CN1313528C - Polyethylene compositions for rotational molding - Google Patents
Polyethylene compositions for rotational molding Download PDFInfo
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- CN1313528C CN1313528C CNB038235455A CN03823545A CN1313528C CN 1313528 C CN1313528 C CN 1313528C CN B038235455 A CNB038235455 A CN B038235455A CN 03823545 A CN03823545 A CN 03823545A CN 1313528 C CN1313528 C CN 1313528C
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Abstract
Polyethylene blend compositions suitable for injection molding, injection molded articles, and processes for injection molding articles are provided. The polyethylene compositions include a first polyethylene having a melt index of 0.1 to 3.0 g/10 min and a density of from 0.905 to 0.938 g/cm<3>; and a second polyethylene having a melt index of 10 to 500 g/10 min and a density of 0.945 to 0.975 g/cm<3>. The composition has a density of from 0.920 to 0.973 g/cm<3> and a melt index of 2 to 200 g/10 min, and the density of the second polyethylene is from 0.037 to 0.062 g/cm<3> greater than the density of the first polyethylene. These compositions exhibit improved physical properties, such as Environmental Stress Crack Resistance, relative to conventional compositions of similar melt index and density.
Description
1. the cross reference of related application
[0001] the present invention's rights and interests of 60/424535 of requiring the U.S. Provisional Application No.60/414952 that submitted on October 1st, 2002 and submitting on November 7th, 2002.
2. invention field
[0002] the present invention relates to the thermoplastic compounds of polyethylene polymer, it is suitable for making useful products by rotational molding.
3. background technology
[0003] rotational molding or rotational casting more often are called rotational moulding, are widely used in the molding hollow piece and have both can be used for the molding small vessels, can be used for the molding large container again, as typically are the jar of 19L-57000L.This rotational molding jar is used for agricultural, chemistry and recreational vehicle industry.The rotational molding container is used for packing and material processing, especially as fluid or solid vessel prepd.Rotational molding also is used for shell, toy and the refuse receptacle of portable toilet, instrument and battery case, lampshade, vacuum cleaner and washer.Compare with other known method, this technology is relatively so expensive and be used for polymer processing and its easily and use day by day and increase.
[0004] for the rotational molding parts, the atomizing fluoropolymer resin is incorporated in the mould crust, typically rotation and heating on two axles causes that molten resin is adhered to mould inside then.After competent heat-up time, mould is moved on in the cooling chamber and after cooling, take out molded parts, begin another molding cycle.Can be in Modern Plastics Encyclopedia 1990, the 317-318 pages or leaves and at Encyclopedia of Polymer Science andEngineering (polymer science and engineering encyclopedia), 659-670 page or leaf (J.Wiley ﹠amp; Sons, 1990) find the more detailed argumentation of rotational molding in.
[0005] rotational molding mainly uses polyolefin resin, wherein mainly uses the thermoplastic polymer of ethene.The key property of rotational molding parts comprises outward appearance and particularly under the situation of container, endurable hole or fracture, chemicals-resistant and through the effective anti-environmental stress cracking of long-time section.Density is the about 0.925g/cm of about 0.900-
3New LDPE (film grade) (LDPE), density be the about 0.940g/cm of about 0.926-
3Linear low density polyethylene (LLDPE), density be the about 0.960g/cm of about 0.940-
3High density polyethylene(HDPE) (HDPE) be used to during rotational molding uses.It is said preferred LLDPE, because it has good low temperature impact strength and good anti-environmental stress cracking (" ESCR ").
[0006] composition of polyvinyl resin has been proposed to improve physicals, comprising shock strength, anti-environmental stress cracking and chemical-resistant.U.S. Patent No. 4438238 discloses the blend that is used for extrusion molding processing, injection moulding and film, and wherein the binding substances of the different two kinds of ethene-alpha-olefin copolymers of the short-chain branched number of density, intrinsic viscosity and per 1000 carbon atoms provides this physicals.U.S. Patent No. 4461873 discloses in the manufacturing of film, perhaps in blow molding technology, available high molecular weight ethylene polymkeric substance in the coating of the production of tubing and electric wire, preferred copolymer, and low-molecular ethylene polymers, the optimal ethylene homopolymer, polyvinyl blend, to be used for improved film properties and anti-environmental stress cracking.EP0423962 discloses the ethylene polymer composition that is particularly useful for gas pipeline, described composition allegedly has improved anti-environmental stress cracking, it comprises two or more ethene polymerss that molecular-weight average is different, wherein at least a be under 135 ℃ in naphthalane intrinsic viscosity be that 4.5-10.0dl/g and density are 0.910 to 0.930g/cm
3The high molecular weight ethylene polymkeric substance, be that the intrinsic viscosity of measuring as first kind of polymkeric substance is that 0.5-2.0dl/g and density are 0.938-0.970g/cm with another kind
3Low-molecular-weight ethene polymers.
[0007] U.S. Patent No. 5082902 discloses the blend of the linear polyethylene that is used for injection moulding and rotational molding, and described blend allegedly has crystallization time and the improved shock strength and the ESCR of reduction.This blend comprises: (a) density is 0.85-0.95g/cm
3With MI be first polymkeric substance of 1-200g/10min; (b) density is than first kind of big 0.015-0.15g/cm of density polymer
3Be not more than 50% second polymkeric substance with difference with the MI of first kind of polymkeric substance.U.S. Patent No. 5306775 discloses polyethylene blend, and described blend allegedly has the equilibrated performance, for by any known thermoplastic process processing, wherein comprises improved anti-environmental stress cracking especially.These compositions have: (a) use chromium oxide-based catalyst manufacturing and density to be 0.955g/cm at least
3And melt index (MI) is between 25 to 400g/10min low molecular weight ethylene resins; (b) density is not higher than 0.955g/cm
3With high capacity melt index (HLMI) between 0.1 to 50g/10min high molecular weight ethylene copolymer resin.
[0008] U.S. Patent No. 5382631 narrow molecular weight distribution (Mw/Mn≤3) is disclosed and/or form to distribute (CDBI) less than the interpolymer polyethylene blend of 50% linearity, wherein this blend does not contain usually than other blend component molecular weight height and the low part of average comonomer content.The improvement performance that is used for film, fiber, coating and moulded parts is owing to this blend.In one embodiment, first component is that density is 0.9042g/cm
3, Mw/Mn be 2.3 and MI be that the ethylene-butene copolymer and second component of 4.0g/10min is that density is 0.9552g/cm
3, Mw/Mn be 2.8 and MI be the HDPE of 5.0dg/min.This blend allegedly has improved tear strength characteristics.
[0009] U.S. Patent No. 6362270 discloses a kind of thermoplastic compounds that rotational molding is used that allegedly is particularly suitable for, and it comprises: (a) main ingredient, described main ingredient can be that density is greater than 0.915g/cm
3Be the ethenyl copolymer of about 2-500g/10min and (b) shock resistance additive with preferred melt index, described shock resistance additive can be that density is less than 0.915g/cm
3Be preferably greater than 0.05g/10min with melt index and less than the ethenyl copolymer of 100g/10min.Improvement physicals owing to these compositions comprises improved shock strength and good ESCR.
[0010] continues to have the composition on the polyethylene basis of improved environmental stress crack resistance and shock strength, be particularly suitable for rotational molding uses those.
4. summary of the invention
[0011], provides the method that is suitable for rotational molding based on polyolefinic blend composition, rotation molded articles and rotation molded articles according to the present invention.
[0012] in one embodiment, the invention provides a kind of polyethylene composition, it comprises that melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3First polyethylene; With melt index be that 10-30g/10min and density are 0.945-0.975g/cm
3Second polyethylene, wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min and wherein first polyethylene and the second poly density difference are 0.030-0.048g/cm
3
[0013] in another embodiment, the invention provides a kind of polyethylene composition, it comprises that melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3The polyethylene of first metallocene catalysis; With melt index be that 10-30g/10min and density are 0.945-0.975g/cm
3The polyethylene of second metallocene catalysis, wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min and wherein first polyethylene and the second poly density difference are 0.030-0.048/cm
3
[0014] in another embodiment, the invention provides and a kind ofly form or comprise the rotation molded articles of polyethylene composition by polyethylene composition, this polyethylene composition comprises that melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3First polyethylene; With melt index be that 10-30g/10min and density are 0.945-0.975g/cm
3Second polyethylene, wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min and wherein first polyethylene and the second poly density difference are 0.030-0.048g/cm
3
[0015] in another embodiment, the invention provides and a kind ofly form or comprise the rotation molded articles of polyethylene composition by polyethylene composition, this polyethylene composition comprises that melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3The polyethylene of first metallocene catalysis; With melt index be that 10-30g/10min and density are 0.945-0.975g/cm
3The polyethylene of second metallocene catalysis, wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min and wherein first polyethylene and the second poly density difference are 0.030-0.048g/cm
3
[0016] in another embodiment, the invention provides the method that forms rotation molded articles, this method is undertaken by following step: polyethylene composition (a) is provided, and this polyethylene composition comprises that melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3First polyethylene; With melt index be that 10-30g/10min and density are 0.945-0.975g/cm
3Second polyethylene, wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min and wherein first polyethylene and the second poly density difference are 0.030-0.048g/cm
3(b) the rotational molding said composition forms rotation molded articles.
[0017] in another embodiment, the invention provides the method that forms rotation molded articles, this method is undertaken by following step: polyethylene composition (a) is provided, and this polyethylene composition comprises that melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3The polyethylene of first metallocene catalysis; With melt index be that 10-30g/10min and density are 0.945-0.975g/cm
3The polyethylene of second metallocene catalysis, wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min and wherein first polyethylene and the second poly density difference are 0.030-0.048g/cm
3(b) the rotational molding said composition forms rotation molded articles.
[0018] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or forming the method for rotation molded articles, the ratio of the Mw/Mn of each that different is in first and second polyethylene is 1.4-4.0.
[0019] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or forming the method for rotation molded articles, the ratio of the Mw/Mn of each that different is in first and second polyethylene is 1.8-3.5.
[0020] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, different is that the first poly density is 0.911-0.926g/cm
3
[0021] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, different is that the second poly density is 0.950-0.970g/cm
3
[0022] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, different is that the second poly density is 0.955-0.965g/cm
3
[0023] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, the density of different is composition is 0.932-0.950g/cm
3
[0024] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, the density of different is composition is 0.935-0.945g/cm
3
[0025] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, different is that the first and second poly density differences are 0.032-0.045g/cm
3
[0026] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, different is that the first and second poly density differences are 0.035-0.042g/cm
3
[0027] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, that different is the melt index I of composition
2.16Be 2-10g/10min.
[0028] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or the method for formation rotation molded articles, wherein based on the first and second poly gross weights, this blend comprises 80wt%-20wt% first polyethylene and 20wt%-80wt% second polyethylene.
[0029] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or the method for formation rotation molded articles, wherein based on the first and second poly gross weights, this blend comprises 65wt%-35wt% first polyethylene and 35wt%-65wt% second polyethylene.
[0030] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or the method for formation rotation molded articles, wherein based on the first and second poly gross weights, this blend comprises 55wt%-45wt% first polyethylene and 45wt%-55wt% second polyethylene.
[0031] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, wherein the ESCR value of composition is 250hr at least.
[0032] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, wherein the ESCR value of composition is 500hr at least.
[0033] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, wherein the ESCR value of composition is 750hr at least.
[0034] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, wherein the ESCR value of composition is 1000hr at least.
[0035] in another embodiment, the invention provides polyethylene composition, rotation molded articles, or form the method for rotation molded articles, wherein for the sample of 3.17mm according to aforementioned any embodiment, under-40 ℃, the izod impact strength of composition is 120kJ/m at least.
[0036] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to aforementioned any embodiment, or form the method for rotation molded articles, wherein at least a in first and second polyethylene is the blend of two or more polyvinyl resins.
[0037] in another embodiment, the invention provides polyethylene composition, rotation molded articles according to the aforementioned any embodiment except the last embodiment of closelying follow, or the method for formation rotation molded articles, wherein said composition only comprises first and second polyethylene except also can having conventional additives in a small amount.
5. accompanying drawing summary
[0038] Fig. 1 is differential scanning calorimetric (DSC) chart of the polymer melting temperature of two kinds of blend compositions.Solid line represents that blend of the present invention (3a-b in the table 1) and dotted line represent the blend (5a-b in the table 1) of comparison.
6. describe in detail
[0039] as mentioned above, former research work usually concentrates on film and the blow molding applications. Therefore, existing research usually relates to the machining feature of the transparency of film, endurable permeability and film processing, such as extrusion molding and blown film processes. Also usually relate to the improvement of ESCR for the blended polyethylene that is used for this application, particularly blow molding applications. Yet prior art does not provide the polyethylene blend compositions for the know-how of rotational molding and specific product requirement. Composition of the present invention astoundingly and advantageously provide improved ESCR and significantly improved izod impact strength, thereby improve the total value of the present composition.
[0040] by preparing several samples of the blended polyethylene component that proposes, then make the blend undergoing analysis test by they preparations, measured difference and melt index (MI) (I when the density of blend component2.16) obtained the ESCR peak value herein in the described specific scope time. At the density contrast of two kinds of components more hour, with respect to the composition of one-component, ESCR is improved, but obviously not as in present composition scope those. Increase within the scope of the invention the density range width between each component, can increase the improvement of ESCR, until reach the peak value that ESCR wherein no longer improves and begins to reduce. Help to illustrate wherein with the melting peak of differential scanning calorimeter (DSC) sample survey blend and no longer realize the improved zone of ESCR by increasing by two kinds of density contrasts between the component. This is by further increasing the width of density range, and the two kinds of components no longer fully point during cocrystallization represent that this is by existing second lower melting peak value to prove in the DSC scintigram. When density range was wider than above-mentioned scope, the evidence of cocrystallization forfeiture became obviously, because second melting peak or acromion begin to occur in scintigram. Demonstrate even ESCR that the blend of minimum second acromion incidence has a minimizing improves, referring to Fig. 1 and table 1.
[0041] linear low density polyethylene copolymers that mainly to be ethene obtain with the coordination polymerization of one or more copolymerisable monomers in a small amount of serving as reasons of the first polyethylene in the blend polymer of the present invention. Use has Narrow Molecular Weight Distribution (Mw/Mn, or MWD), for example Mw/Mn is for from 1.4 or 1.8 or 2.0 the lower this copolymer that is limited to 4.0 or 3.5 or 3.0 the upper limit, can obtain especially improved end product performance, wherein can take in to the scope any upper limit from any lower limit. Suitable comonomer comprises C3-C
20Alpha-olefin, preferred C3-C
8、C
5-C
20Cycloolefin, preferred C7-C
12Cycloolefin, C7-C
20Vi-ny l aromatic monomers, optimization styrene, and C4-C
20Together with disubstituted olefin, preferred isobutene. Most preferred comonomer comprises propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene. Mainly measure the density of copolymer by the content of comonomer, and typically scope is 0.910 or 0.911g/cm3To 0.930 or 0.926g/cm3, wherein can take in to the scope any upper limit from any lower limit. Can have a certain amount of long chain branch, but density limits mainly because of due to the existence of comonomer. These ethylene copolymers have than the high molecular weight of the second polyethylene in the blend, and this passes through according to ASTM D 1238,190 ℃ of conditions, its melt index (MI) I that 2.16kg (condition in the past " E ") measures2.16Represent to about 3.0g/10min for about 0.4. This molecular weight ranges approaches the intrinsic viscosity (in naphthalane, under 135 ℃) that is equivalent to the about 1.7dl/g of about 1.2-.
[0042] the second polyethylene in the blend polymer of the present invention is that Mw/Mn is similar to the first polyethylene, be that Mw/Mn is the lower high density polyethylene (HDPE) that is limited to 4.0 or 3.5 or 3.0 the upper limit from 1.4 or 1.8 or 2.0, wherein can take in to the scope any upper limit from any lower limit. It is derived from ethene and in a small amount above for the cited any comonomer of the first polyethylene randomly. Density can be 0.945 or 0.950 or 0.955g/cm3Be limited to 0.975 or 0.970 or 0.965g/cm down3The upper limit, wherein can take in to the scope any upper limit from any lower limit. Lower molecular weight passes through according to ASTM D 1238,190 ℃ of conditions, the melt index (MI) I that 2.16kg measures2.16For 10-150g/10min represents. This molecular weight ranges approaches the intrinsic viscosity (in naphthalane, under 135 ℃) that is equivalent to the about 1.2dl/g of about 0.9-. The second poly melt index (MI) I2.16Scope can be from 10 12 or 14g/10min lower be limited to 150 or 100 or 50 or the upper limit of 30g/10min, wherein can take in to the scope any upper limit from any lower limit.
[0043] commercial run of production polyethylene component of the present invention is well known in the art, as what exemplify in the above list of references of quoting. Any this method that can produce polyethylene polymer component of the present invention is suitable. This method or comprise separately or in combination gas phase, liquid phase (or solution) and slurry phase polymerisation technique. Just independent, can mention in single-reactor or greater than series connection or serial production in the reactor. The blend of reactor also is suitable, as by make the polymerizing condition of spent mixed catalyst or mixing in single-reactor. In view of economic advantages, gas-phase polymerization is especially suitable. This technique is used the catalyst of carrying, and in polymer reactor, carries out being suitable for preparing by coordination polymerization under the gas phase condition of linear low density ethylene copolymer. Can United States Patent(USP) Nos. 4543399,4588790,5028670,5352749,5382638,5405922,5422999,5436304,5453471,5462999 and 5463999 and International Application No. WO 94/28032, WO95/07942 and WO96/00245 in find the example that exemplifies. These techniques are used or traditional ziegler natta catalyst or be characterized by and have the basically organo-metallic catalyst afterwards of single congruent point (this is because on metal center or due to the arrangement of the assistant ligand around it). Metallocene catalyst is the representative of " single-point catalyst ", and in the present invention, because of the polyolefinic ability of its production Narrow Molecular Weight Distribution, is preferred therefore. Typically under about-100 ℃ to 150 ℃, more typically under about 40 ℃ to 120 ℃, at maximum about 7000kPa, typically carry out this technique under the pressure from about 690kPa to 2415kPa. Preferred use fluid bed and recycle stream are as the continuous processing of fluidizing agent.
[0044] slurry polymerization processes is suitable for this two kinds of components, and is particularly suitable for high-density component of the present invention. These techniques typically are described to wherein, and polymerisation medium can be or liquid monomer, such as propylene, perhaps hydrocarbon solvent or diluent advantageously are aliphatic paraffin such as propane, iso-butane, hexane, heptane, cyclohexane etc., or those techniques of aromatic substances such as toluene. Slurry solids typically comprises the polymer of formation and the catalyst of inert carrier-supported. Catalyst typically is ziegler natta catalyst, and/or one or more single-point catalysts, such as metallocene. Polymerization temperature can be to think lower those, for example less than 50 ℃, typically is 0 ℃ to 30 ℃, perhaps can be in higher scope, such as about 150 ℃ at most, typically from 50 ℃ to about 80 ℃, perhaps in any scope between pointed end points. Pressure can change to about 700psia (0.76-4.8MPa) from about 100. In United States Patent(USP) Nos. 4182810,5274056,6319997,6380325,6420497, WO94/21962 and WO99/32531, provided extra explanation.
[0045] based on the first and second poly gross weight, polyethylene blend compositions of the present invention can comprise consumption from 20 35 or 45wt% lower be limited to 80 or 65 or the first polyethylene of the upper limit of 55wt%, wherein can take in to the scope any upper limit from any lower limit. Similarly, based on the first and second poly gross weights, polyethylene blend compositions of the present invention can comprise consumption from 20 35 or 45wt% lower be limited to 80 or 65 or the second polyethylene of the upper limit of 55wt%, wherein can take in to the scope any upper limit from any lower limit.
[0046] in addition, one of the first polyethylene and second polyethylene or the two can be two or more poly secondary blends (sub-blend), as long as this secondary blend has performance described herein.
[0047] although explanation herein concentrates on the first and second polyethylene, but in some embodiments, polyethylene blend composition can further comprise extra polymers compositions, and comprising extra polyethylene, condition is that total blend composition has cited performance.
[0048] herein the percetage by weight of the first and second cited polyethylene components based on the gross weight (100%) of the first and second polyethylene components.
[0049] density of this blend is from 0.930 or 0.932 or 0.935g/cm3Be limited to 0.955 or 0.950 or 0.945g/cm down3The upper limit, wherein can take in to the scope any upper limit from any lower limit.
[0050] this blend can have from 0.030 or 0.032 or 0.035g/cm3Be limited to 0.048 or 0.045 or 0.042g/cm down3The first and second poly density contrasts of the upper limit, wherein can take in to the scope any upper limit from any lower limit.
[0051] melt index (MI) of blend can be from 1.5 or 2.0g/10min lower be limited to 12 or 10 or the upper limit of 8g/10min.
[0052] polyethylene blend compositions of the present invention demonstrates greater than 250 or greater than 500 or greater than 750 or greater than the ESCR value of 1000hr.
[0053] polyethylene blend compositions of the present invention demonstrates the notched izod impact value (40 ℃, the sample of 3.17mm thickness) greater than 120kJ/m.
[0054] can optionally use additive. Typical additive comprises one or more antioxidants, antistatic additive, UV stabilizing agent, blowing agent, processing aid, nucleator, nano composite material, fibre reinforced materials and pigment. The pigment that exemplifies or colouring agent comprise titanium dioxide, carbon black, cobalt aluminum such as cobalt blue, and chromium oxide such as chrome oxide green. Pigment such as ultramarine blue (it is a kind of silicate). Phthalocyanine blue and iron oxide red also are suitable. Based on the gross weight of the first and second polyethylene components, typically use these with 0wt% to the consumption that is not more than about 15wt%.
[0055] according to the present invention, the resin blend of the foregoing polyolefin base of rotational molding. For this reason, extrudable blend contains or does not contain resin, the granulation of additive and is ground into powder, and typically 35U.S. order (500 microns) this means that particle mean size typically is 60U.S. order (250 microns). Suitable extrusion molding blending temperature typically is about 190-210 ℃. Afterwards, powder is placed in the mould of hollow, described hollow mould is typically in the rotation of two axles and heat in baking oven. In the rotational molding process, under the temperature of the thermoplasticity composition that is enough to the melting powder blend, through the time enough heating powder. Employed time and temperature depend on following factor, and comprising the heat sensitivity of thickness He each composition of the parts that are rotated molding, and skilled those skilled in the art can easily determine suitable processing conditions. In the time of on being applied to polyethylene resin blend of the present invention, the component thickness of about 1/8 ＂ (0.3175cm), setting range are that the oven temperature of about 550 -650 (287.8-343.3 ℃) will typically provide sufficient melting condition through about 10-20 minute.
7. embodiment
[0056] according to ASTM D-256, method A carries out the notched izod test.
[0057] gel permeation chromatography (GPC) that is also referred to as size exclusion chromatography (SEC) be can use, Mz, Mw and Mn measured.This technology utilization comprises the instrument of pillar, eluting solvent and the detector of filling with porous bead, in order that the polymer molecule of separation different size.In typical the measurement, employed GPC instrument is the Waters chromatogram of being furnished with at 145 ℃ of ultrastyro gel columns of operating down.Employed eluting solvent is a trichlorobenzene.Use accurately 16 kinds of polystyrene standards of known molecular amount to proofread and correct this post.The polystyrene retention volume that is obtained by this standard substance and the corresponding relation of the retention volume of the polymkeric substance of being tested obtain the molecular weight of polymkeric substance.
[0058] can calculate molecular-weight average M by following expression formula:
N wherein
iBe to have molecular weight M
iMolecule number.When n=o, M is number-average molecular weight Mn.When n=1, M is weight-average molecular weight Mw.When n=2, M is Z-average molecular weight Mz.Required MWD function (for example Mw/Mn or Mz/Mn) is the ratio of corresponding M value.The measurement of M and MWD is well known in the art and is discussed in for example Slade in more detail, P.E.Ed., PolymerMolecular Weights Part II, Marcel Dekker, Inc., NY, (1975) 287-368; Rodriguez, F., Principles of Polymer Systems 3rd ed., HemispherePub.Corp., NY, (1989) 155-160; U.S. Patent No. 4540753; Verstrate etc., Macromolecules, vol.21, (1988); In each reference of herein quoting.
[0059] according to ASTM D 1693, condition B, 10%IGEPAL
TM, measure anti-environmental stress cracking (ESCR) (curved bar).IGEPAL
TMBe available from Rhone Polenc, Cranbury, the Nonylphenoxy of NJ gathers (vinyloxy group) ethanol tensio-active agent.All ESCR values of herein enumerating are ASTM D1693 condition B, 10%IGEPAL
TMThe F50 value, and hour being that unit provides.
[0060] use compression moulded samples, according to ASTM D 1505-68 and ASTM D1928, program C cools off and at room temperature nursed one's health 40 hours, mensuration density polymer (g/cm with 15 ℃/hour
3).
[006] can be according to ASTM D-1238,190 ℃ of melt flow rate of measuring polymkeric substance down.I
21.6Be according to ASTM D-1238, " flow index " or the melt flow rate of the polymkeric substance that 190 ℃ of conditions, 21.6kg measure, and I
2.16Be according to ASTM D-1238, " melt index " or the melt flow rate of the polymkeric substance that 190 ℃ of conditions, 2.16kg measure.I
21.6With I
2.16Ratio be " melt flow than " or " MFR ".Melt flow rate I
21.6Sometimes be also referred to as " high capacity melt index " or HLMI.Melt flow rate is with unit gram/10 minutes (g/10min) or suitable decigram/minute (dg/min) reports.
Embodiment 1-3, Comparative Examples 1-5
[0062] prepares the embodiment shown in the table 1 according to the embodiment in the U.S. Patent No. 5382631 usually, except indicating in addition.In the Gas-phase reactor that about 185 (85 ℃) operate down, on silica support, use aikyiaiurnirsoxan beta activatory zirconocene, the methylaluminoxane of 12wt% and the zirconium of 3.5wt% are as polymerizing catalyst, wherein gas phase is made up of for nitrogen 70 volume % ethene, 0.5-2.0 volume % hexene, 200-800ppm hydrogen and all the other.Production about 50-75 pound (22.6-33.9kg) in each aggregation test/hour.
[0063] table 1 shows at embodiment 1a-b in 3a-3b and the invention of Comparative Examples Comp1-Comp5a-b.Each " a " row shows first polyethylene component, and each " b " row shows second polyethylene component." Δ density " row provide the density difference for two kinds of components of each blend of listing.Comp1 shows the single polyethylene component relatively that supplies in typical density and melt index range for the rotational molding composition.Comp2 shows for blend relatively, and wherein the melt index of two kinds of components makes difference less than 0.030g/cm near equating with density
3, but average identical with Comp1.Comp3 shows for blend relatively, and wherein high-molecular weight first has the density identical with Comp1 separately with low-molecular-weight second polyethylene.Comp4 shows for blend relatively, and wherein density is identical, but the molecular weight of higher molecular weight part and blend composition increases.Comp5 shows for blend relatively, and wherein the density of high-molecular weight first polyethylene component is lower than 0.910g/cm
3It is evident that very embodiments of the invention have good ESCR separately and each Comparative Examples does not all have.
Table 1
| Embodiment | wt％ | Melt index I 2.16 (g/10min) | Density (g/cm 3) | Δ density (g/cm 3) | Mw/Mn | ESCR，F 50 (hr) |
| 1a 1b 1a/1b blend | 48.4 51.6 100 | 0.86 14.0 2.7 | 0.919 0.950 0.935 | 0.031 | 2.43 3.34 | ＞1000 |
| 2a 2b 2a/2b blend | 45 55 100 | 0.86 14.0 3.1 | 0.919 0.950 0.936 | 0.031 | 2.43 3.34 | ＞1000 |
| 3a 3b 3a/3b blend | 38.5 61.5 100 | 0.46 14.0 2.9 | 0.911 0.950 0.935 | 0.039 | 2.50 3.34 | ＞1000 |
| Comp1 | 100 | 3.05 | 0.935 | 2.82 | ＜220 | |
| Comp2a Comp2b Comp2a/2b blend | 55.5 45.5 100 | 3.0 2.88 3.0 | 0.947 0.920 0.935 | 0.027 | 2.87 2.43 | ＜180 |
| Comp3a Comp3b Comp3a/3b blend | 58 42 100 | 0.97 14 3.0 | 0.934 0.934 0.934 | 0 | 2.93 2.58 | ＜250 |
| Comp4a Comp4b Comp4a/4b blend | 48 52 100 | 3.0 14 7.6 | 0.935 0.934 0.935 | 0.01 | 2.82 2.58 | ＜100 |
| Comp5a* Comp5b Comp5a/5b blend | 30 70 100 | 1.2 14 7.6 | 0.900 0.950 0.935 | 0.050 | 2.0 3.34 | ＜100 |
* commercial hexene plastomer (Exact based on ethene
TM3132, ExxonMobilChemical)
[0064] Fig. 1 further shows, Comparative Examples 5a-b (dotted line) locates to demonstrate double melting peaks by DSC at 95.9 ℃ and 127.7 ℃.Embodiment of the invention 3a-b (solid line) locates to demonstrate single melt temperature at 128.4 ℃.The embodiment of these two comparisons has identical density (identical density is the sign of suitable basically average comonomer content), but only realizes cocrystallization effectively under the situation that adopts blend of the present invention.
Embodiment 4-5, Comparative Examples 6
[0065] prepares the embodiment 4 and 5 of table 2 by melt blending two kinds of selected components of the present invention.Employed high-molecular weight first polyethylene is the hexene copolymer (Exceed of commercial membranes level based on ethene
TM1023CA, ExxonMobil Chemical Company), with in the commercial slurry loop reactor of ExxonMobilChemical, use zirconocene with methylaluminoxane activatory silica supported, producing under the employed condition of high density polyethylene(HDPE), produce low-molecular-weight second polyethylene.The blend of table 2 and Comparative Examples comprise the additive near a great deal of: Irganox in addition
TM3114 main anti-oxidants (CIBA); Irgafos
TM168 antioxidants (CIBA); And acid neutralizing agent (Zinic stearas, or Equivalent).Below show the two density, melt index I
2.16And Mw/Mn.Comp6 is a Comparative Examples, and it has illustrated the performance of the commercial single component LLDPE resin of selling for the rotational molding application and has been described as having good ESCR and toughness.Embodiment 4 and 5 demonstrates low high capacity melt index I in addition
21.6, ASTM-D1238 (190 ℃, 21.6kg), its numerical value respectively does for oneself 17.9, and by contrast, the numerical value of Comp6 sample is 82.5.
[0066] as seen from Table 2, compare with composition relatively, ESCR and notched izod performance all demonstrate significant improvement.The embodiment of the invention 4 and 5 ESCR value are reported as＞288hr, because test stops when 288hr.Can expect reasonably that total performance will be complementary with the sample of the present invention of table 1, if the words of equally long time period are carried out in test.The outer data of the amount of income show, compare with composition relatively, and blend of the present invention demonstrates improved astoundingly ARM (dropping hammer) shock strength, modulus in flexure and tensile break stress in the table 2.
Table 2
| Embodiment | wt％ | Melt index I 2.16(g/10min) | Density (g/cm 3) | Δ density (g/cm 3) | Mw/Mn | ESCR，F 50 (hr) | Notched izod-40 ℃ | |
| (ft-lb/in) | (kJ/m) | |||||||
| 3.17mm** | 6.35mm** | |||||||
| 4a 4b 4a/4b blend | 55 45 100 | 1.0 21.2 3.0 | 0.923 0.958 0.939 | 0.035 | 2.9 2.7 3.2 | ＞288 | 2.58 137.8 | 1.62 86.5 |
| 5a 5b 5a/5b blend | 45 55 100 | 1.0 21.2 3.7 | 0.923 0.958 0.942 | 0.035 | 3.1 3.1 | ＞288 | 1.97 105.2 | 1.5 80.1 |
| Comp6* | 100 | 3.3 | 0.939 | 3.6 | 52 | 1.94 103.6 | 1.20 64.1 | |
* the commercial LLDPE of ethene and hexene (LL8460, ExxonMobil Chemical)
The * thickness of sample
[0067] extensive stock name as used herein is with symbol
TMExpression, it shows that these titles can be subjected to the protection of some trade mark privileges.In various authorities, some such titles also can be the registrar entitling.
[0068] all patents of herein quoting, testing sequence and other document comprising priority documents, are all introduced for referencely, and it is that disclosed content is not inconsistent with the present invention with reference to degree, and is used to allow all authorities of this introducing.
Claims (45)
1. polyethylene composition, it comprises:
(a) melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3First polyethylene; With
(b) melt index is that 10-30g/10min and density are 0.945-0.975g/cm
3Second polyethylene,
Wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min, and wherein the first and second poly density differences are 0.030-0.048g/cm
3, and be 20-65wt% based on the first and second poly gross weight second poly weight percentage wherein.
2. the composition of claim 1, wherein at least a in first and second polyethylene is the polyethylene of metallocene catalysis.
3. the composition of claim 1, wherein first and second polyethylene are polyethylene of metallocene catalysis.
4. the composition of claim 1, wherein each the ratio of Mw/Mn of first and second polyethylene is 1.4-4.0.
5. the composition of claim 4, the ratio of wherein said Mw/Mn is 1.8-3.5.
6. the composition of claim 1, wherein the first poly density is 0.911-0.926g/cm
3
7. the composition of claim 1, wherein the second poly density is 0.950-0.970g/cm
3
8. the composition of claim 1, wherein the second poly density is 0.955-0.965g/cm
3
9. the composition of claim 1, wherein the density of said composition is 0.932-0.950g/cm
3
10. the composition of claim 1, wherein the density of said composition is 0.935-0.945g/cm
3
11. the composition of claim 1, wherein the first and second poly density differences are 0.032-0.045g/cm
3
12. the composition of claim 1, wherein the melt index I of composition
2.16Be 2-10g/10min.
13. the composition of claim 1, wherein based on the first and second poly gross weights, said composition comprises 80wt%-35wt% first polyethylene.
14. the composition of claim 1, wherein based on the first and second poly gross weights, said composition comprises 65wt%-35wt% first polyethylene and 35wt%-65wt% second polyethylene.
15. the composition of claim 1, wherein based on the first and second poly gross weights, said composition comprises 55wt%-45wt% first polyethylene and 45wt%-55wt% second polyethylene.
16. the composition of claim 1, wherein the ESCR value of said composition is 250hr at least.
17. the composition of claim 1, wherein the ESCR value of said composition is 500hr at least.
18. the composition of claim 1, wherein the ESCR value of said composition is 750hr at least.
19. the composition of claim 1, wherein the ESCR value of said composition is 1000hr at least.
20. the composition of claim 1, wherein under-40 ℃, for the sample of 3.17mm, the izod impact strength of said composition is 120kJ/m at least.
21. the composition of claim 1, wherein said composition is made up of first and second polyethylene basically.
22. the composition of claim 1, the wherein at least a blend that comprises two or more polyvinyl resins in first and second polyethylene.
23. a rotation molded articles, it comprises polyethylene composition, and described polyethylene composition comprises:
(a) melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3First polyethylene; With
(b) melt index is that 10-30g/10min and density are 0.945-0.975g/cm
3Second polyethylene,
Wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min, and wherein the first and second poly density differences are 0.030-0.048g/cm
3, and be 20-65wt% based on the first and second poly gross weight second poly weight percentage wherein.
24. the rotation molded articles of claim 23, wherein at least a in first and second polyethylene is the polyethylene of metallocene catalysis.
25. the rotation molded articles of claim 23, wherein first and second polyethylene are polyethylene of metallocene catalysis.
26. the rotation molded articles of claim 23, wherein each the ratio of Mw/Mn of first and second polyethylene is 1.4-4.0.
27. the rotation molded articles of claim 25, the ratio of wherein said Mw/Mn is 1.8-3.5.
28. the rotation molded articles of claim 23, wherein the first poly density is 0.911-0.926g/cm
3
29. the rotation molded articles of claim 23, the second poly density is 0.950-0.970g/cm
3
30. the rotation molded articles of claim 23, wherein the second poly density is 0.955-0.965g/cm
3
31. the rotation molded articles of claim 23, wherein the density of said composition is 0.932-0.950g/cm
3
32. the rotation molded articles of claim 23, wherein the density of said composition is 0.935-0.945g/cm
3
33. the rotation molded articles of claim 23, wherein the first and second poly density differences are 0.032-0.045g/cm
3
34. the rotation molded articles of claim 23, wherein the melt index I of composition
2.16Be 2-10g/10min.
35. the rotation molded articles of claim 23, wherein based on the first and second poly gross weights, said composition comprises 80wt%-35wt% first polyethylene.
36. the rotation molded articles of claim 23, wherein based on the first and second poly gross weights, said composition comprises 65wt%-35wt% first polyethylene and 35wt%-65wt% second polyethylene.
37. the rotation molded articles of claim 23, wherein based on the first and second poly gross weights, said composition comprises 55wt%-45wt% first polyethylene and 45wt%-55wt% second polyethylene.
38. the rotation molded articles of claim 23, wherein the ESCR value of said composition is 250hr at least.
39. the rotation molded articles of claim 23, wherein the ESCR value of said composition is 500hr at least.
40. the rotation molded articles of claim 23, wherein the ESCR value of said composition is 750hr at least.
41. the rotation molded articles of claim 23, wherein the ESCR value of said composition is 1000hr at least.
42. the rotation molded articles of claim 23, wherein under-40 ℃, for the sample of 3.17mm, the izod impact strength of said composition is 120kJ/m at least.
43. the rotation molded articles of claim 23, wherein said composition is made up of first and second polyethylene basically.
44. the rotation molded articles of claim 23, the wherein at least a blend that comprises two or more polyvinyl resins in first and second polyethylene.
45. a method that forms rotation molded articles, this method comprises the steps:
(a) provide polyethylene composition, described polyethylene composition comprises:
(i) melt index is that 0.4-3.0g/10min and density are 0.910-0.930g/cm
3First polyethylene; With
(ii) melt index is that 10-30g/10min and density are 0.950-0.975g/cm
3Second polyethylene,
Wherein the density of said composition is 0.930-0.955g/cm
3And melt index is 1.5-12g/10min, and wherein the first and second poly density differences are 0.030-0.048g/cm
3, and be 20-65wt% based on the first and second poly gross weight second poly weight percentage wherein; With
(b) this polyethylene composition of rotational molding forms rotation molded articles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41495202P | 2002-10-01 | 2002-10-01 | |
| US60/414,952 | 2002-10-01 | ||
| US60/424,535 | 2002-11-07 |
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| CN1313528C true CN1313528C (en) | 2007-05-02 |
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| CNB038235455A Expired - Lifetime CN1313528C (en) | 2002-10-01 | 2003-09-18 | Polyethylene compositions for rotational molding |
| CNB038234742A Expired - Lifetime CN100420711C (en) | 2002-10-01 | 2003-09-18 | Polyethylene compositions for injection molding |
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| JP5103289B2 (en) * | 2007-06-11 | 2012-12-19 | 日本ポリエチレン株式会社 | Polyethylene resin composition for injection molded container lid |
| CA2752407C (en) * | 2011-09-19 | 2018-12-04 | Nova Chemicals Corporation | Polyethylene compositions and closures for bottles |
| CN102731881B (en) * | 2012-03-30 | 2016-08-17 | 中国石油化工股份有限公司 | For cross-linked polyolefin composition for rotational molding and preparation method thereof |
| CN103665528B (en) * | 2012-09-20 | 2015-12-02 | 中国石油化工股份有限公司 | Be applicable to polyolefine resin composition of rotation molding processing and preparation method thereof |
| CA2834068C (en) * | 2013-11-18 | 2020-07-28 | Nova Chemicals Corporation | Enhanced escr bimodal rotomolding resin |
| EP3158001A1 (en) * | 2014-11-13 | 2017-04-26 | Total Research & Technology Feluy | Rotomolded articles comprising metallocene-catalyzed polyethylene resin |
| BR112017010058A2 (en) * | 2014-11-13 | 2018-01-02 | Total Res & Technology Feluy | rotational molded article comprising at least one layer comprising a metallocene catalyzed polyethylene resin |
| ITUB20153248A1 (en) * | 2015-08-26 | 2017-02-26 | Versalis Spa | POLYETHYLENE POWDER, PROCEDURE FOR ITS PREPARATION AND ITS USE FOR ROTATIONAL MOLDING |
| CN106554535B (en) * | 2015-09-30 | 2019-04-26 | 神华集团有限责任公司 | Rotational moulding expanded polyethylene composition and polyethylene foam product |
| WO2017160243A1 (en) * | 2016-03-18 | 2017-09-21 | Scg Chemicals Company Limited | Polyolefin composition for rotational molding |
| CN108239322B (en) * | 2016-12-27 | 2020-12-04 | 上海凯波电缆特材股份有限公司 | High-hardness polyethylene cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264402A (en) * | 1997-06-20 | 2000-08-23 | 陶氏化学公司 | Ethylene polymer compositions and article fabricated from the same |
| EP1236770A1 (en) * | 2001-03-01 | 2002-09-04 | Borealis Technology Oy | Polyethylene compositions for rotomolding |
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|---|---|---|---|---|
| US5082902A (en) * | 1988-07-22 | 1992-01-21 | Mobil Oil Corporation | Method for reducing cycle time and improving molded part impact energy and ESCR of linear high density polyethylene using a blend of two linear polyethylenes of different densities |
| JPH0776673A (en) * | 1993-09-07 | 1995-03-20 | Oji Kako Kk | Tacky tape |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1264402A (en) * | 1997-06-20 | 2000-08-23 | 陶氏化学公司 | Ethylene polymer compositions and article fabricated from the same |
| EP1236770A1 (en) * | 2001-03-01 | 2002-09-04 | Borealis Technology Oy | Polyethylene compositions for rotomolding |
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| CN100420711C (en) | 2008-09-24 |
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