metal surfaces of the mill. The mill was installed under the conditions indicated below. 180 grams of each compound were used. The test procedure was as follows: (1) The mill rolls were cleaned using stearic acid. (2) The mill was left running for 10 minutes to allow the temperature to equilibrate. (3) The compound was added between the point of attachment of the cylinders until it was banded, that is, adhered to the cylindricals. (4) The time for the banded was noted. (5) Using a brass knife and alternating from left to right, the banded blade was cut and folded 12 times. (6) After 5 minutes, the sheet was removed from the cylinders and wound up through the fastening point. (7) Steps 5 to 8 were repeated until the sheet could no longer be removed from the cylinders. This time was noted and designated as the time of adhesion. The present lubricant used was A-c (R) 307A, oxidized polyethylene which can be obtained commercially from AlliedSignal Inc. of Morristown, New Jersey, United States of America. The properties of this oxidized polyethylene are the following:
Polyethylene Number of Acid Density Oxidized Viscosity (mgKOH / gram) (gr / cc) Brookkfield! Cps at 140 ° C)
A-C < R) 307A 5 - 9 0.98 > 85,000
The Comparison Examples were carried out in the same manner as the examples, with the exception that the external lubricants used at present were used instead of the external lubricants present. For each example of comparison and example, the resin used was Shintech 650 PVC resin, K56-58 and the
used modifier was Kanace B22 which is MBS. The tin stabilizers used were Thermolite 83 which is octyltin thioglycolate and Thermolite 890 which is octyltin thioglycolate. The internal lubricant was
, -_, Loxiol G16 which is a glycerol ester or Lubol 515 which is 0 a glycerol ester. The external lubricant used was
Loxiol G70S which is pentaerythritol adipate stearate or
A-C (R) 316, high density oxidized polyethylene wax having an acid number of 16 and a viscosity
Brookfield of 8,500 centipoises that is measured at 140 ° C. 5 EXAMPLE OF COMPARISON A AND EXAMPLE 1
> - > '' - COMPONENT COMP. EXAMPLE 1
0 PVC 100 100
Modifier 5.00 5.00
Thermolite 831 1.25 1.25 5 Thermolite 890 1.25 1.25 Loxiol G16 or Lubol 516 0. 75 0. 875
Loxiol G70S 0.25
Polyethylene A-C < R) 307 0.125
Brabender Fusion Test (165 ° C, 30 RPM, 54gr): Melting Time (min) 1.3 1.2
Maximum Torque Torque (meter-grams) 3,200 2,800
Torque of Balance (meter-grams) 2,075 2,100
Brabender stability (190 ° C, 60 RPM, 54 gr): Stability time (min) 29 38
Maximum Torque Torque (meter-grams) 3,400 3,300 Torque of Balance (meter-gram) 1,150 1,200
Fusion Time (min) 0.3 0.3
Spiral Flow (cm) 54 53
Transmittance of Light 88.98 93.43
Two Cylinder Mill Grinding Test: Time to Adhesion (min) 20 60
172 ° C / 163 ° C / 23 RPM Mill 15 Adhered Non-adhesion
Thinning Observation None None
EXAMPLES OF COMPARISON B TO I AND EXAMPLES 2 TO 4
For Comparison Examples B to I and Examples 2 to 4, the type and amount of external lubricant was varied. The other components indicated in the following table remained the same:
PVC 100 PHR
PHR modifier
, - Sn Stabilizer 1.25 PHR 10 Internal Lubricant 0.75 PHR
For Comparison Examples B and C and 5 Example 2, the test conditions were as follows:
Temperature Temperature Speed of Graduation Material Cylinder 0 (° C) (° C) (RPM)
Front Cylinder 204 171 18.5
Rear Cylinder 193 163 23 5 The space of the fastening point was .381 mm. In order to obtain an adhesion time, the amount of the external lubricant used was halved as compared to the amount of the external lubricant used in Comparative Example A and Example 1.
LUBRICANT EXTERNAL TIME TIME BAND ADHESION
COMP. B 0.125 Loxiol 30 seconds 20 minutes G70S at 1 minute
COMP. 0.0625 of 30 seconds After a Polyethylene at 1 minute hour, no A-C (R) 316 adhesion
EXAMPLE 2 0.0625 of 30 seconds After a Polyethylene at 1 minute hour, no A-C <R) 307 adhesion
For Example B Comparison, no visible thinning occurred but the product had a slightly brownish tint when banded and some defects on the surface so that it did not result in a clear product. For Comparison Example C, the thinning occurred in the initial cylinder but appeared to be cleared with a possible blue nebulosity in the cylinders and more defects occurred on the surface compared to Example B of Comparison but no brownish tinge occurred. For example 2, thinning occurred in the initial cylinder but it seemed to clear with a
,, possible blue nebulosity on the surface of the cylinder and 0 more defects occurred on the surface compared to Comparison Example C but the brownish tint did not occur. For Comparison Examples D and E and Example 3, high cylinder temperatures were used to obtain an adhesion time for the Loxiol G70S:
Temperature Temperature Speed of Graduation Material Cylinder 0 or Adjustment (° C) (RPM)
Front Cylinder 216 185 18.5
Rear Cylinder 204 177 23 5 The space of the fixing point was .381 mm
LUBRICANT EXTERNAL TIME TIME BAND ADHESION
COMP. D 0.125 Loxiol from 0 to 30 5 minutes G70S seconds
COMP. 0.0625 from 0 to 30 after Polyethylene seconds 30 minutes, A-C < R) 316 non-adherence
EXAMPLE 3 0.625 from 0 to 30 after Polyethylene seconds 1.5 hours, A-C < R) 307 non-adhesion
For Example D Comparison, thinning did not occur but the product had a slightly brownish dye during banding and some defects on the surface so that it did not result in a clear product. For Comparative Example E, the thinning occurred in the initial cylinder and more defects occurred on the surface compared to Comparative Example D but no brownish tinge occurred. For Example 3, the thinning occurred in the initial cylinder and more defects occurred on the surface compared to the Comparative Example E but no brownish tinge occurred. For Comparison Examples 1F and G and Example 4, the amount of external lubricant used was increased to determine if slimming would occur:
LUBRICANT EXTERNAL TIME TIME BAND ADHESION BAND
COMP. 0.25 Loxiol from 0 to 30 After 40 G70S second minutes non-adhesion
COMP. G 0.125 from 0 to 30 After 40 Polyethylene seconds, A-C < R) 316 non-adherence
EXAMPLE 4 0.125 from 0 to 30 After 40 seconds polyethylene, A-c'R) 307 non-adhesion For Example F Comparison, no thinning occurred but some defects occurred on the surface so that it did not result in a clear product. For Comparative Example G, thinning occurred in the initial cylinder but was cleared after banding and more defects occurred on the surface compared to Comparative Example F, but in total the color was better. For Example 4, thinning occurred in the initial cylinder that appeared to clear after banding and more defects occurred on the surface compared to Example G Comparison. For Comparison Examples H and I, the amount of Polyethylene A-C (R) 316 was reduced in order to try to obtain an adhesion time.
LUBRICANT EXTERNAL TIME TIME BAND ADHESION
COMP. H 0.03125 from 0 to 30 Polyethylene adhered seconds after 5 A-C (R) 316 minutes
COMP, 0.0416 from 0 to 30 after 30 Polyethylene seconds, not Ac (R > 316 adhesion Field tests have shown that Ac (R) 316 polyethylene becomes thinner over time while with polyethylene Ac (R) 307, no thinning has been observed.
Claims (10)
1. A composition comprising: (a) a vinyl polymer; 5 (b) an amount effective to stabilize the vinyl polymer of a tin stabilizer; and (c) an effective amount to lubricate the polyethylene vinyl polymer having a viscosity - Brookfield at a temperature of 140 ° C greater than 0 about 85,000 centipoise, and an acid number as determined by normalized KOH titration of between about 5 and about 9.
The composition according to claim 1, in where the vinyl polymer is polyvinyl chloride.
3. The composition according to claim 1, wherein the tin stabilizer is a tin thioglycolate.
4. The composition according to claim 3, wherein the tin thioglycolate is octyltin thioglycolate.
The composition according to claim 1, wherein the polyethylene is present in an amount of about 0.01 to about 10 5 parts by weight per 100 parts of the vinyl polymer.
6. The composition according to claim 1, wherein the polyethylene is present in an amount of about 0.05 to about 5 parts by weight per 100 parts of the vinyl polymer.
7. A calendered sheet comprising: (a) vinyl polymer; (b) an amount effective to stabilize the vinyl polymer of a tin stabilizer; and, K. (c) an amount effective to lubricate the polyethylene vinyl polymer having a Brookfield viscosity at a temperature of 140 ° C greater than about 85,000 centipoise and an acid number as determined by standardized KOH titration of between about 5 and about 9.
The calendered sheet according to claim 7, wherein the vinyl polymer is polyvinyl chloride.
9. The calendered sheet according to claim 7, wherein the tin stabilizer is 0 tin thioglycolate. The calendered sheet according to claim 7, wherein the polyethylene is present in an amount of about 0.01 to about 10 parts by weight per 100 parts of the vinyl polymer.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/270,078 US5414035A (en) | 1994-07-01 | 1994-07-01 | Calendered rigid vinyl polymer compositions |
US08270078 | 1994-07-01 | ||
PCT/US1995/008073 WO1996001290A1 (en) | 1994-07-01 | 1995-06-26 | Calendered rigid vinyl polymer compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
MXPA97000142A true MXPA97000142A (en) | 1998-01-01 |
MX9700142A MX9700142A (en) | 1998-01-31 |
Family
ID=23029814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
MX9700142A MX9700142A (en) | 1994-07-01 | 1995-06-26 | Calendered rigid vinyl polymer compositions. |
Country Status (8)
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US (1) | US5414035A (en) |
EP (1) | EP0769035B1 (en) |
JP (1) | JP3746512B2 (en) |
AT (1) | ATE169652T1 (en) |
DE (1) | DE69504078T2 (en) |
ES (1) | ES2120757T3 (en) |
MX (1) | MX9700142A (en) |
WO (1) | WO1996001290A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US5600097A (en) * | 1994-11-04 | 1997-02-04 | Lucent Technologies Inc. | Fire resistant cable for use in local area network |
DE10015593A1 (en) * | 2000-03-29 | 2001-10-11 | Clariant Gmbh | Use of polyolefin waxes in plastics processing |
US20040000741A1 (en) * | 2002-06-26 | 2004-01-01 | Lindner Robert A. | Manufacture of polyvinylchloride articles |
TWI341856B (en) * | 2003-03-14 | 2011-05-11 | Honeywell Int Inc | Cellulose reinforced resin compositions |
WO2010017155A2 (en) * | 2008-08-05 | 2010-02-11 | Polyone Corporation | High flow polyvinyl halide compound and methods of making and using same |
JP6191752B1 (en) * | 2016-11-02 | 2017-09-06 | 住友ベークライト株式会社 | Vinyl chloride resin composition and sheet material |
CN110050029B (en) | 2016-12-14 | 2023-01-31 | 吉昂功能材料(东莞)有限公司 | Flexible polyvinyl halide for injection over-molding |
CN110396262A (en) * | 2019-09-03 | 2019-11-01 | 罗春华 | A kind of dedicated enhancing composite plastic of heavy caliber blow-off line and preparation method |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2705089C2 (en) * | 1976-02-10 | 1986-12-11 | Henkel KGaA, 4000 Düsseldorf | Lubricant for the shaping processing of thermoplastics |
US4040997A (en) * | 1976-03-09 | 1977-08-09 | American Hoechst Corporation | Method for incorporating processing additives in polyvinyl chloride resins and additive concentrate for use therein |
US4218353A (en) * | 1976-11-18 | 1980-08-19 | Allied Chemical Corporation | External lubricant compositions for rigid vinyl polymers |
US4132691A (en) * | 1977-04-06 | 1979-01-02 | M&T Chemical Inc. | Lubricant composition for vinyl chloride polymers |
FR2401953A1 (en) * | 1977-08-29 | 1979-03-30 | Seperef | COMPOSITION BASED ON RIGID POLYVINYL CHLORIDE, AND ARTICLES CONFORMING WITH SUCH COMPOSITION |
DE2964004D1 (en) * | 1978-05-19 | 1982-12-16 | Ciba Geigy Ag | Additives system for use in polymers |
US4203880B1 (en) * | 1978-11-13 | 1994-04-26 | M & T Chemicals Inc | Lubricant composition for halogen-containing polymers |
US4332702A (en) * | 1981-01-12 | 1982-06-01 | Henkel Corporation | Polyvinyl chloride compositions and processing |
US4336176A (en) * | 1981-01-12 | 1982-06-22 | Henkel Corporation | Polyvinyl chloride processing |
DE3630783A1 (en) * | 1986-09-10 | 1988-03-24 | Neynaber Chemie Gmbh | LUBRICANTS FOR THERMOPLASTIC PLASTICS |
US5032634A (en) * | 1988-12-02 | 1991-07-16 | Akzo America Inc. | Stabilized vinyl halide resins and stabilizer combination |
US5002989A (en) * | 1989-09-01 | 1991-03-26 | The Dow Chemical Company | Formulation for extrudable vinylidene chloride copolymers having high barrier properties |
US5087669A (en) * | 1989-09-18 | 1992-02-11 | The Dow Chemical Company | Vinyl chloride polymer composition with improved fusion properties |
ATE154376T1 (en) * | 1993-08-11 | 1997-06-15 | Allied Signal Inc | EXTERNAL LUBRICANT COMPOSITIONS FOR HARD VINYL POLYMERS |
-
1994
- 1994-07-01 US US08/270,078 patent/US5414035A/en not_active Expired - Lifetime
-
1995
- 1995-06-26 JP JP50389596A patent/JP3746512B2/en not_active Expired - Fee Related
- 1995-06-26 DE DE69504078T patent/DE69504078T2/en not_active Expired - Fee Related
- 1995-06-26 ES ES95924074T patent/ES2120757T3/en not_active Expired - Lifetime
- 1995-06-26 WO PCT/US1995/008073 patent/WO1996001290A1/en active IP Right Grant
- 1995-06-26 AT AT95924074T patent/ATE169652T1/en not_active IP Right Cessation
- 1995-06-26 MX MX9700142A patent/MX9700142A/en unknown
- 1995-06-26 EP EP95924074A patent/EP0769035B1/en not_active Expired - Lifetime
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