CN117980351A - Polyethylene and vulcanizable chlorinated polyethylene composition using the same - Google Patents
Polyethylene and vulcanizable chlorinated polyethylene composition using the same Download PDFInfo
- Publication number
- CN117980351A CN117980351A CN202280063075.7A CN202280063075A CN117980351A CN 117980351 A CN117980351 A CN 117980351A CN 202280063075 A CN202280063075 A CN 202280063075A CN 117980351 A CN117980351 A CN 117980351A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- chlorinated polyethylene
- vulcanizable
- weight
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004709 Chlorinated polyethylene Substances 0.000 title claims abstract description 121
- -1 Polyethylene Polymers 0.000 title claims abstract description 119
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 91
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 91
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000009826 distribution Methods 0.000 claims abstract description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- DJCISYVIXPWVHY-UHFFFAOYSA-N 5-[(2-sulfanylidene-3h-1,3,4-thiadiazol-5-yl)disulfanyl]-3h-1,3,4-thiadiazole-2-thione Chemical compound S1C(=S)NN=C1SSC1=NNC(=S)S1 DJCISYVIXPWVHY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 3
- NQYKSVOHDVVDOR-UHFFFAOYSA-N n-hexadecylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCC NQYKSVOHDVVDOR-UHFFFAOYSA-N 0.000 claims description 3
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000000913 palmityl 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])C([H])([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 claims description 2
- 150000004867 thiadiazoles Chemical group 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 7
- 230000007423 decrease Effects 0.000 abstract description 6
- 230000002028 premature Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 21
- 238000004073 vulcanization Methods 0.000 description 20
- 238000005227 gel permeation chromatography Methods 0.000 description 17
- 229920001903 high density polyethylene Polymers 0.000 description 17
- 239000004700 high-density polyethylene Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000005660 chlorination reaction Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 241001441571 Hiodontidae Species 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 150000007529 inorganic bases Chemical class 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000013013 elastic material Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 230000005483 Hooke's law Effects 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 238000000136 cloud-point extraction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
In the present invention, there is provided a polyethylene having a reduced proportion of a high molecular region in a molecular structure, optimized in viscosity and melt index and having a narrow molecular weight distribution. Thus, it is possible to prevent premature crosslinking of the chlorinated polyethylene obtained by reacting the polyethylene with chlorine, thereby minimizing a decrease in viscosity even during long-term storage and improving extrusion processability. In addition, it provides a vulcanizable chlorinated polyethylene composition using the polyethylene.
Description
Technical Field
Cross reference to related applications
The present application claims priority from korean patent application No. 10-2021-0159747, filed on 11-18, 2021, and No. 10-2022-0154687, filed on 17, 2022, 11, 2022, to korean patent office, the disclosures of which are incorporated herein by reference in their entirety.
The present invention relates to polyethylene and vulcanizable chlorinated polyethylene compositions using the same.
Background
Chlorinated polyethylene prepared by reacting polyethylene with chlorine is known to have more improved physical and mechanical properties than polyethylene. In particular, since chlorinated polyethylene can withstand a severe external environment, chlorinated polyethylene can be used as a packaging material such as various containers, fibers, hoses, etc., as well as a heat transfer material.
The chlorinated polyethylene is widely used as a material for rubber products and resin products or as a raw material for adhesives and paints due to its excellent heat resistance, oil resistance, weather resistance, ozone resistance and abrasion resistance. In particular, chlorinated polyethylene is attracting attention as a rubber material having excellent heat resistance, oil resistance, weather resistance, ozone resistance.
Regarding the vulcanization of chlorinated polyethylene, various proposals have been made. For example, various sulfur-containing compounds such as organic peroxides and mercaptotriazoles have been proposed as vulcanizing agents for chlorinated polyethylene, and it is known to use various organic vulcanization accelerators such as amine compounds in combination with the vulcanizing agents. Furthermore, it is common knowledge to those skilled in the art that an acid absorber that absorbs a small amount of acidic components generated during the vulcanization of chlorinated polyethylene must be added to the composition for vulcanization. For example, japanese patent laid-open publication No. 1980-039250 proposes a metal compound selected from the group consisting of oxides, hydroxides, carboxylates, silicates, carbonates, phosphites, borates, basic sulfites and tribasic sulfates of metals of group IVA of the periodic Table as an acid absorbent.
Further, japanese patent laid-open publication No. 1978-003439 describes that a composition for vulcanization containing a thiadiazole-based compound and the like are used as a vulcanizing agent for chlorinated polyethylene, and an alkali metal oxide, an alkali metal salt, an alkali metal hydroxide and the like are used as a compounding agent.
The vulcanizing agent and the mixture thereof can be used for improving the strength of the vulcanized product or keeping white. However, when the chlorinated polyethylene is stored after being compounded with a vulcanizing agent, there is a disadvantage in that extrusion processability is deteriorated due to an increase in Mooney Viscosity (MV).
Thus, in order to improve the processability during extrusion and the excellent strength of the vulcanized product, there has been a need to develop a technique capable of maintaining high crosslinking efficiency while minimizing the rate of change of the Mooney Viscosity (MV) over time during long-term storage of the chlorinated polyethylene composition.
Disclosure of Invention
Technical problem
Polyethylene having a reduced proportion of high molecular regions in the molecular structure, optimized viscosity and melt index, and having a narrow molecular weight distribution is provided. The polyethylene is capable of minimizing the rate of change of the Mooney Viscosity (MV) with time upon long-term storage of the chlorinated polyethylene composition, thereby improving processability during extrusion and having excellent strength of vulcanized products.
Further, a vulcanizable chlorinated polyethylene composition containing a chlorinated polyethylene using the above polyethylene and a chlorinated polyethylene vulcanizate obtained by vulcanizing the same are provided.
Technical proposal
According to one embodiment of the present invention, there is provided a polyethylene satisfying the following conditions:
the integrated value in a region where Log MW is 5.5 or more in a GPC chart with Log MW on the x-axis and dw/dlogMw on the y-axis is 14% or less of the total integrated value,
A molecular weight distribution (Mw/Mn) of 5.8 or less,
A complex viscosity (η (ω500)) measured at a frequency (ω) of 500rad/s of 650pa·s to 850pa·s, and
MI 5 (melt index measured at 190 ℃ C. And 5kg load) was 1.2g/10min to 3.0g/10min.
Furthermore, a vulcanizable chlorinated polyethylene composition comprising a chlorinated polyethylene using the polyethylene is provided.
Further, a chlorinated polyethylene vulcanizate obtained by vulcanizing the vulcanizable chlorinated polyethylene composition is provided.
Advantageous effects
According to the present invention, there is provided a polyethylene having a reduced proportion of high molecular regions in the molecular structure, optimized viscosity and melt index, and a narrow molecular weight distribution. Thus, the polyethylene is capable of minimizing the rate of change of the Mooney Viscosity (MV) with time upon long-term storage of the chlorinated polyethylene composition, thereby improving processability during extrusion and having excellent vulcanizate strength.
Detailed Description
In the present invention, the terms "first", "second", etc. are used to describe various components, and these terms are used only to distinguish certain components from others.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless the context clearly indicates otherwise, singular forms are intended to include plural forms. It will be further understood that the terms "comprises," "comprising," "includes" and "including," when used in this specification, specify the presence of stated features, integers, steps, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.
The terms "about" and "approximately" are intended to have a meaning that is close to the specified value or range with the allowable error and to prevent the exact or absolute value disclosed for the understanding of the present invention from being illegally or illegally used by any unreasonable third party.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example and will herein be described in detail. It should be understood, however, that there is no intention to limit the invention to the specific forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Hereinafter, the present invention will be described in more detail.
Polyethylene
According to one embodiment of the present invention, there is provided a polyethylene having a reduced proportion of high molecular regions in the molecular structure, optimized viscosity and melt index, and having a narrow molecular weight distribution. Thus, the polyethylene is capable of minimizing the rate of change of MV over time upon long-term storage after processing into a chlorinated polyethylene composition, thereby improving processability during extrusion and excellent strength of vulcanized products.
The polyethylene is characterized in that the integral value of a region having Log MW of 5.5 or more in a GPC graph having an x-axis of Log MW and a y-axis of dw/dlogMw is 14% or less of the total integral value, the molecular weight distribution (Mw/Mn) is 5.8 or less, the complex viscosity (η (ω500)) measured at a frequency (ω) of 500rad/s is 650 Pa.s to 850 Pa.s, and the MI 5 (melt index measured at 190 ℃ and a load of 5 kg) is 1.2g/10min to 3.0g/10min.
The polyethylene according to the invention optimizes the polymer structure and achieves a narrow molecular weight distribution. In addition, when chlorinated polyethylene is prepared from the polyethylene according to the present invention and compounded, the premature crosslinking effect is suppressed and the rate of change of compound MV over time during storage before extrusion can be improved.
In particular, when the content of the high molecular weight region in the polymer structure of High Density Polyethylene (HDPE) as a material of Chlorinated Polyethylene (CPE) is adjusted, the HDPE polymer structure remains almost unchanged in CPE as a chlorination reaction product. Thus, the high molecular weight region is reduced and premature crosslinking reactivity is controlled, enabling the rate of change of compound MV over time to be minimized.
Meanwhile, the polyethylene according to the present invention may be an ethylene homopolymer without a separate copolymer.
The polyethylene is characterized in that the polymer region ratio is optimized such that the integrated value of the region having Log MW of 5.5 or more in GPC chart with x-axis of Log MW and y-axis of dw/dlogMw is 14% or less of the total integrated value, and complex viscosity and melt index MI 5 (measured at 190 ℃ and 5kg load) at high frequency are maintained in the optimum range while having a narrow molecular weight distribution.
Specifically, the polyethylene may have an integral value of less than about 14% or from about 0.5% to about 14%, less than about 13% or from about 0.8% to about 13%, less than about 12% or from about 1% to about 12%, less than about 11% or from about 3% to about 11%, less than about 10.5%, or from about 5% to about 10.5% of the total integral value in a GPC trace having a Log MW on the x-axis and a dw/dlogMw on the y-axis. The polyethylene may have the above-mentioned optimized ratio of high molecular regions in the molecular structure in the GPC diagram, thereby improving mechanical properties such as tensile strength while ensuring high chlorination yield and workability due to the occurrence of uniform chlorination reaction.
The polyethylene of the present invention is characterized in that the ratio of the high molecular regions in the molecular structure is in the optimum range as described above, and at the same time, the molecular weight distribution (Mw/Mn) is also optimized.
The polyethylene may have a molecular weight distribution of about 5.8 or less or about 2.0 to about 5.8. This means that the molecular weight distribution of the polyethylene is narrow. When the molecular weight distribution is wide, the difference in molecular weight between polyethylenes is large, and thus the chlorine content of the polyethylenes after the chlorination reaction may be different, and thus uniform distribution of chlorine is difficult. In addition, when the low molecular weight component is melted, the fluidity becomes high, and thus the pores of the polyethylene particles may be blocked, thereby reducing the chlorination yield. In contrast, since the polyethylene of the present invention has the molecular weight distribution as described above, the difference in molecular weight between polyethylenes after the chlorination reaction is not large, and thus, chlorine can be uniformly substituted.
For example, gel permeation chromatography (GPC, manufactured by Water) can be used to measure the proportion and molecular weight distribution (MW/Mn, polydispersity index) of a region having Log MW of 5.5 or more in a GPC diagram.
Here, the molecular weight distribution (Mw/Mn, PDI, polydispersity index) may be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyethylene and then dividing the weight average molecular weight by the number average molecular weight.
Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyethylene can be measured using a polystyrene calibration curve. For example, PL-GPC220 manufactured by Waters can be used as a Gel Permeation Chromatography (GPC) instrument, and Polymer Laboratories PLgel MIX-B300 mm column can be used. The evaluation temperature may be 160℃and the flow rate 1mL/min using 1,2, 4-trichlorobenzene as solvent. Each polyethylene sample may be pretreated by dissolving in 1,2, 4-trichlorobenzene containing 0.0125% BHT at 160 ℃ for 10 hours using a GPC analyzer (PL-GP 220), and a sample having a concentration of 10mg/10mL may be provided in an amount of 200 μl. Calibration curves formed from polystyrene standards can be used to obtain Mw and Mn. 9 polystyrene standards having a molecular weight of 2000g/mol, 10000g/mol, 30000g/mol, 70000g/mol, 200000g/mol, 700000g/mol, 2000000g/mol, 4000000g/mol and 10000000g/mol were used.
The polyethylene may have a weight average molecular weight of about 100000g/mol to about 158000g/mol. Preferably, the weight average molecular weight of the polyethylene may be about 11000g/mol or more, about 120000g/mol or more, about 125000g/mol or more, about 130000g/mol or more, or about 135000g/mol or more. Further, the weight average molecular weight of the polyethylene may be about 155000g/mol or less, about 152000g/mol or less, about 150000g/mol or less, about 148000g/mol or less, about 146000g/mol or less, about 145000g/mol or about 143000g/mol or less.
Meanwhile, the polyethylene exhibits a complex viscosity (η. Omega.: 500)) measured at a frequency (ω) of 500rad/s in an optimal range of about 650 Pa.s to about 850 Pa.s. Specifically, the complex viscosity (η (ω500)) measured at a frequency (ω) of 500 rad/sec may be about 670pa·s or more, about 680pa·s or more, about 700pa·s or more, about 720pa·s or more, about 740pa·s or more, about 750pa·s or more, about 760pa·s or more, about 770pa·s or more, or about 780pa·s or less, and about 840pa·s or less, about 830pa·s or less, about 820pa·s or less, about 815pa·s or less, about 810pa·s or less, about 805pa·s or less, about 800pa·s or less, or about 795pa·s or less. The polyethylene of the present invention can maintain the above range of complex viscosity (η (ω500)) measured at a frequency (ω) of 500rad/s in terms of improving the chlorination yield while appropriately maintaining the processing load in the extrusion process of processing the blended product after the chlorination process.
In particular, complex viscosity can be measured using a rotational rheometer, for example using the ARES of TA Instruments (Advanced Rheometric Expansion System, ARES G2). Parallel plates 25.0mm in diameter were used at 190℃to give a gap of 2.0mm for the polyethylene sample. The measurement is performed in a dynamic strain frequency sweep mode with a strain rate of 5% and a frequency in the range of 0.05rad/s to 500 rad/s. 10 points can be measured for every ten samples, 41 points total.
In general, for a perfectly elastic material, deformation occurs in direct proportion to the elastic shear stress, which is known as hooke's law. Furthermore, for a purely viscose liquid, the deformation occurs in direct proportion to the viscous shear stress, which is known as newtonian law. For a fully elastic material, deformation can be recovered again when elastic energy accumulates and elastic shear stress is removed. However, for a perfectly viscous material, energy is completely lost through deformation, and therefore deformation cannot be recovered even when elastic shear stress is removed. In addition, the viscosity of the material itself does not change.
However, in the molten state, the polymer has properties intermediate between those of a perfectly elastic material and a viscous liquid, which is called viscoelasticity. In other words, when a shear stress is applied to a polymer in a molten state, deformation is not proportional to the shear stress, and its viscosity varies with the variation of the shear stress, which is called a non-newtonian fluid. Because polymers have large molecular sizes and complex intermolecular structures, these properties are due to the complexity of deformation caused by shear stress.
In particular, when polymers are used to produce molded articles, the phenomenon of shear thinning is considered to be one of the important characteristics of non-newtonian fluids. The shear thinning phenomenon means a phenomenon in which the viscosity of a polymer decreases as the shear rate increases. The method of shaping the polymer is determined by these shear thinning properties. In particular, when manufacturing large molded articles such as large diameter pipes or complex pipes as in the present invention, or molded articles requiring high-speed extrusion of a polymer, it is necessary to apply a reasonable pressure to the molten polymer. Thus, unless the polymer exhibits shear thinning properties, it is difficult to manufacture molded articles. Therefore, the shear thinning properties are considered important.
The present invention therefore measures the shear-thinning properties by complex viscosity (eta [ Pa.s ]) as a function of frequency (omega [ rad/s ]). In particular, by optimizing the complex viscosity at a frequency (ω) of 500rad/s, excellent chlorination yields and excellent compounding properties can be achieved. In particular, by means of the complex viscosity at a frequency (ω) of 500rad/s, it is possible to predict the range of physical properties of the chlorinated polyethylene, such as the Mooney Viscosity (MV).
Meanwhile, the polyethylene is characterized by exhibiting a ratio of high molecular regions in a molecular structure within an optimal range while maintaining a complex viscosity and a melt index MI 5 (melt index measured at 190 ℃ and a load of 5 kg) at a high frequency within the optimal range and maintaining a narrow molecular weight distribution (Mw/Mn).
Specifically, the polyethylene has a melt index MI 5 of about 1.2g/10min to 3.0g/10min when measured according to ASTM D1238 at 190℃and a load of 5 kg. Preferably, the melt index MI 5 can be about 1.3g/10min or more, about 1.4g/10min or more, about 1.5g/10min or more, about 1.8g/10min or more, about 2.0g/10min or more, or about 2.2g/10min or more, and about 2.95g/10min or less, about 2.9g/10min or less, about 2.85g/10min or less, about 2.8g/10min or less, about 2.75g/10min or less, about 2.7g/10min or less, about 2.6g/10min or about 2.5g/10min or less.
Furthermore, the high load melt index MI 21.6 may be about 3g/10min to 33.6g/10min when measured at a load of 21.6kg along with MI 5 measured at a load of 5 kg.
When one of MI 5 and MI 21.6 is too high, the low molecular weight content increases and the shape change of the particles increases, for example, by melting of the low molecules at high temperature during the chlorination process to form agglomerates, resulting in low thermal stability. Thus, for excellent thermal stability, the melt indices MI 5 and MI 21.6 should be about 2.8g/10min or less and about 33.6g/10min or less, respectively. However, as the melt indexes MI 5 and MI 21.6 are lower, the viscosity increases, and physical properties such as mooney viscosity may be out of the optimum range when chlorinated polyethylene is produced, resulting in a problem of poor dispersibility of inorganic matters. Thus, MI 5 and MI 21.6 can be about 1.5g/10min or more and about 33.6g/10min or more, respectively, in terms of reducing extrusion processing load and ensuring excellent physical properties during product processing.
In addition, the polyethylene of the present invention is preferably optimized with the melt index MI 5 optimized as described above and with the melt flow rate ratio (MFRR 21.6/5, a value obtained by dividing the melt index measured at 190℃and a load of 21.6kg by the melt index measured at 190℃and a load of 5kg according to ASTM D1238). At this time, the melt flow rate ratio (MFRR 21.6/5, a value obtained by dividing the melt index measured at 190 ℃ and a load of 21.6kg by the melt index measured at 190 ℃ and a load of 5kg according to ASTM D1238) of the polyethylene may be about 2 to about 12. Specifically, the melt flow rate ratio may be about 2 or more in terms of processability during extrusion, and may be about 12 or less in terms of ensuring excellent mechanical properties by increasing the Mooney Viscosity (MV) of the CPE.
Meanwhile, the polyethylene may have a density of about 0.945g/cm 3 to about 0.960g/cm 3, about 0.948g/cm 3 to about 0.958g/cm 3, about 0.950g/cm 3 to about 0.957g/cm 3, about 0.951g/cm 3 to about 0.956g/cm 3, or about 0.952g/cm 3 to about 0.955g/cm 3. In particular, a density of polyethylene of about 0.945g/cm 3 or more means that the crystalline fraction content of polyethylene is high and dense, and thus it is difficult to change the crystal structure of polyethylene during chlorination. However, when the density of the polyethylene exceeds about 0.960g/cm 3, the content of the crystalline structure of the polyethylene becomes excessively high, and thus, the TREF crystallinity distribution becomes excessively broad and high, and the molecular weight distribution becomes broad, and thus, the heat of fusion increases and the processability decreases during CPE processing. Thus, in terms of application to electric wires and cables and the like, excellent extrusion processability and dimensional stability are ensured even in a high-speed extrusion process and excellent mechanical properties such as tensile strength are exhibited, it is desirable that the density of the polyethylene of the present invention is within the above range.
Meanwhile, the polyethylene according to an embodiment of the present invention may be prepared by polymerizing ethylene in the presence of a Ziegler-Natta catalyst in terms of maintaining complex viscosity and melt index MI 5 (measured at 190 ℃ and 5kg load) within an optimal range at a high frequency and maintaining a narrow molecular weight distribution (Mw/Mn) while exhibiting a proportion of a high molecular region in a molecular structure within an optimal range.
Vulcanizable chlorinated polyethylene composition
According to another embodiment of the present invention, there is provided a vulcanizable chlorinated polyethylene composition comprising a chlorinated polyethylene using the polyethylene described above.
Specifically, the vulcanizable chlorinated polyethylene composition comprises a chlorinated polyethylene prepared by reacting the above polyethylene with chlorine, a sulfide-based crosslinking agent or a derivative thereof, and an amine compound or a derivative thereof.
Hereinafter, each component constituting the vulcanizable chlorinated polyethylene composition of one embodiment will be described in detail.
(A) Chlorinated polyethylene
In the vulcanizable chlorinated polyethylene composition according to the invention, the chlorinated polyethylene can be prepared by reacting the above polyethylene with chlorine, wherein the polyethylene has a molecular structure with a reduced proportion of high molecular area, is optimized in viscosity and melt index, and has a narrow molecular weight distribution.
The reaction with chlorine can be performed by dispersing the prepared polyethylene in water, an emulsifier and a dispersant and then adding a catalyst and chlorine thereto.
The emulsifier may be a polyether or a polyalkylene oxide. The dispersant may be a polymer salt or an organic acid polymer salt, and the organic acid may be methacrylic acid or acrylic acid.
The catalyst may be a chlorination catalyst used in the art, for example, benzoyl peroxide may be used. Chlorine may be used alone or with an inert gas.
The chlorination reaction may be preferably carried out at about 60 ℃ to about 150 ℃, about 70 ℃ to about 145 ℃, about 80 ℃ to about 140 ℃, and the reaction time may preferably be about 10 minutes to about 10 hours, about 1 hour to about 9 hours, or about 2 hours to about 8 hours.
The chlorinated polyethylene prepared by the above reaction may be further subjected to a neutralization process, a washing process and/or a drying process, and thus may be obtained in the form of powder.
In particular, when the content of the high molecular weight region is adjusted in the polymer structure of High Density Polyethylene (HDPE), the HDPE polymer structure remains almost unchanged in CPE as a chlorination reaction product. Thus, the high molecular weight region is reduced and premature crosslinking reactivity is controlled, enabling minimizing the rate of change of compound MV over time.
Meanwhile, the chlorinated polyethylene may have a chlorine content of about 20 to about 50wt%, about 31 to about 45 wt%, or about 35 to about 40 wt%. Here, the chlorine content of chlorinated polyethylene can be measured using combustion ion chromatography (combustion IC, ion chromatography). For example, combustion ion chromatography uses a combustion IC (ICS-5000/AQF-2100H) device equipped with an IonPac AS18 (4X 250 mm) column. The chlorine content can be measured at a flow rate of 1mL/min using KOH (30.5 mM) as eluent at an inlet temperature of 900 ℃ and an outlet temperature of 1000 ℃. In addition, the conventional method in the art can be applied to the equipment conditions and measurement conditions for measuring the chlorine content.
The chlorinated polyethylene may be, for example, randomly chlorinated polyethylene.
Furthermore, the chlorinated polyethylene may be a mixture of polymers of different chlorine content, for example, a blend of a high proportion of chlorinated polyethylene and a low proportion of other rubbers and/or resins. For example, the chlorinated polyethylene may be blended with nitrile rubber, acrylate rubber, and the like. Such blending is performed for the purpose of improving oil resistance, heat resistance, and the like.
The chlorinated polyethylene described above is the main component in the vulcanizable chlorinated polyethylene composition of the invention.
(B) Sulfide-based crosslinking agent or derivative thereof
Meanwhile, the vulcanizable chlorinated polyethylene composition of the present invention comprises a chlorinated polyethylene prepared by reacting the above-mentioned polyethylene with chlorine and a sulfide-based crosslinking agent for a vulcanization process or a derivative thereof.
Specifically, the sulfide cross-linking agent can be a thiadiazole compound or a disulfide compound.
Preferably, the sulfide-based crosslinking agent may be at least one selected from the group consisting of 2, 5-dimercapto-1, 3, 4-thiadiazole and 5,5' -dithiobis-1, 3, 4-thiadiazole-2 (3H) -thione (manufacturer: vanderbilt Chemicals, LLC, product name: vanax-829).
In particular, in terms of controlling the vulcanization reaction of chlorinated polyethylene so that the change rate of MV with time is low, it is more advantageous to use a dithiothiadiazole-based crosslinking agent.
The content of the sulfide-based crosslinking agent or the derivative thereof may be 0.1 to 4 parts by weight based on 100 parts by weight of the chlorinated polyethylene. When the amount of the sulfide-based crosslinking agent or the derivative thereof is less than 0.1 parts by weight based on 100 parts by weight of the chlorinated polyethylene, the vulcanization performance may be lowered, resulting in deterioration of physical properties of the final product. Further, when the disulfide-based crosslinking agent or its derivative is used in an amount exceeding 4 parts by weight based on 100 parts by weight of the chlorinated polyethylene, the change rate of MV increases or the crosslinking rate decreases due to excessive vulcanization reaction, resulting in a decrease in yield. The content of the disulfide-based crosslinking agent or its derivative is 0.5 parts by weight or more and 1 part by weight or more, 1.5 parts by weight or more and 1.8 parts by weight or more, and 3.5 parts by weight or less, 3 parts by weight or less, 2.5 parts by weight or less, or 2.45 parts by weight or less.
For reference, "parts by weight" as used herein refers to the relative concept of the weight ratio of the remaining materials based on the weight of the particular material. For example, in a mixture containing 50g of material a, 20g of material B, and 30g of material C, the amounts of material B and material C are 40 parts by weight and 60 parts by weight, respectively, based on 100 parts by weight of material a.
Further, "wt%" (in% by weight) refers to the absolute concept of representing the weight of a particular material in percent based on the total weight. In the above mixture, the contents of materials A, B and C were 50 wt%, 20 wt% and 30 wt%, respectively, based on the total weight of the mixture of 100 wt%. At this time, the sum of the contents of the respective components does not exceed 100% by weight.
(C) Amine compound or derivative thereof
Meanwhile, the vulcanizable chlorinated polyethylene composition according to the invention mixes a crosslinking agent such as a sulfide-based crosslinking agent or a derivative thereof with the chlorinated polyethylene, and contains an amine compound or a derivative thereof as an organic vulcanization accelerator.
In particular, when only a sulfide-based crosslinking agent or a compound other than an amine compound is used, vulcanization reaction may not be performed. When an amine compound or a derivative thereof is added to the crosslinking agent, a vulcanization reaction is performed, so that physical properties of the final product can be ensured.
Specifically, the amine compound is characterized in that it is a secondary amine compound or a tertiary amine compound. For example, the amine compound may comprise at least 2C 4～20 alkyl groups, preferably at least 2C 5～15 alkyl groups, C 6～12 alkyl groups or C 7～1 alkyl groups.
For example, the amine compound may be a high molecular weight aliphatic amine and may be a secondary or tertiary amine containing at least two alkyl groups having 5 or more carbon atoms. For example, the amine compound may be at least one selected from the group consisting of di (hexadecyl) amine, tri (hexadecyl) amine, and mixtures thereof.
These amine compounds may be used alone or in combination of two or more.
The amine compound or its derivative is contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the chlorinated polyethylene. The content of the amine compound or its derivative is 0.2 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, or 0.8 parts by weight or more, and 1.9 parts by weight or less, 1.8 parts by weight or less, 1.7 parts by weight or less, or 1.5 parts by weight or less.
Specifically, the vulcanizable chlorinated polyethylene composition of the present invention contains 0.1 to 4 parts by weight of a sulfide-based crosslinking agent or derivative thereof and 0.1 to 2 parts by weight of an amine compound or derivative thereof, based on 100 parts by weight of the above-described chlorinated polyethylene.
(D) Other additives
Meanwhile, the vulcanizable chlorinated polyethylene composition according to the invention blends a sulfide-based crosslinking agent or derivative thereof and an amine compound or derivative thereof with the chlorinated polyethylene, and may further comprise at least one additive, such as an inorganic vulcanization accelerator, for example, a calcium-based inorganic base.
In particular, in the case of additionally comprising one or more additives such as an inorganic vulcanization accelerator, for example, a calcium-based inorganic base containing calcium ions (Ca 2 +), the rate of change of the Mooney Viscosity (MV) is minimized when the vulcanizable chlorinated polyethylene composition is stored for a long period of time, thereby improving extrusion processability.
Specifically, the vulcanizable chlorinated polyethylene composition may include at least one additive selected from the group consisting of calcium stearate ([ CH 3(CH2)16COO]2 Ca), calcium carbonate (CaCO 3), calcium hydroxide (Ca (OH) 2), and calcium oxide (CaO).
These additives may be used alone or in combination of two or more.
Meanwhile, the pH (20 ℃ C., H 2 O) of the calcium-based inorganic base may be 7 to 12, 7.5 to 11 or 8 to 10.
The pH can be measured by a pH titration method or a potentiometric pH meter commonly used in the technical field of the present invention. Specifically, a pH meter having a glass electrode, such as Metter Toleo SevenExellence pH meter, can be used. When the sample is in the form of a solid rather than an aqueous solution, the pH can be measured after mixing 10g of the solid sample in 100g of distilled water followed by stirring for 10 minutes.
The content of the calcium-based inorganic base is 0.1 to 4.5 parts by weight based on 100 parts by weight of the chlorinated polyethylene. When the content of the calcium-based inorganic base is less than 0.1 parts by weight based on 100 parts by weight of the chlorinated polyethylene, agglomeration between CPEs may occur, which may cause problems in subsequent processing, or the change rate of MV may increase due to excessive vulcanization. Further, when the calcium-based inorganic base is used in an amount exceeding 4.5 parts by weight based on 100 parts by weight of the chlorinated polyethylene, the vulcanization performance may be lowered, resulting in a decrease in physical properties of the final product or affecting the change rate or processability of MV. The content of the disulfide-based crosslinking agent or derivative thereof is 0.3 parts by weight or more and 0.4 parts by weight or more and 0.45 parts by weight or more and 0.48 parts by weight or more and 0.5 parts by weight or more and 4.0 parts by weight or less, 3.8 parts by weight or less, 3.5 parts by weight or less, 3.05 parts by weight or less, 2.8 parts by weight or less, 2.5 parts by weight or less, or 2 parts by weight or less.
Specifically, the vulcanizable chlorinated polyethylene composition of the present invention may comprise 0.1 to 4 parts by weight of a sulfide-based crosslinking agent or derivative thereof, 0.1 to 2 parts by weight of an amine compound or derivative thereof, and 0.1 to 4.5 parts by weight of one or more additives selected from the group consisting of calcium stearate, calcium carbonate, calcium hydroxide, and calcium oxide, based on 100 parts by weight of the above chlorinated polyethylene.
At the same time, the vulcanizable chlorinated polyethylene according to the invention is able to minimize the rate of change of MV over time, even when the chlorinated polyethylene composition is stored for a long period of time, thereby improving the processability during extrusion and the excellent strength of the vulcanized product.
Specifically, the rate of change (%) of the mooney viscosity of the vulcanizable chlorinated polyethylene composition with time according to the following equation 1 may be 20% or less, or 0 to 20%.
[ Equation 1]
The rate of change in mooney viscosity over time (%) = [ (MV 2-MV 1)/MV 1] ×100
In the equation 1 of the present invention,
MV1 is the initial Mooney viscosity measured immediately after preparation of the vulcanizable chlorinated polyethylene composition under ML1+4 (125 ℃) conditions according to ASTM D1646, and
MV2 is the Mooney viscosity after aging of the vulcanizable chlorinated polyethylene composition after 2 weeks of storage in an oven at 40℃under ML1+4 (125 ℃) conditions according to ASTM D1646.
The change rate (%) of the mooney viscosity of the vulcanizable chlorinated polyethylene composition according to equation 1 over time is preferably 18% or less, 17% or less, 16.8% or less, 16.5% or less, 16.0% or less, 15.8% or less, or 15.5% or less. However, considering that the mooney viscosity may be greatly increased during long-term storage, the rate of change (%) of the mooney viscosity over time according to equation 1 may be 0.1% or more, 0.2% or more, or 0.3% or more.
At this time, as described above, the initial mooney viscosity (MV 1) of the vulcanizable chlorinated polyethylene composition may be 40MU to 90MU, 43MU to 80MU, 45MU to 75MU, 48MU to 72MU, or 50MU to 70MU, wherein the initial mooney viscosity is measured immediately after mixing the specific disulfide-based crosslinking agent or derivative thereof, amine compound or derivative thereof, and calcium-based inorganic base with the chlorinated polyethylene composition under the condition of ML1+4 (125 ℃) according to ASTM D1646.
In addition, the curable chlorinated polyethylene composition may have a mooney viscosity after aging of 45MU to 100MU, 48MU to 90MU, 50MU to 88MU, 52MU to 85MU, or 53MU to 82MU, wherein the mooney viscosity after aging is measured under ML1+4 (125 ℃) conditions according to ASTM D1646 after storage of the curable chlorinated polyethylene composition in an oven at 40 ℃ for 2 weeks.
For reference, the unit of mooney viscosity is expressed as MU (mooney unit), and the value of ml1+4 is obtained at 125 ℃, where M is mooney, L is the plate size, 1 means preheating for 1 minute, and 4 means reading the value after running the rotor of the mooney viscometer for 4 minutes. Specific measurement methods and conditions are shown in test examples to be described later, and detailed description is omitted.
As described above, the vulcanizable polyethylene composition according to the present invention is characterized in that it maintains high crosslinking efficiency while minimizing the rate of change of Mooney Viscosity (MV) with time even during long-term storage.
Specifically, the initial crosslinking efficiency (MH-ML, dNm) of the vulcanizable chlorinated polyethylene composition may be 6.5dNm to 15dNm, preferably 6.8dNm or more, 7.0dNm or more, 7.5dNm or more, or 7.8dNm or more, and 13.5dNm or less, 11dNm or less, 10dNm or less, 9.0dNm or less, or 8.8dNm or less, when measured under the conditions of a vibration angle of 0.5 degrees, a temperature of 180 ℃ and a duration of 1 hour according to ASTM D5289.
Meanwhile, the vulcanizable polyethylene composition of the invention comprises various compounding agents commonly used in the art, such as fillers, reinforcing agents, plasticizers, stabilizers, anti-aging agents, lubricants, tackifiers, pigments, flame retardants, ultraviolet absorbers, foaming agents, vulcanizing agents, and the like. Further, short fibers or the like may be added to improve strength and rigidity.
In order to obtain the vulcanizable chlorinated polyethylene composition according to the invention, the above compounded materials are kneaded using conventional mixing rolls, van Barry mixers, twin-screw kneading extruders, various kneaders, etc., and then the obtained kneaded product is formed into a desired shape, for example, into a sheet using an open roll, etc. Molding or vulcanization can be performed using a press, extruder, injection molding machine, or the like to obtain a rubber product having a desired shape. The curing conditions are suitably selected in the range of 100 ℃ to 200 ℃ for several minutes to 2 hours.
Vulcanization products
According to another embodiment of the present invention, there is provided a vulcanized product having excellent vulcanization properties obtained by vulcanizing the above-mentioned vulcanizable chlorinated polyethylene composition.
In particular, by vulcanizing a vulcanizable chlorinated polyethylene composition comprising a chlorinated polyethylene prepared using the above polyethylene, which has a molecular structure optimized for the high molecular region, a complex viscosity and melt index MI 5 (measured at 190 ℃ and 5kg load) at high frequencies, and a narrow molecular weight distribution (Mw/Mn), a vulcanized product having excellent strength and improved processability during extrusion is provided.
In order to obtain a laminate or laminate hose having a layer consisting of the vulcanizable chlorinated polyethylene composition, well known conventional lamination methods or extrusion molding techniques can be used. For example, a laminate can be obtained by directly laminating a layer composed of the vulcanizable chlorinated polyethylene composition on a layer composed of epichlorohydrin rubber, nitrile rubber blended with polyvinyl chloride, or acrylate rubber, and vulcanizing the composition. Further, a hose comprising an inner layer composed of epichlorohydrin rubber, nitrile rubber blended with polyvinyl chloride or acrylate rubber and an outer layer composed of the composition for vulcanization is formed, and then the composition is vulcanized to obtain a laminated hose.
Hereinafter, preferred embodiments will be provided to aid in understanding the present invention. However, these examples are for illustrative purposes only and are not intended to limit the invention by these examples.
Examples
Examples 1-1 to 1-3 and comparative examples 1-1 to 1-9
In examples 1-1 to 1-3 and comparative examples 1-1 to 1-9, ethylene was polymerized in the presence of a Ziegler-Natta catalyst to prepare High Density Polyethylene (HDPE) having properties as shown in Table 1 below.
The physical properties of the High Density Polyethylene (HDPE) were measured in the following manner, and the results are shown in table 1 below.
(1) Melt index (MI, g/10 min):
Melt index (MI 5) was measured according to ASTM D1238 at 190℃under a load of 5 kg. The weight (g) of the polymer melted for 10 minutes was recorded as melt index.
(2) Density:
The density (g/cm 3) of each polyethylene was measured according to the ASTM D1505 method.
(3) Complex viscosity of polyethylene (pa·s,500 rad/s):
the complex viscosity of each of the polyethylenes of examples 1 to 2 and comparative examples 1 to 5 was measured using a rotational Rheometer (ARES Rheometer) at 190℃and a frequency (. Omega.) of 0.05rad/s to 500 rad/s.
Specifically, the complex viscosity of each polyethylene was determined by measuring the complex viscosity η (ω0.05) and η (ω500) as a function of frequency using a rotary rheometer ARES (Advanced Rheometric Expansion System, ARES G2) of TA Instruments (NEW CASTLE, delaware). A predetermined amount of polyethylene was injected into the ARES-G2 instrument, 25mm parallel plates and rings, and the gap between the parallel plates having a diameter of 25.0mm was changed to 2.0mm by pressing the upper and lower fixtures at 190 ℃. The measurement is performed in a dynamic strain frequency sweep mode with a strain rate of 5% and a frequency (angular frequency) of 0.05rad/s to 500 rad/s. 10 points were measured for every ten samples, 41 points in total. Wherein the complex viscosity measured at a frequency (ω) of 500rad/s is shown in Table 1 below.
(4) Molecular weight distribution (Mw/Mn, polydispersity index) and Log MW (5.5 above) ratios:
the molecular weight distribution (PDI, mw/Mn) is determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyethylene using gel permeation chromatography (GPC, manufactured by Water), and then dividing the weight average molecular weight by the number average molecular weight.
Specifically, PL-GPC220 manufactured by Waters was used as a Gel Permeation Chromatography (GPC) instrument, and Polymer Laboratories PLgel MIX-B300 mm column was used. The temperature was evaluated at 160℃and 1,2, 4-trichlorobenzene was used as solvent at a flow rate of 1mL/min. Each polyethylene sample was pretreated by dissolving in 1,2, 4-trichlorobenzene containing 0.0125% BHT at 160 ℃ for 10 hours using a GPC analyzer (PL-GP 220), and the sample was provided at a concentration of 10mg/10mL in an amount of 200 μl. Calibration curves formed using polystyrene standards were used to obtain Mw and Mn. 9 polystyrene standards having a molecular weight of 2000g/mol, 10000g/mol, 30000g/mol, 70000g/mol, 200000g/mol, 700000g/mol, 2000000g/mol, 4000000g/mol and 10000000g/mol were used.
In addition, the ratio (%) of the integral value of the region having Log Mw of 5.5 or more to the total integral value in a logarithmic graph (GPC graph having Log Mw on the x-axis and dw/dlogMw on the y-axis) of the weight average molecular weight (Mw) with respect to the polyethylene thus prepared was calculated, and is shown in table 1 below.
TABLE 1
As shown in table 1, it was confirmed in examples that the ratio of the high molecular region in the molecular structure is in the optimum range, the complex viscosity and melt index MI 5 (measured at 190 ℃ and 5kg load) at high frequency are optimized, and the molecular weight distribution (Mw/Mn) is narrow, as compared with comparative examples.
Examples 2-1 to 2-3 and comparative examples 2-1 to 2-9
Chlorinated Polyethylene (CPE) powder was prepared using High Density Polyethylene (HDPE) according to one of examples 1-1 to 1-3 and comparative examples 1-1 to 1-9 as follows, and then a cross-linking agent and co-cross-linking agent/additive were added thereto and mixed to obtain vulcanizable chlorinated polyethylene compositions according to one of examples 2-1 to 2-3 and comparative examples 2-1 to 2-9.
I) Preparation of chlorinated polyethylene
5000L of water and 550kg of the high-density polyethylene prepared in example 1-1 were added to the reactor, and then sodium polymethacrylate as a dispersing agent, vinyl alcohol and allyl alcohol copolyethers as an emulsifying agent, and benzoyl peroxide as a catalyst were added thereto. Then, the temperature was increased from 80 ℃ to 132 ℃ at a rate of 17.3 ℃/hour, and chlorination was performed by injecting gaseous chlorine at the final temperature of 132 ℃ for 3 hours. At this time, the chlorination reaction was performed by injecting gaseous chlorine at a reactor pressure of 0.3MPa while raising the temperature, and the total addition amount of chlorine was 700kg. The chlorinated reaction was neutralized with NaOH for 4 hours, washed again with running water for 4 hours, and finally dried at 120 ℃ to prepare chlorinated polyethylene in powder form.
In addition, the High Density Polyethylene (HDPE) of examples 1-2 to 1-3 and comparative examples 1-1 to 1-9 was also used in the same manner as described above to prepare chlorinated polyethylene in powder form.
II) preparation of chlorinated polyethylene compositions
As described above, 2.25 parts by weight of 5,5' -dithiobis-1, 3, 4-thiadiazole-2 (3H) -thione (manufacturer: vanderbilt Chemicals, LLC, product name: vanax-829) as a crosslinking agent and 0.9 parts by weight of a high molecular weight fatty amine (di (hexadecyl) amine, NH ((CH 2)15CH3)2, manufacturer: vanderbilt Chemicals, LLC, product name: vanax-882B) were mixed with 100 parts by weight of a chlorinated polyethylene powder prepared using a High Density Polyethylene (HDPE) of one of examples 1-1 to 1-3 and comparative examples 1-1 to 1-9, respectively, to obtain vulcanizable chlorinated polyethylene compositions of examples 2-1 to 2-3 and comparative examples 2-1 to 2-9.
The vulcanizable chlorinated polyethylene compositions of examples 2-1 to 2-3 and comparative examples 2-1 to 2-9 prepared as described above were rolled at room temperature to prepare sheet-like samples, and the physical properties of the sheets were measured as follows.
1) Initial Mooney viscosity (MV 1) and Mooney viscosity after aging (MV 2)
The initial Mooney viscosity (MV 1) and the aged Mooney viscosity (MV 2) were measured according to the ASTM D1646 method under ML1+4 (125 ℃).
Specifically, the initial Mooney viscosity (MV 1) was measured immediately after preparing a sheet-like sample using the chlorinated polyethylene compositions of examples and comparative examples as described above. In addition, the sheet thus prepared was stored in an oven at 40 ℃ for 2 weeks, and then MV after 2 weeks of aging was measured and expressed as mooney viscosity (MV 2) after aging. Using the initial mooney viscosity (MV 1) and the aged mooney viscosity (MV 2) measured as described above, the rate of change (%) of the mooney viscosity with time was calculated according to the following equation 1.
[ Equation 1]
The rate of change in mooney viscosity over time (%) = [ (MV 2-MV 1)/MV 1] ×100
In the equation 1 of the present invention,
MV1 is the initial Mooney viscosity measured immediately after preparation of the vulcanizable chlorinated polyethylene composition under ML1+4 (125 ℃) conditions according to ASTM D1646, and
MV2 is the Mooney viscosity after aging of the vulcanizable chlorinated polyethylene composition after 2 weeks of storage in an oven at 40℃under ML1+4 (125 ℃) conditions according to ASTM D1646.
For reference, the unit of mooney viscosity is expressed as MU (mooney unit), and the value of ml1+4 is obtained at 125 ℃, where M is mooney, L is the plate size, 1 means preheating for 1 minute, and 4 means reading the value after running the rotor of the mooney viscometer for 4 minutes.
The initial mooney viscosities (MV 1) and the aged mooney viscosities (MV 2) of the vulcanizable chlorinated polyethylene compositions of examples and comparative examples thus measured, and the change rates (%) of the mooney viscosities over time calculated therefrom are shown in table 2 below.
TABLE 2
As shown in table 2, it was confirmed that the vulcanizable chlorinated polyethylene compositions of examples 2-1 to 2-3, which had a molecular structure with a reduced proportion of high molecular regions, were optimized in viscosity and melt index, and had a narrow molecular weight distribution, and the chlorinated polyethylene compositions according to the invention, which contained chlorinated polyethylenes prepared using the polyethylene of one of examples 1-1 to 1-3, significantly improved the rate of change of mooney viscosity over time (2 weeks), as compared with the comparative examples, to 11.7% to 15.5%.
Claims (18)
1. A polyethylene satisfying the following conditions:
the integrated value in a region where Log MW is 5.5 or more in a GPC chart with Log MW on the x-axis and dw/dlogMw on the y-axis is 14% or less of the total integrated value,
A molecular weight distribution (Mw/Mn) of 5.8 or less,
A complex viscosity (η (ω500)) measured at a frequency (ω) of 500rad/s of 650pa·s to 850pa·s, and
MI 5 (melt index measured at 190 ℃ C. And 5kg load) was 1.2g/10min to 3.0g/10min.
2. The polyethylene of claim 1, wherein the polyethylene is an ethylene homopolymer.
3. The polyethylene according to claim 1, wherein the polyethylene has an integrated value of 0.5% to 14% of the total integrated value in a region having Log MW of 5.5 or more in a GPC diagram having a Log MW in the x-axis and dw/dlogMw in the y-axis.
4. The polyethylene of claim 1, wherein the polyethylene has a molecular weight distribution (Mw/Mn) of 2.0 to 5.8.
5. The polyethylene of claim 1, wherein the polyethylene has a complex viscosity (η x (ω500)) measured at a frequency (ω) of 500rad/s of 700 Pa-s to 820 Pa-s.
6. The polyethylene of claim 1, wherein the polyethylene has a MI 5 (melt index measured at 190 ℃ and 5kg load) of 1.5g/10min to 2.8g/10min.
7. The polyethylene of claim 1, wherein the polyethylene has a MI 21.6 (melt index measured at 190 ℃ and 21.6kg load) of 3g/10min to 33.6g/10min.
8. The polyethylene of claim 1, wherein the polyethylene has a melt flow rate ratio (MFRR 21.6/5, a value obtained by dividing the melt index measured at 190 ℃ and a load of 21.6kg by the melt index measured at 190 ℃ and a load of 5kg according to ASTM D1238) of 2 to 12.
9. The polyethylene of claim 1, wherein the polyethylene has a density of 0.945g/cm 3 to 0.960g/cm 3.
10. A vulcanizable chlorinated polyethylene composition comprising a chlorinated polyethylene prepared by reacting the polyethylene of any one of claims 1 to 9 with chlorine, a sulfide-based crosslinking agent or derivative thereof, and an amine compound or derivative thereof.
11. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the sulfide-based cross-linking agent is a thiadiazole-based compound or a disulfide-based compound.
12. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the sulfide-based cross-linking agent is at least one selected from the group consisting of 2, 5-dimercapto-1, 3, 4-thiadiazole and 5,5' -dithiobis-1, 3, 4-thiadiazole-2 (3H) -thione.
13. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the content of the sulfide-based cross-linking agent or derivative thereof is 0.1 to 4 parts by weight based on 100 parts by weight of the chlorinated polyethylene.
14. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the amine compound comprises at least two C 4～20 alkyl groups.
15. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the amine compound is at least one selected from the group consisting of di (hexadecyl) amine and tri (hexadecyl) amine.
16. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the amine compound or derivative thereof is contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the chlorinated polyethylene.
17. The vulcanizable chlorinated polyethylene composition according to claim 10, wherein the change rate (%) of the mooney viscosity over time calculated according to the following equation 1 is 20% or less:
[ equation 1]
The rate of change in mooney viscosity over time (%) = [ (MV 2-MV 1)/MV 1] ×100
In the equation 1 of the present invention,
MV1 is the initial Mooney viscosity measured according to ASTM D1646 under ML1+4 (125 ℃) immediately after preparation of the vulcanizable chlorinated polyethylene composition, and
MV2 is the Mooney viscosity after aging of the vulcanizable chlorinated polyethylene composition after 2 weeks of storage in an oven at 40℃under ML1+4 (125 ℃) conditions according to ASTM D1646.
18. A chlorinated polyethylene vulcanizate obtained by vulcanizing the composition of claim 10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0159747 | 2021-11-18 | ||
| KR1020220154687A KR20230073130A (en) | 2021-11-18 | 2022-11-17 | Polyethylene and vulcanizable chlorinated polyethylene compositions using the same |
| KR10-2022-0154687 | 2022-11-17 | ||
| PCT/KR2022/018292 WO2023090931A1 (en) | 2021-11-18 | 2022-11-18 | Polyethylene and vulcanizable chlorinated polyethylene composition using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117980351A true CN117980351A (en) | 2024-05-03 |
Family
ID=90848145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280063075.7A Pending CN117980351A (en) | 2021-11-18 | 2022-11-18 | Polyethylene and vulcanizable chlorinated polyethylene composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117980351A (en) |
-
2022
- 2022-11-18 CN CN202280063075.7A patent/CN117980351A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101072826B (en) | Peroxide vulcanizable butyl compositions useful for rubber articles | |
| KR101678049B1 (en) | Thermoplastic elastomer composition and use thereof | |
| EP3458515B1 (en) | Rubber composition | |
| CA2750903A1 (en) | Processing additive, molding composition, masterbatch of processing additive and molding article | |
| US4624989A (en) | Thermoplastic elastomers containing cross-linked epihalohydrin rubbers | |
| CN117980351A (en) | Polyethylene and vulcanizable chlorinated polyethylene composition using the same | |
| KR20230073130A (en) | Polyethylene and vulcanizable chlorinated polyethylene compositions using the same | |
| KR100477345B1 (en) | Process for preparing thermoplastic elastomer composition | |
| JP2018119097A (en) | Rubber composition for automobile aqueous hose | |
| JPS614745A (en) | Rubber composition | |
| CN114901448A (en) | Polymer blends | |
| JP2983623B2 (en) | Thermoplastic elastomer based on ethylene / acrylate copolymer and polynorbornene | |
| KR20230075201A (en) | Vulcanizable chlorinated polyethylene compositions and vulcanized products using the same | |
| JP3800797B2 (en) | Chlorinated polyolefin | |
| KR20230073597A (en) | Vulcanizable chlorinated polyethylene compositions and vulcanized products using the same | |
| JP3364999B2 (en) | Rubber composition with excellent extrusion processability | |
| JPS60219244A (en) | Chlorinated polyethylene composition | |
| KR20230075910A (en) | Chlorinated polyethylene composition and vulcanizable chlorinated polyethylene composition comprising the same | |
| JPH01263038A (en) | Rubber belt | |
| WO2024116768A1 (en) | Polymer, rubber composition, and crosslinked rubber composition | |
| JP2902781B2 (en) | Thermoplastic composition having elastic memory and method for producing the same | |
| CN115058079A (en) | Preparation method of flame-retardant polypropylene | |
| JP2021143222A (en) | ETHYLENE/α-OLEFINE/NONCONJUGATED POLYENE COPOLYMER COMPOSITION AND ITS APPLICATION | |
| JPH0535739B2 (en) | ||
| JPH045692B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |