CN1284822C - Polyethylene resin composition used for rotational moulding and rotational moulded product made with said composition - Google Patents
Polyethylene resin composition used for rotational moulding and rotational moulded product made with said composition Download PDFInfo
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- CN1284822C CN1284822C CN 00120777 CN00120777A CN1284822C CN 1284822 C CN1284822 C CN 1284822C CN 00120777 CN00120777 CN 00120777 CN 00120777 A CN00120777 A CN 00120777A CN 1284822 C CN1284822 C CN 1284822C
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Abstract
The polyethylene resin composition for rotational molding according to the invention is a composition comprising an ethylene-alpha-olefin copolymer (A) and an ethylene-alpha-olefin copolymer (B), wherein the weight ratio (A)/(B) of the component (A) to the component (B) is in the range of 10/90 to 50/50, and a blend consisting of these components (A) and (B). The component (A) is preferably a copolymer prepared by the use of a metallocene type olefin polymerization catalyst, and the component (B) is preferably a copolymer prepared by the use of a metallocene type or Ziegler type olefin polymerization catalyst. the rotational molding product has impact resistance and environmental stress cracking resistance.
Description
The present invention relates to polyethylene resin composition that rotational moulding uses and with the rotomoulded articles of this composition system.More particularly, the present invention relates to be used in the polyethylene resin composition of preparation hollow mould plastic or complex die plastic such as water storing tank, particularly relate to the polyethylene resin composition that is used for rotational moulding, composition can make and have the goods of excellent in resistance towards property and environmental stress crack resistance (ESCR) thus, the invention still further relates to the rotomoulded articles with this composition system.
So far, produce various goods such as jar, container, daily necessities, kitchen utensils, garden articles for use and outdoor appliances with the rotational moulding legal system.The material require that is used to make these goods is in physical strength, and particularly these aspect of performances of shock-resistance and environmental stress crack resistance (ESCR) are excellent.As the rotational moulding material that meets these needs, polyvinyl resin is mainly used.
Is excellent with polyvinyl resin through in shock-resistant rigidity and environmental stress crack resistance one or both of article that rotational moulding makes, but aspect all properties all excellent then seldom.Therefore, be that people expect at moulded work much better aspect these performance balances.
In the applicant's day disclosure special permission communique 194537/1997, a kind of rotational moulding resin has been described, it comprises the ethene-alpha-olefin random copolymers, and its density is 0.920-0.955g/cm
3, melt index (MFR) restrains/10 minutes for 1-20, and molecular weight distribution (Mw/Mn) is 2-3, and particle diameter is not more than 30 orders.The rotomoulded articles made of resin is being excellent aspect balance shock-resistance, rigidity and the environmental stress crack resistance (ESCR) especially thus, and the use aspect is without any problem.
Yet its rotomoulded articles that can provide is still desired at the polyvinyl resin that is better than aspect shock-resistance and the environmental stress crack resistance (ESCR) with above-mentioned resinous rotomoulded articles now.
In these cases, the present inventor has carried out conscientious research to satisfy these demands, and as its result, they find, by following resin combination being carried out the polyethylene rotomoulded articles that rotational moulding makes, be excellent aspect shock-resistance and the environmental stress crack resistance, this resin combination contains: (A) ethene-alpha-olefin copolymer, it contains ethene and has the alpha-olefin of 3-20 carbon atom, and density (ASTM D1505) is 0.880-0.930g/cm
3, melt flow rate (MFR) (ASTMD1238,190 ℃, load 2.16Kg) is 0.01-5 gram/10 minutes, (B) contains the Alathon of ethene, or contains ethene and have the multipolymer of the alpha-olefin of 3-20 carbon atom.Its density is 0.931-0.974g/cm
3, melt flow rate (MFR) is 0.5-20 gram/10 minutes, wherein (A)/(B) weight ratio is in specified range, and the density that comprises the blend of ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B) is 0.920-0.960g/cm
3, melt flow rate (MFR) is 1-10 gram/10 minutes.Finished the present invention based on this discovery.
An object of the present invention is to provide the polyethylene resin composition that a kind of rotational moulding is used, composition can make its shock-resistance and environmental stress crack resistance (ESCR) all is better than the rotomoulded articles of common rotomoulded articles thus, and the rotomoulded articles of this composition system of use is provided.
The polyethylene resin composition that rotational moulding thing according to the present invention is used is a kind of resin combination, and it comprises:
(A) contain the ethene-alpha-olefin copolymer of alpha-olefin of ethene and 3-20 carbon atom of band, its density (ASTM D1505) is 0.880-0.930g/cm
3, melt flow rate (MFR) (MFR) (ASTM D1238,190 ℃, load: 2.16Kg) for 0.01-5 restrains/10 minutes, and
(B) contain the Alathon of ethene or contain ethene and the ethene-alpha-olefin copolymer of alpha-olefin of 3-20 carbon atom of band, its density (ASTM D1505) is 0.931-0.974g/cm
3, melt flow rate (MFR) (MFR) (ASTM D1238,190 ℃, load: 2.16Kg) for 0.5-20 restrains/10 minutes,
Wherein,
Ethene-alpha-olefin copolymer (A) is 10/90-50/50 with the weight ratio ((A)/(B)) of Alathon or ethene-alpha-olefin copolymer (B), and
By ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer
(B) density of the blend of Zu Chenging (ASTM D1505) is 0.920-0.960g/cm
3, melt flow rate (MFR) (MFR) (ASTM D1238,190 ℃, load: 2.16Kg) restrain/10 minutes for 1-10.
The polyethylene resin composition that is used for rotational moulding according to the present invention can adopt following four concrete schemes, and these concrete schemes are based on making ethene-alpha-olefin copolymer (A), Alathon
(B) type of used olefin polymerization catalyst is divided and during ethene-alpha-olefin copolymer (B).
(1) a kind of resin combination, each in therein ethylene-alpha-olefin copolymer (A), Alathon (B) and the ethene-alpha-olefin copolymer (B) all are (being total to) polymkeric substance with the preparation of two metallocene-type olefin polymerization catalysts;
(2) a kind of resin combination, therein ethylene-alpha-olefin copolymer (A) is the co-polymer with two metallocene-type olefin polymerization catalyst systems, and Alathon (B) and ethene-alpha-olefin copolymer (B) are to prepare with the Ziegler-type olefin polymerization catalyst;
(3) a kind of resin combination, therein ethylene-alpha-olefin copolymer (A), Alathon (B) and ethene-alpha-olefin copolymer (B) are to prepare with the Ziegler-type olefin polymerization catalyst; And
(4) a kind of resin combination, therein ethylene-alpha-olefin copolymer (A) is to prepare with the Ziegler-type olefin polymerization catalyst, and Alathon (B) and ethene-alpha-olefin copolymer (B) are to prepare with two metallocene-type olefin polymerization catalysts.
In above-mentioned resin combination (1)-(4), preferably resin combination (1) and (2), in them each contains the ethene-alpha-olefin copolymer (A) of useful two metallocene-type olefin polymerization catalysts preparation, and uses the Alathon and the ethene-alpha-olefin copolymer (B) of the preparation of Ziegler-type olefin polymerization catalyst.Particularly, contain the ethene-alpha-olefin copolymer (A) of useful two metallocene-type olefin polymerization catalysts preparation, it is superior reaching with the Alathon of Ziegler-type olefin polymerization catalyst preparation or the composition of ethene-alpha-olefin copolymer (B).
Rotomoulded articles according to the present invention contains the above-mentioned polyethylene resin composition that is used for rotational moulding.
The polyethylene resin composition that rotational moulding according to the present invention is used and with the rotomoulded articles of this composition system details are as follows.
The polyethylene resin composition that rotational moulding according to the present invention is used contains ethene-alpha-olefin copolymer (A), and density is different from the Alathon or the ethene-alpha-olefin copolymer (B) of multipolymer (A), when this resin combination by ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B) when forming, the density and the melt flow rate (MFR) of this resin combination are in specified range.
Ethene-alpha-olefin copolymer (A)
Be used for the multipolymer that ethene-alpha-olefin copolymer of the present invention (A) is the alpha-olefin of ethene and 3-20 carbon atom, density (ASTM D1505) is 0.880-0.930g/cm
3, be preferably 0.885-0.925g/cm
3, 0.890-0.920g/cm more preferably
3, its melt flow rate (MFR) (MFR) (ASTM D1238,190 ℃, load 2.16Kg) is preferably 0.05-4.5 gram/10 minutes for 0.01-5 restrains/10 minutes, and more preferably the 0.1-4.0 gram is/10 minutes.
The alpha-olefin example of 3-20 carbon atom comprises propylene, 1-butylene, 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene.The 3-Methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butylene, the 1-heptene, methyl isophthalic acid-hexene, dimethyl-1-amylene, trimethylammonium-1-butylene, ethyl-1-amylene, 1-octene, Methyl-1-pentene, dimethyl-1-hexene, trimethylammonium-1-amylene, ethyl-1-hexene, methylethyl-1-amylene, diethyl-1-butylene, propyl group-1-amylene, 1-decene, methyl isophthalic acid-nonene, dimethyl-1-octene, trimethylammonium-1-heptene.Ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecylene, cetene.
These alpha-olefins can be used separately, and perhaps two or more share.
The preferred in the present invention ethene-alpha-olefin copolymer (A) that uses is ethene-butene-1 copolymer, ethene-1-pentene copolymer, ethene-1-hexene copolymer, ethene-1-methyl-1 pentene copolymer or ethene-1-octene copolymer.
Ethene-alpha-olefin copolymer (A) with above-mentioned performance can be in the presence of common Ziegler-type or two metallocene-type olefin polymerization catalysts, preferred two metallocene-type olefin polymerization catalysts, with the alpha-olefin copolymer of ethene and 3-20 carbon atom and make.
Alathon or ethene-alpha-olefin copolymer (B)
Alathon of Shi Yonging or ethene-alpha-olefin copolymer (B) are the polymkeric substance that only contains ethene in the present invention, or the multipolymer of the alpha-olefin of ethene and 3-20 carbon atom, and its density (ASTMD1505) is 0.931-0.974g/cm
3, be preferably 0.935-0.970g/cm
3, 0.938-0.968g/cm more preferably
3, (ASTM D1238,190 ℃, load: 2.16Kg) for 0.5-20 restrains/10 minutes, be preferably 1.0-19 gram/10 minutes, more preferably the 1.5-18 gram is/10 minutes for melt flow rate (MFR) (MFR).
The alpha-olefin example of 3-20 carbon atom comprises the identical alpha-olefin of alpha-olefin with 3-20 the carbon atom that is used to constitute above-mentioned ethene-alpha-olefin copolymer (A).The alpha-olefin of 3-20 carbon atom can use separately, and perhaps two or more share.
The ethene-alpha-olefin copolymer (B) that is preferred among the present invention is ethene-butene-1 copolymer, ethene-1-pentene copolymer, ethene-1-hexene copolymer, ethene-4 methyl 1 pentene copolymer or ethene-1-octene copolymer.
Having the Alathon of above-mentioned performance or ethene-alpha-olefin copolymer (B) can be in the presence of common Ziegler-type or two metallocene-type olefin polymerization catalyst, with ethylene homo or with the alpha-olefin copolymer of ethene and 3-20 carbon atom and make.
When using the ethene-alpha-olefin copolymer produce with two metallocene-type olefin polymerization catalysts as ethene-alpha-olefin copolymer of the present invention (A), can use the Alathon that makes with two metallocene-type olefin polymerization catalysts or ethene-alpha-olefin copolymer as Alathon or ethene-alpha-olefin copolymer (B), perhaps, can be used as Alathon or ethene-alpha-olefin copolymer (B) by Alathon or the ethene-alpha-olefin copolymer that makes with the Ziegler-type polymerisation catalysts.
When using the ethene-alpha-olefin copolymer produce with the Ziegler-type olefin polymerization catalyst, then use the Alathon produced with the Ziegler-type olefin polymerization catalyst or ethene-alpha-olefin copolymer as Alathon or ethene-alpha-olefin copolymer (B) as ethene-alpha-olefin copolymer of the present invention (A).
In above-mentioned situation, be preferred with mixture by using the Alathon (component (B)) that the Ziegler-type olefin polymerization catalyst makes by the ethene-alpha-olefin copolymer (A) that makes with two metallocene-type olefin polymerization catalysts.
The polyethylene resin composition that is used for rotational moulding
The polyethylene resin composition that is used for rotational moulding according to the present invention comprises ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B).
In this resin combination, the weight ratio ((A)/(B)) of ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B) is 10/90-50/50, is preferably 15/85-45/55, more preferably 20/80-40/60.
As for the polyethylene resin composition that is used for rotational moulding according to the present invention, the density (ASTM D1505) of the blend of being made up of ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B) is 0.920-0.960g/cm
3, be preferably 0.922-0.958g/cm
3, 0.925-0.955g/cm more preferably
3, be preferably 0.930-0.955g/cm especially
3, and melt flow rate (MFR) (MFR) (ASTM D1238,190 ℃, load: 2.16Kg) be 1-10 gram/10 minutes, be preferably 1.5-9 gram/10 minutes, more preferably the 2.0-8 gram is/10 minutes.When the density of this resin combination is in the above-mentioned scope, can make rotomoulded articles with excellent rigidity and physical strength.When the melt flow rate (MFR) of this resin combination was in the above-mentioned scope, this resin combination showed excellent rotational moulding, and can make the polyethylene rotomoulded articles with good appearance.
Be used for the preparation of the polyethylene resin composition of rotational moulding
As mentioned above, the polyethylene resin composition that is used for rotational moulding according to the present invention comprises ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B).
In this polyethylene resin composition, can add additive, as organic or mineral filler, antioxidant, thermo-stabilizer, ultraviolet absorbers, fire retardant, static inhibitor, lubricant, whipping agent, tinting material, releasing agent and Weather-stable agent, added amount should not influence purpose of the present invention.
The polyethylene resin composition that is used for rotational moulding according to the present invention can be Powdered or particulate state, and in the time will carrying out rotational moulding, then this composition is only required Powdered.
When the polyethylene resin composition that is used for rotational moulding according to the present invention is particulate state, carrying out before the rotational moulding particle being crushed into powder.
The hope particle diameter that is used for the polyethylene resin composition powder of rotational moulding according to the present invention is not more than 30 orders, is preferably the 40-100 order.When the particle diameter of the powder that uses was above-mentioned scope, its rotational moulding excellence can obtain the good rotomoulded articles of outward appearance.
The polyethylene resin composition that is used for rotational moulding according to the present invention can followingly make: with ethene-alpha-olefin copolymer (A), Alathon or ethene-alpha-olefin copolymer (B) and the above-mentioned additive of mentioning, carry out melt kneading with common kneading device such as forcing machine, Ban Buli mixing machine, kneader or Han Xieer mixing machine; With freezing and pulverizing method or mechanical crushing method kneaded material is made powder then.
In addition, can be according to the polyethylene resin composition that is used for rotational moulding of the present invention by carrying out a copolymerization step and homopolymerization or copolymerization step continuously, pulverize then and make: copolymerization is in the presence of two metallocene-type olefin polymerization catalysts the alpha-olefin of ethene and 3-20 carbon atom to be carried out copolymerization, with preparation ethene-alpha-olefin copolymer (A), with in the presence of two metallocene-type or Ziegler-type polymerisation catalysts, utilize the alkene of a step homopolymerization or copolymerization of ethylene and 3-20 carbon atom, with preparation Alathon or ethene-alpha-olefin copolymer (B); With freezing and pulverizing method or mechanical crushing method the resin combination that makes is made powder subsequently.Before pulverizing, can resin combination and additive be carried out melt kneading with mediating device.
When ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B) all prepare with the Ziegler-type olefin polymerization catalyst, the polyethylene resin composition that rotational moulding according to the present invention is used can be by carrying out a copolymerization step and homopolymerization or copolymerization step continuously, pulverize then and make: copolymerization is in the presence of the Ziegler-type olefin polymerization catalyst alpha-olefin of ethene and 3-20 carbon atom to be carried out copolymerization to make ethene-alpha-olefin copolymer (A), homopolymerization or copolymerization are ethylene homo to be made Alathon (B) in the presence of the Ziegler-type olefin polymerization catalyst or with the alpha-olefin copolymer of ethene and 3-20 carbon atom, make ethene-alpha-olefin copolymer (B); With freezing and pulverizing method or mechanical crushing method the resin combination of gained is made powder subsequently.Before pulverizing, can resin combination and additive be carried out melt kneading with mediating device.
The polyethylene resin composition that rotational moulding according to the present invention is used can be by carrying out a copolymerization step and homopolymerization or copolymerization step continuously, pulverize then and make: copolymerization is in the presence of the Ziegler-type olefin polymerization catalyst alpha-olefin of ethene and 3-20 carbon atom to be carried out copolymerization, with preparation ethene-alpha-olefin copolymer (A), homopolymerization or copolymerization be in the presence of two metallocene-type olefin polymerization catalysts with ethylene homo with preparation Alathon (B) or with the alpha-olefin copolymer of ethene and 3-20 carbon atom, to prepare ethene-alpha-olefin copolymer (B); With freezing and pulverizing method or mechanical crushing method the resin combination of gained is made powder subsequently.Before pulverizing, can resin combination and additive be carried out melt kneading with mediating device.
Rotomoulded articles
Rotomoulded articles according to the present invention makes by the above-mentioned polyethylene resin composition that is used for rotational moulding is carried out rotational moulding.Being carried out the polyethylene resin composition of rotational moulding, is Powdered as mentioned above.
Rotomoulded articles of the present invention can be used known method preparation so far.In particular, will be according to the polyethylene resin composition powder that is used for rotational moulding of the present invention, put into one in single shaft rotation or be in decussate biaxial rotated mould, or put into one and make the mould that rock and roll moves, under sealed state, make internal surface and the fusion of powder distribution at mould.Then, with mold cools down, and will take out at the moulded parts that mould inner surface forms.So just obtained rotomoulded articles of the present invention.
The internal surface of mould can have embossing pattern, also can have.
Rotational moulding according to the present invention contains two kinds of special ethene-alpha-olefin copolymers with polyethylene resin composition, or containing a kind of special ethene-alpha-olefin copolymer and a kind of Alathon, the blend of being made up of these two kinds of (being total to) polymkeric substance has specific density and specific melt flow rate (MFR).Therefore, this polyethylene resin composition has excellent rotational moulding and can make at the rotomoulded articles that is better than common polyethylene molded article aspect shock-resistance and the environmental stress crack resistance (ESCR).
Rotomoulded articles according to the present invention is made by polyethylene resin composition of the present invention, and therefore rotomoulded articles of the present invention is being better than common polyethylene molding product aspect shock-resistance and the environmental stress crack resistance (ESCR).
Therefore, the polyethylene resin composition that is used for rotational moulding according to the present invention is applicable to and makes hollow piece and complex-shaped goods.More particularly, polyethylene resin composition of the present invention is applicable to system jar (as water storing tank) large size or small size, container, and spheroid, garden supplies, kitchen utensils, mechanical component have the slush molding product at special position, outdoor appliances, or the like.
Embodiment
With reference to the following example the present invention is further described earlier, but should be realized that the present invention never is subject to these embodiment.
Be used for the ethene-alpha-olefin copolymer and the Alathon of embodiment and comparing embodiment, be prepared as follows.
Prepare Alathon and ethene-alpha-olefin copolymer with one-step polymerization method.
(1) ethene-1-hexene copolymer (M-PE (1))
Catalyzer: zirconic two metallocene-type olefin polymerization catalysts
Density (ASTM D1505): 0.905g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 1 gram/10 minutes
(2) ethene-1-hexene copolymer (M-PE (2))
Catalyzer: zirconic two metallocene-type olefin polymerization catalysts
Density (ASTM D1505): 0.905g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 4 grams/10 minutes
(3) ethene-butene-1 copolymer (Z-PE (1))
Catalyzer: Ziegler-type olefin polymerization catalyst
Density (ASTM D1505): 0.957g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 8.3 grams/10 minutes
(4) ethylene-propylene copolymer (Z-PE (2))
Catalyzer: Ziegler-type olefin polymerization catalyst
Density (ASTM D1505): 0.966g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 12.5 grams/10 minutes
(5) ethylene-propylene copolymer (Z-PE (3))
Catalyzer: Ziegler-type olefin polymerization catalyst
Density (ASTM D1505): 0.970g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 16 grams/10 minutes
(6) ethylene-propylene copolymer (Z-PE (4))
Catalyzer: Ziegler-type olefin polymerization catalyst
Density (ASTM D1505): 0.965g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 11 grams/10 minutes
(7) Alathon (Z-PE (5))
Catalyzer: Ziegler-type olefin polymerization catalyst
Density (ASTM D1505): 0.968g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 5.2 grams/10 minutes
(8) ethene-4 methyl 1 pentene copolymer (Z-PE (6))
Catalyzer: Ziegler-type olefin polymerization catalyst
Density (ASTM D1505): 0.944g/cm
3
MFR (ASTM D1238,190 ℃, load: 2.16Kg): 7.1 grams/10 minutes
Embodiment 1
The single screw extrusion machine that with diameter is 40mm carries out melt kneading at 200 ℃ of following 30 parts by weight of ethylene-1-hexene copolymers (M-PE (1)) and 70 parts by weight of ethylene-butene-1 copolymer (Z-PE (1)), with the preparation polyethylene resin composition.
Then, this composition is carried out freezing and pulverizing and be not more than 30 purpose powder with the preparation particle diameter.Powder is put into a cylindrical container, and carry out rotational moulding under 270 ℃ of mould temperature, the molding cycle condition is: heat-up time: 8 minutes, and the pressing time: 2 minutes, and cooling time: 5 minutes is the moulded work (cylindrical container) of 3mm to obtain thickness.
From layered product, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test, and environmental stress crack resistance test according to following method.Gained the results are shown in table 1.
Test method
(1) tension test
Under draw speed 50 mm/min, carry out tension test according to ASTM D-638, stress, fracture tensile strength and extension at break when producing to measure.
(2) Ao Erxun bone test
Carry out the Ao Erxun bone test according to ASTM D-747.
(3) Izod impact test
Carry out Izod impact test at-20 ℃ in the otch condition according to JIS K-7110.
(4) environmental stress cracking test
According to ASTM D-1698 50 ℃ with 10% peace Ta Luokesi (Antarox) (C0-630) solution carry out environmental stress cracking test.Used thickness is the sample of 3mm.Value representation in the table 1 be 50% rupture time (hour).
Embodiment 2
Make polyethylene resin composition with the method identical with embodiment 1, different is, the consumption of ethene-1-hexene copolymer (M-PE (1)) is 40 weight parts, and replaces 70 parts by weight of ethylene-butene-1 copolymer (Z-PE (1)) with 60 parts by weight of ethylene-propylene copolymer (Z-PE (2)).
Then, use the mode identical, prepare particle diameter with this polyethylene resin composition and be not more than 30 purpose powder, and this powder is carried out rotational moulding to obtain moulded parts with embodiment 1.
From moulded parts, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test and environmental stress cracking test with aforesaid method.The results are shown in Table 1.
Embodiment 3
Make polyethylene resin composition with the method identical with embodiment 1, the consumption of different is ethene-1-hexene copolymer (M-PE (1)) is 45 weight parts, and replaces 70 parts by weight of ethylene-butene-1 copolymer (Z-PE (1)) with 55 parts by weight of ethylene-propylene copolymer (Z-PE (3)).
Then, use the mode identical, prepare particle diameter with this polyethylene resin composition and be not more than 30 purpose powder, and this powder is carried out rotational moulding to obtain moulded parts with embodiment 1.
From moulded parts, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test and environmental stress cracking test with aforesaid method.The results are shown in Table 1.
Embodiment 4
Make polyethylene resin composition with the method identical with embodiment 1, different is, the consumption of ethene-1-hexene copolymer (M-PE (2)) is 30 weight parts, and replaces 70 parts by weight of ethylene-butene-1 copolymer (Z-PE (1)) with 70 parts by weight of ethylene-propylene copolymer (Z-PE (4)).
Then, use the mode identical, prepare particle diameter with this polyethylene resin composition and be not more than 30 purpose powder, and this powder is carried out rotational moulding to obtain moulded parts with embodiment 1.
From moulded parts, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test and environmental stress cracking test with aforesaid method.The results are shown in Table 1.
Embodiment 5
Make polyethylene resin composition with the method identical with embodiment 1, different is, the consumption of ethene-1-hexene copolymer (M-PE (1)) is 25 weight parts, and replaces 70 parts by weight of ethylene-butene-1 copolymer (Z-PE (1)) with the equal multipolymer of 75 parts by weight of ethylene (Z-PE (5)).
Then, use the mode identical, prepare particle diameter with this polyethylene resin composition and be not more than 30 purpose powder, and this powder is carried out rotational moulding to obtain moulded parts with embodiment 1.
From moulded parts, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test and environmental stress cracking test with aforesaid method.The results are shown in Table 1.
Embodiment 6
In a polymerization reactor, containing in the presence of the zirconium two metallocene-type olefin polymerization catalysts, it is 0.904g/cm to prepare its density (ASTM D1505) that ethene and 1-hexene are carried out copolymerization
3, MFR (ASTM D1238,190 ℃, load: 2.16Kg) be ethene-1-hexene copolymer (M-PE (3)) of/10 minutes of 1 gram.
Subsequently, ethene-1-hexene copolymer (M-PE (3)) is sent in another polymerization reactor with a last reactors in series, in this reactor, in the presence of zirconic two metallocene-type olefin polymerization catalysts, ethene and 1-hexene are carried out copolymerization, are 0.957g/cm with preparation density (ASTM D1505)
3, MFR (ASTM D1238,190 ℃, load: 2.16Kg) be ethene-1-hexene copolymers (M-PE (4)) of/10 minutes of 8.8 grams, make density (ASTM D1505) by it and be 0.940g/cm
3, MFR (ASTM D1238,190 ℃, load: 2.16Kg) be/10 minutes polyethylene resin compositions of 3.9 grams.In this resin combination, ethene-1-hexene copolymer (M-PE
(3)) weight ratio with ethene-1-hexene copolymer (M-PE (4)) is 30/70.
Then, use the mode identical, prepare particle diameter with this polyethylene resin composition and be not more than 30 purpose powder, and this powder is carried out rotational moulding to obtain moulded parts with embodiment 1.
From moulded parts, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test and environmental stress cracking test with aforesaid method.The results are shown in Table 1.
Comparing embodiment 1
Prepare particle diameter with the mode identical with embodiment 1 and be not more than 30 purpose powder, different is replaces polyethylene resin composition among the embodiment 1 with ethene-4 methyl 1 pentene copolymer (Z-PE (6)).This powder is carried out rotational moulding to obtain moulded parts.
From moulded parts, take out sample, carry out tension test, Ao Erxun bone test, Izod impact test and environmental stress cracking test with aforesaid method.The results are shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparing embodiment | |
| Ethene-alpha-olefin copolymer (A) density (g/cm 3) | 0.905 | 0.905 | 0.905 | 0.905 | 0.905 | 0.904 | - |
| MFR (g/10min) | 1 | 1 | 1 | 4 | 1 | 1 | - |
| Alathon or ethene-alpha-olefin copolymer (B) density (g/cm 3) | 0.957 | 0.966 | 0.970 | 0.965 | 0.968 | 0.957 | - |
| MFR (g/10min) | 8.3 | 12.5 | 16 | 11 | 5.2 | 8.8 | - |
| (A)/(B) weight ratio in the resin combination | 30/70 | 40/60 | 45/55 | 30/70 | 25/75 | 30/75 | - |
| Performance (the g/cm of resin combination or resin 3) | 0.940 | 0.940 | 0.940 | 0.945 | 0.951 | 0.940 | 0.944 |
| MFR (g/10min) | 3.6 | 3.2 | 3.2 | 7.8 | 3.4 | 3.9 | 7.1 |
| Stress (Mpa) when the performance tensile property of rotomoulded articles produces | 17 | 19 | 19 | 19 | 22 | 17 | 18 |
| Fracture tensile strength (Mpa) | 32 | 30 | 33 | 28 | 28 | 33 | 26 |
| Extension at break (%) | 860 | 750 | 760 | 900 | 820 | 890 | 760 |
| Ao Erxun rigidity (Mpa) | 420 | 430 | 420 | 490 | 680 | 420 | 500 |
| Cantilever-type impact strength (J/m) | ＞690 | NB | ＞690 | 83 | ＞690 | ＞690 | 45 |
| RSCR (hr) | ＞600 | ＞600 | ＞600 | 93 | ＞600 | ＞600 | 16 |
(1) resin combination of embodiment 1-5 each all are melt blending things of component (A) and component (B).
(2) resin combination of embodiment 6 is the resin combination that the preparation of preparation by carrying out component (A) continuously and component (B) obtains.
(3) " NB " refers to that sample does not break in the table in shock test.
Claims (7)
1. polyethylene resin composition that rotational moulding is used is characterized in that it comprises:
(A) contain ethene and with the ethene-alpha-olefin copolymer of the alpha-olefin of 3～20 carbon atoms, its density is 0.880～0.930g/cm according to ASTM D1505
3, melt flow rate (MFR) is according to ASTM D1238, at 190 ℃, and load: be measured as 0.01～5 gram/10 minutes under the 2.16Kg condition, and
(B) contain the Alathon of ethene or contain ethene and with the ethene-alpha-olefin copolymer of the alpha-olefin of 3～20 carbon atoms, its density is measured as 0.931～0.974g/cm according to ASTM D1505
3, melt flow rate (MFR) is according to ASTM D1238, at 190 ℃, and load: be measured as 0.5～20 gram/10 minutes under the 2.16Kg condition,
Wherein,
Ethene-alpha-olefin copolymer (A) is 10/90～50/50 with the weight ratio (A)/(B) of Alathon or ethene-alpha-olefin copolymer (B), and
The density of the blend of being made up of ethene-alpha-olefin copolymer (A) and Alathon or ethene-alpha-olefin copolymer (B) is 0.920～0.960g/cm according to ASTM D1505
3, melt flow rate (MFR) is according to ASTM D1238, at 190 ℃, and load: be 1.5～10 grams/10 minutes under the 2.16Kg condition.
2. the polyethylene resin composition that desired rotational moulding is used as claim 1, therein ethylene-alpha-olefin copolymer (A), Alathon (B) and ethene-alpha-olefin copolymer (B) all are the polymkeric substance with the preparation of two metallocene-type olefin polymerization catalysts.
3. the polyethylene resin composition that desired rotational moulding is used as claim 1, therein ethylene-alpha-olefin copolymer (A) is the multipolymer with two metallocene-type olefin polymerization catalyst systems, and Alathon (B) and ethene-alpha-olefin copolymer (B) are to prepare with the Ziegler-type olefin polymerization catalyst.
4. the polyethylene resin composition that desired rotational moulding is used as claim 1, therein ethylene-alpha-olefin copolymer (A), Alathon (B) and ethene-alpha-olefin copolymer (B) are with the preparation of Ziegler-type olefin polymerization catalyst.
5. the polyethylene resin composition that desired rotational moulding is used as claim 1, therein ethylene-alpha-olefin copolymer (A) is to prepare with the Ziegler-type olefin polymerization catalyst, and Alathon (B) and ethene-alpha-olefin copolymer (B) are to prepare with two metallocene-type olefin polymerization catalysts.
6. as any the desired polyethylene resin composition among the claim 1-5, wherein the powder diameter of this polyethylene resin composition is not more than 30 orders.
7. rotomoulded articles that comprises among the claim 1-6 any rotational moulding with polyethylene resin composition.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP202678/1999 | 1999-07-16 | ||
| JP20267899 | 1999-07-16 | ||
| JP194925/2000 | 2000-06-23 | ||
| JP2000194925A JP2001089615A (en) | 1999-07-16 | 2000-06-23 | Rotational molding polyethylene resin composition and rotational molding product using the same composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1281003A CN1281003A (en) | 2001-01-24 |
| CN1284822C true CN1284822C (en) | 2006-11-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00120777 Expired - Lifetime CN1284822C (en) | 1999-07-16 | 2000-07-14 | Polyethylene resin composition used for rotational moulding and rotational moulded product made with said composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2001089615A (en) |
| CN (1) | CN1284822C (en) |
| AU (1) | AU764796B2 (en) |
| NZ (1) | NZ505712A (en) |
| TW (1) | TW593500B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7396878B2 (en) | 2002-10-01 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for injection molding |
| US7396881B2 (en) | 2002-10-01 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for rotational molding |
| US7943700B2 (en) | 2002-10-01 | 2011-05-17 | Exxonmobil Chemical Patents Inc. | Enhanced ESCR of HDPE resins |
| DE60331562D1 (en) * | 2002-10-01 | 2010-04-15 | Exxonmobil Chem Patents Inc | |
| JP5832098B2 (en) * | 2003-02-17 | 2015-12-16 | 三井化学株式会社 | Application to ethylene polymers and molded products |
| JP4231309B2 (en) * | 2003-03-14 | 2009-02-25 | リケンテクノス株式会社 | Method for producing sol-like thermoplastic resin composition |
| EP1600478A1 (en) * | 2004-05-28 | 2005-11-30 | Total Petrochemicals Research Feluy | Use of thermoplastic composition comprising thermoplastic polyurethanes as additive |
| EP1600477A1 (en) * | 2004-05-28 | 2005-11-30 | Total Petrochemicals Research Feluy | Use of thermoplastic composition comprising polyethylene glycol as additive |
| EP1600476A1 (en) * | 2004-05-28 | 2005-11-30 | Total Petrochemicals Research Feluy | Use of polyetheresters for rotomolding |
| EP1600474A1 (en) * | 2004-05-28 | 2005-11-30 | Total Petrochemicals Research Feluy | Use of fluoropolymers for rotomolding |
| EP1600475A1 (en) | 2004-05-28 | 2005-11-30 | Total Petrochemicals Research Feluy | Use of Thermoplastic Composition Comprising Polyether-Block Copolyamides as Additive |
| US7230054B2 (en) | 2004-06-29 | 2007-06-12 | Equistar Chemicals, Lp | Polymer resins with improved environmental stress crack resistance |
| US8486323B2 (en) | 2009-08-28 | 2013-07-16 | Dow Global Technologies Llc | Rotational molded articles, and method of making the same |
| CN101844654B (en) * | 2010-04-13 | 2012-01-18 | 无锡新龙科技有限公司 | Manufacturing process of storage tank with plastic steel composite structure |
| ES2648297T3 (en) | 2011-03-04 | 2017-12-29 | Total Research & Technology Feluy | Polyethylene blend preparation process comprising resins produced with metallocene and resins produced with Ziegler-Natta |
| CN103665505A (en) * | 2012-08-29 | 2014-03-26 | 中国石油化工股份有限公司 | Ethylene polymer composition, ethylene polymer material and fruit milk bottle |
| 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 |
| CN105131411B (en) * | 2015-08-27 | 2017-07-18 | 浙江瑞堂塑料科技有限公司 | A kind of rotation molding urea box polythene material and preparation method thereof |
| CN108794869B (en) * | 2017-04-28 | 2021-04-13 | 中国石油化工股份有限公司 | Polyolefin composition for rotational molding storage tank and preparation method thereof |
| JP7431743B2 (en) * | 2018-03-22 | 2024-02-15 | ダウ グローバル テクノロジーズ エルエルシー | Process for forming rotomolded parts |
| CN111073119A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Assistant composition, linear medium-density polyethylene composition, preparation method thereof and polyethylene rotational molding product |
| US11746220B2 (en) | 2020-06-12 | 2023-09-05 | Braskem S.A. | High flow rotomolding compositions, processes thereof, and articles therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2821480B2 (en) * | 1988-09-08 | 1998-11-05 | 多摩川精機株式会社 | Rotor core |
| JP2967937B2 (en) * | 1990-09-10 | 1999-10-25 | 三井化学株式会社 | Rotational molding |
| JP2000007849A (en) * | 1998-04-23 | 2000-01-11 | Mitsui Chemicals Inc | Polyethylene resin and its production |
-
2000
- 2000-06-23 JP JP2000194925A patent/JP2001089615A/en active Pending
- 2000-07-06 TW TW89113425A patent/TW593500B/en not_active IP Right Cessation
- 2000-07-12 NZ NZ50571200A patent/NZ505712A/en unknown
- 2000-07-14 CN CN 00120777 patent/CN1284822C/en not_active Expired - Lifetime
- 2000-07-14 AU AU48619/00A patent/AU764796B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU764796B2 (en) | 2003-08-28 |
| AU4861900A (en) | 2001-01-18 |
| JP2001089615A (en) | 2001-04-03 |
| NZ505712A (en) | 2002-02-01 |
| TW593500B (en) | 2004-06-21 |
| CN1281003A (en) | 2001-01-24 |
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