CA1229450A - 1-butene polymer and its use - Google Patents
1-butene polymer and its useInfo
- Publication number
- CA1229450A CA1229450A CA000453997A CA453997A CA1229450A CA 1229450 A CA1229450 A CA 1229450A CA 000453997 A CA000453997 A CA 000453997A CA 453997 A CA453997 A CA 453997A CA 1229450 A CA1229450 A CA 1229450A
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- CA
- Canada
- Prior art keywords
- butene
- tert
- polymer
- acid
- titanium
- 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.)
- Expired
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- Extrusion Moulding Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A B S T R A C T
A butene-1 polymer containing 0 to 1 mole% of an olefin with 2 to 20 carbon atoms other than 1-butene and having (1) an intrinsic viscosity [?] of from 1.5 to 4.0 dl/g, (2) a molecular weight distribution, expressed by the ratio of its weight average molecular weight (?w) to its number average molecular weight (?n), of not more than 6, and (3) an isotacticity value of at least 95%.
A butene-1 polymer containing 0 to 1 mole% of an olefin with 2 to 20 carbon atoms other than 1-butene and having (1) an intrinsic viscosity [?] of from 1.5 to 4.0 dl/g, (2) a molecular weight distribution, expressed by the ratio of its weight average molecular weight (?w) to its number average molecular weight (?n), of not more than 6, and (3) an isotacticity value of at least 95%.
Description
o Litton POLO IRE AND ITS USE
This invention relates to a l-butcne puller which has high rigidity, excellent creep resistance, excellent impact strength and a high crystal trueness-lion speed and exhibits its excellent improved pro-parties as a shaped article, particularly a shaped article in the form of a pipe structure, and to it use.
More specifically, this invention relates to a l~butene polymer containing O to 1 mole, of an olefin with 2 to 20 carbon atoms other than l-butene and having (1) an intrinsic viscosity no of prom 1.5 to 4.0 dug I a molecular weight distribution, express sod by the ratio of its weight average molecular weight (ow) to its number average molecular weight no of not more than 6, and (3) an isotacticity value of at least 95~.
Metallic pipes such as Zinc-plated steel pipes, copper pipes or lead pipes have been used as water supplying pipes. These metallic pipes, however, have some defects, and new piping materials free from these defects have been desired. So far, plastic pipes such as pipes of polyvinyl chloride, polyethylene and poly-l-butene free from pinhole formation owing to rust or electroly~c corrosion have gained some act sweetness.
Because ox its excellent pressure-resisting strength, creep resistance to internal pressures at high temperatures, abrasion resistances, and excellent flexibility, a l-butene polymer I among those prefer-red synthetic resins for use as a material or water supplying pipes.
Shaped articles, particularly in the form of a pipe structure, of the l~butene polymer are wrier Jo - -to be further improved in rne~larlical Steinway; .-3;, sun as rigidity, creep characteristics end impact s,ren~tn.
It is known that when solid1~ied 1 r em it molten state, the button polymer initially as~mef , a pseudo stable II type (tetragonal system ransom Sheehan, and then slowly passes into a stable I type ,'L/caf;C",~, (hexagonal system over several days.
In the state of the II type, a shaped article of the 1-butane polymer is soft. If, therefore, the shaped anti-ale undergoes deformation by transportation or otherwise while it is of the II type and is transformed in this state to the I type, the deformation remains in the en-tide to make it valueless as a commercial product. Act cordingly, the handling of the shaped article before complete transition to the I type is troublesome and much expertise and labor are spent in trying to prevent the remaining of such undesirable deformation.
Attempts have been made to increase the crystal transition speed of the l-butene polymer. For example, it was proposed to shorten the time required for crystal transition by modifying the molding method (see or example, Japanese Laid-Open Patent Public cation No. 42-92/1972), or to achieve it by using additives (see, for example, Japanese Laid-Open Patent Publications Nos. 36140/1982 and 92038/1982). None have yet been able to achieve an industrially sails-factory improvement The present inventors, Iron a different standpoint from the prior attempts to use an additional means or additives, have made investigations to provide a new l-butene polymer itself which has high rigidity, excellent creep resistance characteristics, and excel-lent impact strength and a hither crystal transition speed.
These invest1~ations have led to the disk covey that there can be provided a l-butene polymer character led by having (1) an intrinsic viscosity on]
of from 1.5 to 4.0 dug (2) a molsc~llar Lyon,, do-;-tribution, expressed by the ratio of its ~Gioht average molecular weight I ) to its number ~-rGrage molecular weight (Len), of not more than 6, and (3, an isotacticity value of at least 95%, and that the 1-butane polymer having the characteristics I to (3 above overcomes the aforesaid technical problem, exhibits high rigidity, excellent creep resistance characteristics, excellent impact strength and an lo increased crystal transition speed and gives a shaped article, particular in the form of a pipe structure having excellent improved properties.
It is an object of this invention to provide a button polymer having the aforesaid excellent improved properties and its use, particularly as a shaped article in the form of a pipe structure.
The above and other objects and advantages of this invention will become more apparent from the following description.
According to this invention, there is pro-voided a l-butene polymer containing 0 to 1 mole% of an olefin with 2 to 20 carbon atoms other than button and having (l) an intrinsic viscosity [n] of from 1.5 to 4.0 do
This invention relates to a l-butcne puller which has high rigidity, excellent creep resistance, excellent impact strength and a high crystal trueness-lion speed and exhibits its excellent improved pro-parties as a shaped article, particularly a shaped article in the form of a pipe structure, and to it use.
More specifically, this invention relates to a l~butene polymer containing O to 1 mole, of an olefin with 2 to 20 carbon atoms other than l-butene and having (1) an intrinsic viscosity no of prom 1.5 to 4.0 dug I a molecular weight distribution, express sod by the ratio of its weight average molecular weight (ow) to its number average molecular weight no of not more than 6, and (3) an isotacticity value of at least 95~.
Metallic pipes such as Zinc-plated steel pipes, copper pipes or lead pipes have been used as water supplying pipes. These metallic pipes, however, have some defects, and new piping materials free from these defects have been desired. So far, plastic pipes such as pipes of polyvinyl chloride, polyethylene and poly-l-butene free from pinhole formation owing to rust or electroly~c corrosion have gained some act sweetness.
Because ox its excellent pressure-resisting strength, creep resistance to internal pressures at high temperatures, abrasion resistances, and excellent flexibility, a l-butene polymer I among those prefer-red synthetic resins for use as a material or water supplying pipes.
Shaped articles, particularly in the form of a pipe structure, of the l~butene polymer are wrier Jo - -to be further improved in rne~larlical Steinway; .-3;, sun as rigidity, creep characteristics end impact s,ren~tn.
It is known that when solid1~ied 1 r em it molten state, the button polymer initially as~mef , a pseudo stable II type (tetragonal system ransom Sheehan, and then slowly passes into a stable I type ,'L/caf;C",~, (hexagonal system over several days.
In the state of the II type, a shaped article of the 1-butane polymer is soft. If, therefore, the shaped anti-ale undergoes deformation by transportation or otherwise while it is of the II type and is transformed in this state to the I type, the deformation remains in the en-tide to make it valueless as a commercial product. Act cordingly, the handling of the shaped article before complete transition to the I type is troublesome and much expertise and labor are spent in trying to prevent the remaining of such undesirable deformation.
Attempts have been made to increase the crystal transition speed of the l-butene polymer. For example, it was proposed to shorten the time required for crystal transition by modifying the molding method (see or example, Japanese Laid-Open Patent Public cation No. 42-92/1972), or to achieve it by using additives (see, for example, Japanese Laid-Open Patent Publications Nos. 36140/1982 and 92038/1982). None have yet been able to achieve an industrially sails-factory improvement The present inventors, Iron a different standpoint from the prior attempts to use an additional means or additives, have made investigations to provide a new l-butene polymer itself which has high rigidity, excellent creep resistance characteristics, and excel-lent impact strength and a hither crystal transition speed.
These invest1~ations have led to the disk covey that there can be provided a l-butene polymer character led by having (1) an intrinsic viscosity on]
of from 1.5 to 4.0 dug (2) a molsc~llar Lyon,, do-;-tribution, expressed by the ratio of its ~Gioht average molecular weight I ) to its number ~-rGrage molecular weight (Len), of not more than 6, and (3, an isotacticity value of at least 95%, and that the 1-butane polymer having the characteristics I to (3 above overcomes the aforesaid technical problem, exhibits high rigidity, excellent creep resistance characteristics, excellent impact strength and an lo increased crystal transition speed and gives a shaped article, particular in the form of a pipe structure having excellent improved properties.
It is an object of this invention to provide a button polymer having the aforesaid excellent improved properties and its use, particularly as a shaped article in the form of a pipe structure.
The above and other objects and advantages of this invention will become more apparent from the following description.
According to this invention, there is pro-voided a l-butene polymer containing 0 to 1 mole% of an olefin with 2 to 20 carbon atoms other than button and having (l) an intrinsic viscosity [n] of from 1.5 to 4.0 do
(2) a molecular weight distribution express sod by the ratio of its weight average molecular weight (ow) to its number average molecular weight (on), of not more than 6, and
(3) an isotacticity value of at least 95~.
The l-butene polymer is especially useful as a shaped article in the form Or a pipe structure.
The l-butene polymer in accordance with this invention may contain up to l mole Or an oleYin having 2 to 20 carbon atoms other than l-butene. Examples of such an olefin are ethylene, propylene, l-pentene, l-octene, l-d-cene, l-dodecene, i-octa(lecene Ann 4-meth~lpentene.
The l-butene pol~rner of trio invention his an intrinsic viscosity [no of from 1.5 to 4.0 dug preferably from 2 to 3.5 dug [characteristic lo If the intrinsic viscosity is too low beyond the specified range, the creep resistance characteristics and impact strength of the polymer are deteriorated If it is too high beyond the specified range, the polymer has inferior moldability. Moreover, the crystal transition speed of the polymer becomes us-satisfactorily low. Hence, the intrinsic viscosity of the polymer should be within the specified range.
The l-butene polymer of this invention has a molecular weight distribution, expressed by the ratio of its weight average molecular weight ow) to its number average molecular weight (My), i.e. Lillian, of not more than 6, preferably from 2 to 6, more preferably from 3.3 to 5.5, characteristic (2)]. I, its molecular weight distribution exceeds the upper limit specified, the polymer has inferior impact strength Hence, the molecular weight distribution should be not more than 6.
Furthermore the l-butene polymer of this invention has an isotacticity value of at least 95,~, preferably at least 95.5%, more preferably 95.5 to I
[characteristic I the isotacticity value of the polymer is less than 95~, the polymer has inferior rigidity and an unsatisfactorily low crystal transition speed. Lyons, the polymer should meet the above is-tactlcity value condition.
The Winnie is determined in the following manner.
I Using standard polystyrene ox a known molecular weight (mono-dispersed polystyrene, a product Or Toy Soda Mug Co., Ltd., Japan), the molecular weight M Or the polystyrene sample end its Pi (gel - ~29~5 permeation chromatography) court are measure. A
calibration curve for the molecular weight I no r (elusion volume) is drawn.
(2) A gel permeation chromatogr~m of the sample is taken by the GPC measuring method, and the number average molecular weight My Rand tune weight average molecular weight (Mw=~MiNNi) are calculated for polymer by (1) above, and the Join is determined.
The sample is prepared under the following conditions, and the conditions for GPC are as shown below.
Preparation of the sample (a) The polymer is taken into an Erlenmeyer flask together with o-dichlorobenzene so as to provide 15 mg-polymer/20 ml solvent solution.
(b) Into the Erler~eyer flask containing the sample is added 0.1% by weight, based on the polymer solution, of 2,6-dl-tert.-butyl-p-cresol as an anti-oxidant.
(c) The erlenmeyer is maintained at 140C
for one hour and then the contents are stirred for about one hour to dissolve the polymer and the antioxidant.
(d) Then, at 135 to 140C, the solution is filtered by a Millipore filter of 0.5 in an opening size.
(e) The filtrate is subjected to gel permeation chromatography.
Conditions for gel permeation chromatography (a) Device: Model 150C~ made by Waters Company ; (b) Column: TUSK GMH-6(6mm~ x 600 mm) made by Toy Soda Mfg. Co., Ltd.
I Amount of the sample: 400 (do Temperature: 135C
(e) Flow rate: 1 ml/min.
The isotacticity value is tri~dtact city determined from 13C-NMR (500 l~lHz) using the signal of carbon of the methane group of l-Dutene. in tune case of a copolymer of l-butene with another olefin~ tune methane group of the l-butene adjacent to the owner olefin is excluded in determining its triadtacticity.
The specific procedure of measuring the isotacticity value is as foliates:
Preparation of a sample (a) The polymer is taken into an NOR measure in sample tube having a diameter of 10 mm together with hexachlorobutadiene as a solvent so as to provide a 200 mg-polymer/1.5 ml solvent solution.
(b) The sample tube is left to stand at 120C for 12 hours, and then further maintained at about 250C for 2 to 3 minutes to dissolve the polymer completely and uniformly.
(c) The solution was further left to stand 20 at 120C for 1 to 2 hours.
The measurement was made on the sample so prepared.
Conditions for measurement . _ (a) Device 500 MHZ FIT NO (made by Nippon Danish OK
(b) measuring temperature The l-butene polymer of the Invention meets the combination of parameters (1) to (3). To the best of the Xno~ledges ox the present inventors, no l-butene polymer has been known which meets these parameters in combination. The l-butene polymers previously used for providing shaped articles, particlulary pipe structures, have an intrinsic viscosity [I] of about 2.5 to about 4.8 dug and a won ratio of about 6 to about 12 end an isotacticlty value of not more than I
The l-butene polymer of the invGnt.on can be shaped into pipe structures of the desired shape and size by utilizing melt-shaping methods Xno~Jn Don so.
For example, the l-butene polymer of the invention can be shaped, with or without additives of the types and amounts Russia do not substantially affect the excel-lent properties of the polymer, into pipe structures of the desired shape and size by a known melt-shaping method, for example melt-extrusion, and cooling the shaped article. Any suitable method can be selected for the above shaping and cooling. For example, a pipe structure may be produced by melting the polymer in an extrude, shaping it into a pipe by means of a straight head die a crosshead die, an offset die, or the like, and cooling the pipe with cooling air, cooling water, etc. while restricting its outside diameter by a sizing plate method, an outside mandrel method, a sizing box method, a inside mandrel method, etch The melt-shaping conditions and cooling con-dictions can be suitably selected. For example, the melt-shaping is carried out at a temperature of about 180 to about ~50C under an extruding pressure of about 70 to about 130 kg/cm , and the cooling may be carried out at a temperature of 0 to about 30C.
The additives which may be incorporated in the molding l-butene polymers as required may be those additives which are normally used for polyolefins.
They include, for example weatherabil~ty stabilizers, heat stabilizers, lubricant and slip agents, anti block-in agents, nucleating agents, pigments and dyes, anti-haze agents, Hal absorbers and inorganic and organic fillers.
Specific examples of these additives include heat~stabili~ers Or the phenol, sulfur, amine or phosphorus type, such as p-hydroxyanlsole, 3-methyl-4_1sopropyl phenol, ascorbic acid, 2-tert-butyl-4,6-.~' dim ethyl phenol, 2,6-di-tert-butyl Nazi., ,ropJl gullet, styrenated mixed crossly, 2-(1-m-thJ~
- cyclohexyl)-4,6-dimethyl phenol, 2,4-di-tert-b,ityl-5-methyl phenol, 3,5-di-tert-butyl-4-hydro~ Tony, 2,5-di-tert-butyl-4-hydroxy phenol, 4-hydroxymethyi-2,6-di-tert-butyl phenol, 2,4,6-tri-tert-butyl phenol, 2,6-di-tert-butyl-~-dimethylamino-p-cresol, l,l-bis-(4-hydroxy phenol) cyclohexane, octal alto, nordihydroguaiaretic acid, dodecyl alto, butylated bisphenol A, 4,4'-methylene-bis(2-tert-butyl-6-methyl phenol), 2,2'-methylene-bis(4-methyl-6-tert-bu~yl phenol), 4,4'-thio-bls~2-methyl-6-tert-butyl phenol),
The l-butene polymer is especially useful as a shaped article in the form Or a pipe structure.
The l-butene polymer in accordance with this invention may contain up to l mole Or an oleYin having 2 to 20 carbon atoms other than l-butene. Examples of such an olefin are ethylene, propylene, l-pentene, l-octene, l-d-cene, l-dodecene, i-octa(lecene Ann 4-meth~lpentene.
The l-butene pol~rner of trio invention his an intrinsic viscosity [no of from 1.5 to 4.0 dug preferably from 2 to 3.5 dug [characteristic lo If the intrinsic viscosity is too low beyond the specified range, the creep resistance characteristics and impact strength of the polymer are deteriorated If it is too high beyond the specified range, the polymer has inferior moldability. Moreover, the crystal transition speed of the polymer becomes us-satisfactorily low. Hence, the intrinsic viscosity of the polymer should be within the specified range.
The l-butene polymer of this invention has a molecular weight distribution, expressed by the ratio of its weight average molecular weight ow) to its number average molecular weight (My), i.e. Lillian, of not more than 6, preferably from 2 to 6, more preferably from 3.3 to 5.5, characteristic (2)]. I, its molecular weight distribution exceeds the upper limit specified, the polymer has inferior impact strength Hence, the molecular weight distribution should be not more than 6.
Furthermore the l-butene polymer of this invention has an isotacticity value of at least 95,~, preferably at least 95.5%, more preferably 95.5 to I
[characteristic I the isotacticity value of the polymer is less than 95~, the polymer has inferior rigidity and an unsatisfactorily low crystal transition speed. Lyons, the polymer should meet the above is-tactlcity value condition.
The Winnie is determined in the following manner.
I Using standard polystyrene ox a known molecular weight (mono-dispersed polystyrene, a product Or Toy Soda Mug Co., Ltd., Japan), the molecular weight M Or the polystyrene sample end its Pi (gel - ~29~5 permeation chromatography) court are measure. A
calibration curve for the molecular weight I no r (elusion volume) is drawn.
(2) A gel permeation chromatogr~m of the sample is taken by the GPC measuring method, and the number average molecular weight My Rand tune weight average molecular weight (Mw=~MiNNi) are calculated for polymer by (1) above, and the Join is determined.
The sample is prepared under the following conditions, and the conditions for GPC are as shown below.
Preparation of the sample (a) The polymer is taken into an Erlenmeyer flask together with o-dichlorobenzene so as to provide 15 mg-polymer/20 ml solvent solution.
(b) Into the Erler~eyer flask containing the sample is added 0.1% by weight, based on the polymer solution, of 2,6-dl-tert.-butyl-p-cresol as an anti-oxidant.
(c) The erlenmeyer is maintained at 140C
for one hour and then the contents are stirred for about one hour to dissolve the polymer and the antioxidant.
(d) Then, at 135 to 140C, the solution is filtered by a Millipore filter of 0.5 in an opening size.
(e) The filtrate is subjected to gel permeation chromatography.
Conditions for gel permeation chromatography (a) Device: Model 150C~ made by Waters Company ; (b) Column: TUSK GMH-6(6mm~ x 600 mm) made by Toy Soda Mfg. Co., Ltd.
I Amount of the sample: 400 (do Temperature: 135C
(e) Flow rate: 1 ml/min.
The isotacticity value is tri~dtact city determined from 13C-NMR (500 l~lHz) using the signal of carbon of the methane group of l-Dutene. in tune case of a copolymer of l-butene with another olefin~ tune methane group of the l-butene adjacent to the owner olefin is excluded in determining its triadtacticity.
The specific procedure of measuring the isotacticity value is as foliates:
Preparation of a sample (a) The polymer is taken into an NOR measure in sample tube having a diameter of 10 mm together with hexachlorobutadiene as a solvent so as to provide a 200 mg-polymer/1.5 ml solvent solution.
(b) The sample tube is left to stand at 120C for 12 hours, and then further maintained at about 250C for 2 to 3 minutes to dissolve the polymer completely and uniformly.
(c) The solution was further left to stand 20 at 120C for 1 to 2 hours.
The measurement was made on the sample so prepared.
Conditions for measurement . _ (a) Device 500 MHZ FIT NO (made by Nippon Danish OK
(b) measuring temperature The l-butene polymer of the Invention meets the combination of parameters (1) to (3). To the best of the Xno~ledges ox the present inventors, no l-butene polymer has been known which meets these parameters in combination. The l-butene polymers previously used for providing shaped articles, particlulary pipe structures, have an intrinsic viscosity [I] of about 2.5 to about 4.8 dug and a won ratio of about 6 to about 12 end an isotacticlty value of not more than I
The l-butene polymer of the invGnt.on can be shaped into pipe structures of the desired shape and size by utilizing melt-shaping methods Xno~Jn Don so.
For example, the l-butene polymer of the invention can be shaped, with or without additives of the types and amounts Russia do not substantially affect the excel-lent properties of the polymer, into pipe structures of the desired shape and size by a known melt-shaping method, for example melt-extrusion, and cooling the shaped article. Any suitable method can be selected for the above shaping and cooling. For example, a pipe structure may be produced by melting the polymer in an extrude, shaping it into a pipe by means of a straight head die a crosshead die, an offset die, or the like, and cooling the pipe with cooling air, cooling water, etc. while restricting its outside diameter by a sizing plate method, an outside mandrel method, a sizing box method, a inside mandrel method, etch The melt-shaping conditions and cooling con-dictions can be suitably selected. For example, the melt-shaping is carried out at a temperature of about 180 to about ~50C under an extruding pressure of about 70 to about 130 kg/cm , and the cooling may be carried out at a temperature of 0 to about 30C.
The additives which may be incorporated in the molding l-butene polymers as required may be those additives which are normally used for polyolefins.
They include, for example weatherabil~ty stabilizers, heat stabilizers, lubricant and slip agents, anti block-in agents, nucleating agents, pigments and dyes, anti-haze agents, Hal absorbers and inorganic and organic fillers.
Specific examples of these additives include heat~stabili~ers Or the phenol, sulfur, amine or phosphorus type, such as p-hydroxyanlsole, 3-methyl-4_1sopropyl phenol, ascorbic acid, 2-tert-butyl-4,6-.~' dim ethyl phenol, 2,6-di-tert-butyl Nazi., ,ropJl gullet, styrenated mixed crossly, 2-(1-m-thJ~
- cyclohexyl)-4,6-dimethyl phenol, 2,4-di-tert-b,ityl-5-methyl phenol, 3,5-di-tert-butyl-4-hydro~ Tony, 2,5-di-tert-butyl-4-hydroxy phenol, 4-hydroxymethyi-2,6-di-tert-butyl phenol, 2,4,6-tri-tert-butyl phenol, 2,6-di-tert-butyl-~-dimethylamino-p-cresol, l,l-bis-(4-hydroxy phenol) cyclohexane, octal alto, nordihydroguaiaretic acid, dodecyl alto, butylated bisphenol A, 4,4'-methylene-bis(2-tert-butyl-6-methyl phenol), 2,2'-methylene-bis(4-methyl-6-tert-bu~yl phenol), 4,4'-thio-bls~2-methyl-6-tert-butyl phenol),
4,4'-thio-bis(3-methyl-6-tert-butyl phenol), 2,2'-thio-bis(4-methyl-6-tert-butyl phenol), 2,2'-methylene-bis(4-ethyl-6-tert-butyl phenol), n-stearoyl-p-arnino-phenol, 4,4'-butylidene-bis(6-tert-butyl-m-cresol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide,, 2,2'-methylene-bis(4-methyl-6-cyclohexyl phenol), 4,4'-bis(2,6-di-tert-butyl phenol), 2,2'-dihydroxy-3,3'-di-(~-methylcyclohexyl)-5,5'-dimethyl dim ethyl diphenyl methane, 4,4'-methylene-bis(2,6-di-tert-butyl phenol), d,~-~-tecopherol, 2,2'-methylene-bis(6-~-rnethylbenzyl-p-cresol), 2,6-bis(2'-hydroxy-3'-tert-butyl-5'-rnethylbenzyl)-4-methyl phenol, n-oct~decyl-3-(4'-hydroxy-3',5'-di-tert-butyl phenyl)prop1onate, 1,1,3-tris(2-rnethyl-4-hydroxy-5-tert-butyl phenol)-butane, 4,4'-butylidene-bis(3-methyl-tert-butyl phenol), 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis-(octylthio)-1,3,5-triazine, 2,4-bis(4-hydroxy-3,5-di-tert-butylanllino)-6-(n-octylthlo)-1,3 J treason, 1,3,5-trls(4-tert-blltyl-3-hydroxy-2,6-dimethylbennzyl)-s-triazine-2,4,6~ triune, tris(3,5-di-~ert-butyl-4-hydroxy~phosphate, 1,3,5-trimethyl-2,4, G-tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzyl Bunsen, 35 1,3,5-tris(3'~5'-dl-tert-butyl-4'~hydroxybenzyl)-ss-treason (lH,3H,5H)-trione, di-stearyl(4-hydroxy-3-rnethyl-5-tert-butylbenzyl)malorlate, ethyleneglycol-bis[~,3-bis(3'-tert-butJl-4t-hydrox~fph-n,~ `ou~,Jra',, tris[2-ter~-butyl-4-thio(2'-met'nyl-4'-hydroxy-5'--tert-butylphenyl3-5-metlnylp'rienyl~phosphite, Tories-[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenJl)-propionate]methane, phenol condensation products hindered phenol derivative, 3,5-di-tert-butyl-LI-hydroxybenzyl phosphoric acid, di-stear~-l ester, 2-mercaptobenzimidazole, phenothiazine, '-diphenyl-Thor, tetramethyl thrum disulfide, N-oxydi-ethylene-2-benzothiazolylsulfenamide, N-cyclohexyl-2-benzothiazolylsulfenamide, cyclohexylamine salt ox 2-mercaptobenzothiazole, N,N-diisopropyl-2-benzo-thiazelylsulfenamide, 2-N,N-diethylthio carbamol trio)-benzothiazole~ tetraethylthiuram disulfide, dibenzo-thiazyl disulfide, zinc diethyldithiocarbamate, zincethylphenyldithiocarbamate, zinc di-n-butyldithio-carbamate, dilaulyl thiodipropionate, dilaulyl thud-1-1l-methylbutyrate, dimyristyl-3,3'~thiodipropionate, laurel stearylthiodipropionate, distearyl trio-dlpropionate, distearyl thiodibutyrate, pent-(erysrythyl-tetra-~-mercaptolauryl)propionate, phenol-~-naphthylamine, phenyl-~-naphthyl amine, oxanilide, hydrazine derivatives, 9,10-dihydro-9-oxa-10-p'nos-phenanthrene-10-oxide, triphenyl phosphate, 2-ethyl-: 25 Huxley cold phosphate, dilauryl phosphate, tri-iso-octyl phosphate, tris(2,4-di-tert-butyl phenol phosphate, trilauryl phosphate, trilauryl dl~thiophosphlte~
trilauryl trithiophQsphite, trinonylphenyl phosphate, distearyl pentaerythrltol diphosphite, tris(mixed moo and dlnonyl phenol phosphate, trioctadecyl phosphate, 1,1,3-tri~(2-methyl~4-di-tridecyl phosphate-turret butylphenyl)butane and diphenyl phosphate, 4,4'-but~lidene-bis(3-methyl-6-butyl)trldecyi phosphate, and4,4'-butyl1dene-bis~3-methyl-6-tert-butylphenyl-dii-tridecyl)phosphite; weather ability stabilizers such as2,4-dlhydroxybenzophenone, 2-hydroxy-5-chlorobenzo-phenone, 2-~2'-hydroxy methyl phenyl)ben~zotriazole, so 2-hydroxy-4-methoxy~enzovrlenone, 2,2'-di-:J-ir~xy-~-metnoxybenzophenone, 2,2',4,4'-tetrahydroxJsenzs-phenone, 2-nydroxy-4-methoxy-4'-chlorober!zopncno.r.-, p-tert-butylphenyl salicylate, 2,2'-dihydroxy-4,4'-dimethoxybenzopnenone, ethyl-2-cyono-3,3-diphenyl acrylate 2-hydroxy-4-benzyloxybenzophonone, 2-(2'-hydroxy-3'-tert-butyl-5'-methyl phenol sheller benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl phenyl)benzotriazole, 2-(2'-hydroxy-4'-tert-octoxy lo phenyl)benzotriazole, p-octyl phenol salicylate, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-4'-octoxy phenol)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-hexyl phenyl)benzotriazole, 2~(2'-hydroxy-3'-tert-butyl-5'-Huxley phenyl)benzotriazole, 2-~2'-hydroxy-3',5'-di-tert-butyl phenyl)-5-chlorobenzotriazole, 2-ethyl-2'-ethoxy-5'-tert butyl-N,N'-diphenyl oxamide, Dow-tert-butyl phenyl-3,5-di-tert-butyl-4-hydroxy bonniest, 3,5-di-tert-butyl-4-hydroxy myristyl bonniest, bus-(2,2',6,6' tetramethyl-4-piperidine)sebacate, ~2,2'-thio-bis(4-tert-octyl phenolate)]-tertbutylamino nickel (II), nickel salt of bis(3~5-di-tert-butyl-4-hydroxy-bouncily phosphoric acid moo ethyl ester, nickel salt of bis~3,5-di-tert-butyl-4-hydroxybenzoyl phosphoric acid moo octal ester, nickel salt of Thebes-(4,4'-alkylphenol), dim ethyl succinate~2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperizyl)ethanol~polyconsatlo, polyL~6~(1,1,3,3-tetramethylbutyl)lmino}-1,3,5-triazine-2,4-diyl{4-(2,2,6,G-tetramethyl piperizyl)-imino}he~amethylene~, and 2-hydr~xy-4-dodecyloxy, benzophenone; aliphatic hydrocarbons such as paraffin wax, polyethylene wax and polypropylene wax, higher Patty acids such as caprice cold, Laurie acid, myristic acid, palmitic acid, mar~aric acid, Starkey acid, arachidic acid and bunk acldj metal salts of the higher fatty acids such as the lithium, calcium, sodium, magnesium and potassium salts, aliphat1c I
alcohols such as palmityl alcsrlol, cet-Jl echo and stroll alcohol, aliphatic asides suck as careered, capr~lamide, caprice aside, Laurie aside, rnyr~s,ic amid palmitic aside, strummed, esters Boone fatty acids and alcohols, and fluorine-containing Come pounds such as fluoroalkylcarboxylic acids or the metal salts thereof, and fluoroalkylsul,onic acids or the metal salts thereof; antiblockin~ agents such as silica, talc, clay and diatomaceous earth; antistatic agents such as lauryldiethanolamine, dioxyethylene laurylamine, N,N-bis(2 hydroxyethyl)stearylamine, stroll monoglyceride, sodium ditridecyl sulfosuc-Senate, sorbitan fatty esters, a mixture ox an NUN-bis(2-hydroxyethyl)alkylamine and an n-alkyl alcohol silica, polyoxyethylene laurylamine, and stroll diethanolamine menstruate; anti-haze agents such as glycerin acid esters, sorbitan acid esters, acryl-sarcosines, polyoxyethylene glycerine menstruate and diethanolamide; coloring agents such as titanium dioxide, calcium carbonate, carbon black, lead sub-oxide, cadmium red, vermilion, red iron oxide, brown iron oxide barium yellow titanium yellow, viridian, ultramarine, cobalt blue, cobalt violet, ago pigments nutrias lake pigments, vitro lake pimento, basic dye lakes, phthalocyanine pigments, organic fluorescent pigments and pearl essence; inorganic or organic fillers such as calcium carbonate, clay, talc, silica, diatomaceous earth, siliceous sand, mica powder, slate flour, alumina white, wood flour, hard rubber dust and cellulose powder; Hal absorbers such as calcium oxide, lithium Stewart, sodium Stewart, an epoxlda-lion product of octal Stewart, hydrotalcite~ calcium Stewart, zinc Stewart and calcium 12-hydroxy-Stewart; and nucleating agents such as organic carbox~llc acids or the metal salts thereon and ben~ylidene sorbitol or the derivatives thereof.
The arnollnts of these additives ma ye pro-pertly chosen so long as they do not substantially affect the excellent properties of the Litton polymer. For examples, the amounts may be about 0.05 to about 0.5% by weight for the weather ability stabilizers, to about 0.05 to about 0.5~ by sleight for the heat stabilizers, about 0.05 to about 2% by weight for the slip agents or lubricants, about 0.05 to about 1% by weight for the nucleating agents, about 0.1 to about I by weight for the coloring agents, about 0.01 to about 0.5% by weight for the anti block-in agents, about 0.1 to about 2% by weight for the aunts agents, about 0.1 to about 2% by weight for the antistatic agents, and about 0.1 to about 2% by weight for the fillers, all based on the weight of the button polymer.
The button polymer of this invention suitable for production of shaped articles, portico-laxly pipe structures can be produced by using a selected catalyst. For example, it can be prepared by polymerizing button or copolymerizing l-butene with up to 1 mole of an olefin with 2 to 12 carbon atoms other than l-butene in the presence of a gala-lust composed of (A) a solid highly active titanium catalyst component, (B) a trialkyl aluminum come pound and (C) at least one organosillcon compound selected from the group consisting of triethylmethoxy-Solon triethylethoxysllane, tripropylmethoxysilane, methyltriethoxysilane) ethyltriethoxysilane~ vinyl-triethoxysilane> n-propyltriethoxysilane, phenol-triethoxysilane and tetraethoxysilane.
The solid highly active titaniurrl satal~st component (A that can ye used in this inversion con assay magnesium, titanium, halogen and a divester of a dicarboxylic acid as essential components.
The titanium catalyst component (A) desirably has a magnesium/titanium atomic ratio of from about 2 to about loo preferably from about 4 to about 70, a halogen/titanium atomic ratio of from about 4 to about ; loo preferably from about 6 to about 40, and a divester/
lo titanium mole ratio of from about I to about lo preferably from about 0.4 to about 6. The specific surface area of the titanium catalyst component (A) is preferably at least about 3 mug more preferably at least about 40 m go especially preferably about 15 loo mug to about 800 mug Usually, the titanium catalyst component (A) does not substantially liberate a titanium compound when treated by a simple means such as washing with hexane at room temperature.
The X-ray spectrum of the titanium catalyst component (A) shows that irrespective of the starting magnesium compound used for its preparation, it shows an amorphous nature with regard to the magnesium compound or it is much more amorphous than a usual corr~ercially available magnesium dwelled.
In addition to the aforesaid essential components, the titanium catalyst component PA) may further include other elements, metals, functional groups, electron donors, etc. to an extent that -they do not adversely affect the performance of the catalyst.
Or the component (A) may be diluted with an organic or inorganic delineate.
The titanium catalyst component AYE may be ; prepared by contacting a magnesium compound or metallic magnesium), a titanium compound and a divester or a compound capable of forming a divester with one another with or without using another reagent in accordance with the same method of preparing known highly active I, o titanium catalyst components, which are disclosed, for example, in British Patent Specifications issue. 14~261~, 1554340 and 1554248 and U. S. patent iJos 2157435, 4076924, 4085276, 4250285, 4232139, 4143223, 4315~74, 4330649, 4401589 and 4335015 and European Patent Specification No. 22675.
Some examples of the procedure of producing the titanium catalyst component (A) are summarized below.
(1) A magnesium compound or a complex of a magnesium compound and an electron donor is pro-treated or not-pretreated with an electron donor nor ompo~l nut a reaction aid such as an organoaluminum ~o~poudn or a halogen-containing silicon compound in the presence or absence of an electron donor or a pulverization aid with or without pulverization. The resulting solid is reacted with a titanium compound which is in the liquid state under the reaction conditions.
In the above procedure, a divester of a dicarboxylic acid or a compound capable of forming the divester is used at least once as the electron donor.
(2) A magnesium compound in the liquid state having no reducing ability is reacted with a titanium compound in the liquid state in the presence of a divester of a dicarboxylic acid or a compound capable of forming the divester to precipitate a solid titanium complex.
(3) The product obtained in (2) above is further reacted with a titanium compound.
I The product obtained in I or (?) is further reacted with a titanium compound and as an electron donor a divester of a dicarboxylic acid or a compound capable of forming the divester.
trilauryl trithiophQsphite, trinonylphenyl phosphate, distearyl pentaerythrltol diphosphite, tris(mixed moo and dlnonyl phenol phosphate, trioctadecyl phosphate, 1,1,3-tri~(2-methyl~4-di-tridecyl phosphate-turret butylphenyl)butane and diphenyl phosphate, 4,4'-but~lidene-bis(3-methyl-6-butyl)trldecyi phosphate, and4,4'-butyl1dene-bis~3-methyl-6-tert-butylphenyl-dii-tridecyl)phosphite; weather ability stabilizers such as2,4-dlhydroxybenzophenone, 2-hydroxy-5-chlorobenzo-phenone, 2-~2'-hydroxy methyl phenyl)ben~zotriazole, so 2-hydroxy-4-methoxy~enzovrlenone, 2,2'-di-:J-ir~xy-~-metnoxybenzophenone, 2,2',4,4'-tetrahydroxJsenzs-phenone, 2-nydroxy-4-methoxy-4'-chlorober!zopncno.r.-, p-tert-butylphenyl salicylate, 2,2'-dihydroxy-4,4'-dimethoxybenzopnenone, ethyl-2-cyono-3,3-diphenyl acrylate 2-hydroxy-4-benzyloxybenzophonone, 2-(2'-hydroxy-3'-tert-butyl-5'-methyl phenol sheller benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl phenyl)benzotriazole, 2-(2'-hydroxy-4'-tert-octoxy lo phenyl)benzotriazole, p-octyl phenol salicylate, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-4'-octoxy phenol)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-hexyl phenyl)benzotriazole, 2~(2'-hydroxy-3'-tert-butyl-5'-Huxley phenyl)benzotriazole, 2-~2'-hydroxy-3',5'-di-tert-butyl phenyl)-5-chlorobenzotriazole, 2-ethyl-2'-ethoxy-5'-tert butyl-N,N'-diphenyl oxamide, Dow-tert-butyl phenyl-3,5-di-tert-butyl-4-hydroxy bonniest, 3,5-di-tert-butyl-4-hydroxy myristyl bonniest, bus-(2,2',6,6' tetramethyl-4-piperidine)sebacate, ~2,2'-thio-bis(4-tert-octyl phenolate)]-tertbutylamino nickel (II), nickel salt of bis(3~5-di-tert-butyl-4-hydroxy-bouncily phosphoric acid moo ethyl ester, nickel salt of bis~3,5-di-tert-butyl-4-hydroxybenzoyl phosphoric acid moo octal ester, nickel salt of Thebes-(4,4'-alkylphenol), dim ethyl succinate~2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperizyl)ethanol~polyconsatlo, polyL~6~(1,1,3,3-tetramethylbutyl)lmino}-1,3,5-triazine-2,4-diyl{4-(2,2,6,G-tetramethyl piperizyl)-imino}he~amethylene~, and 2-hydr~xy-4-dodecyloxy, benzophenone; aliphatic hydrocarbons such as paraffin wax, polyethylene wax and polypropylene wax, higher Patty acids such as caprice cold, Laurie acid, myristic acid, palmitic acid, mar~aric acid, Starkey acid, arachidic acid and bunk acldj metal salts of the higher fatty acids such as the lithium, calcium, sodium, magnesium and potassium salts, aliphat1c I
alcohols such as palmityl alcsrlol, cet-Jl echo and stroll alcohol, aliphatic asides suck as careered, capr~lamide, caprice aside, Laurie aside, rnyr~s,ic amid palmitic aside, strummed, esters Boone fatty acids and alcohols, and fluorine-containing Come pounds such as fluoroalkylcarboxylic acids or the metal salts thereof, and fluoroalkylsul,onic acids or the metal salts thereof; antiblockin~ agents such as silica, talc, clay and diatomaceous earth; antistatic agents such as lauryldiethanolamine, dioxyethylene laurylamine, N,N-bis(2 hydroxyethyl)stearylamine, stroll monoglyceride, sodium ditridecyl sulfosuc-Senate, sorbitan fatty esters, a mixture ox an NUN-bis(2-hydroxyethyl)alkylamine and an n-alkyl alcohol silica, polyoxyethylene laurylamine, and stroll diethanolamine menstruate; anti-haze agents such as glycerin acid esters, sorbitan acid esters, acryl-sarcosines, polyoxyethylene glycerine menstruate and diethanolamide; coloring agents such as titanium dioxide, calcium carbonate, carbon black, lead sub-oxide, cadmium red, vermilion, red iron oxide, brown iron oxide barium yellow titanium yellow, viridian, ultramarine, cobalt blue, cobalt violet, ago pigments nutrias lake pigments, vitro lake pimento, basic dye lakes, phthalocyanine pigments, organic fluorescent pigments and pearl essence; inorganic or organic fillers such as calcium carbonate, clay, talc, silica, diatomaceous earth, siliceous sand, mica powder, slate flour, alumina white, wood flour, hard rubber dust and cellulose powder; Hal absorbers such as calcium oxide, lithium Stewart, sodium Stewart, an epoxlda-lion product of octal Stewart, hydrotalcite~ calcium Stewart, zinc Stewart and calcium 12-hydroxy-Stewart; and nucleating agents such as organic carbox~llc acids or the metal salts thereon and ben~ylidene sorbitol or the derivatives thereof.
The arnollnts of these additives ma ye pro-pertly chosen so long as they do not substantially affect the excellent properties of the Litton polymer. For examples, the amounts may be about 0.05 to about 0.5% by weight for the weather ability stabilizers, to about 0.05 to about 0.5~ by sleight for the heat stabilizers, about 0.05 to about 2% by weight for the slip agents or lubricants, about 0.05 to about 1% by weight for the nucleating agents, about 0.1 to about I by weight for the coloring agents, about 0.01 to about 0.5% by weight for the anti block-in agents, about 0.1 to about 2% by weight for the aunts agents, about 0.1 to about 2% by weight for the antistatic agents, and about 0.1 to about 2% by weight for the fillers, all based on the weight of the button polymer.
The button polymer of this invention suitable for production of shaped articles, portico-laxly pipe structures can be produced by using a selected catalyst. For example, it can be prepared by polymerizing button or copolymerizing l-butene with up to 1 mole of an olefin with 2 to 12 carbon atoms other than l-butene in the presence of a gala-lust composed of (A) a solid highly active titanium catalyst component, (B) a trialkyl aluminum come pound and (C) at least one organosillcon compound selected from the group consisting of triethylmethoxy-Solon triethylethoxysllane, tripropylmethoxysilane, methyltriethoxysilane) ethyltriethoxysilane~ vinyl-triethoxysilane> n-propyltriethoxysilane, phenol-triethoxysilane and tetraethoxysilane.
The solid highly active titaniurrl satal~st component (A that can ye used in this inversion con assay magnesium, titanium, halogen and a divester of a dicarboxylic acid as essential components.
The titanium catalyst component (A) desirably has a magnesium/titanium atomic ratio of from about 2 to about loo preferably from about 4 to about 70, a halogen/titanium atomic ratio of from about 4 to about ; loo preferably from about 6 to about 40, and a divester/
lo titanium mole ratio of from about I to about lo preferably from about 0.4 to about 6. The specific surface area of the titanium catalyst component (A) is preferably at least about 3 mug more preferably at least about 40 m go especially preferably about 15 loo mug to about 800 mug Usually, the titanium catalyst component (A) does not substantially liberate a titanium compound when treated by a simple means such as washing with hexane at room temperature.
The X-ray spectrum of the titanium catalyst component (A) shows that irrespective of the starting magnesium compound used for its preparation, it shows an amorphous nature with regard to the magnesium compound or it is much more amorphous than a usual corr~ercially available magnesium dwelled.
In addition to the aforesaid essential components, the titanium catalyst component PA) may further include other elements, metals, functional groups, electron donors, etc. to an extent that -they do not adversely affect the performance of the catalyst.
Or the component (A) may be diluted with an organic or inorganic delineate.
The titanium catalyst component AYE may be ; prepared by contacting a magnesium compound or metallic magnesium), a titanium compound and a divester or a compound capable of forming a divester with one another with or without using another reagent in accordance with the same method of preparing known highly active I, o titanium catalyst components, which are disclosed, for example, in British Patent Specifications issue. 14~261~, 1554340 and 1554248 and U. S. patent iJos 2157435, 4076924, 4085276, 4250285, 4232139, 4143223, 4315~74, 4330649, 4401589 and 4335015 and European Patent Specification No. 22675.
Some examples of the procedure of producing the titanium catalyst component (A) are summarized below.
(1) A magnesium compound or a complex of a magnesium compound and an electron donor is pro-treated or not-pretreated with an electron donor nor ompo~l nut a reaction aid such as an organoaluminum ~o~poudn or a halogen-containing silicon compound in the presence or absence of an electron donor or a pulverization aid with or without pulverization. The resulting solid is reacted with a titanium compound which is in the liquid state under the reaction conditions.
In the above procedure, a divester of a dicarboxylic acid or a compound capable of forming the divester is used at least once as the electron donor.
(2) A magnesium compound in the liquid state having no reducing ability is reacted with a titanium compound in the liquid state in the presence of a divester of a dicarboxylic acid or a compound capable of forming the divester to precipitate a solid titanium complex.
(3) The product obtained in (2) above is further reacted with a titanium compound.
I The product obtained in I or (?) is further reacted with a titanium compound and as an electron donor a divester of a dicarboxylic acid or a compound capable of forming the divester.
(5) A magnesium company or a complex of a magnesiwn compound and an electron donor is pulverized in the presence of a titanium confound and in the presence or absence of an electron donor and a pulverization aid, and with or without pretreatment :~, I
with an electron donor and/or a reaction at' Ill us an organoaluminurn compound or a halogen-conta_riing silicon compound, treated with a halogen a halogen compound or an aromatic hydrocarbon. In tune argyle procedure, a divester of a dicarboxylic acid or a compound capable of forming the divester is used at least once as the electron donor.
Preferred among these methods are those in which a liquid titanium halide is used, or a halogenated hydrocarbon is used after or during the use of tune titanium compound.
The electron donor used in the above methods of preparation is not necessarily limited to the divester or diester-forming compound. There may be used other electron donors such as alcohols, phenols, aldehydes, kittens, ethers, carboxy~ic acids Cry yoke, carboxylic acid anhydrides,-c~r~sn c acid esters, - monstrous and amine. It is essential however that the divester of a dicarboxylic acid or the divester-forming compound be used at least once.
Preferred examples of the divester as an essential component of the solid highly active titanium catalyst component (A) used in this invention include divesters of dicarboxylic acids in which two carboxyl groups are attached to one carbon atom of the hydrocarbon moiety or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carton atoms of the hydrocarbon moiety, and divesters of dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of the heterocyclic compound moiety containing at least two carbon atoms.
More specific examples of the preferred divesters are divesters, preferably di(C1-C20)a1kyl esters in which the two alkyd groups may be identical or different, of dicarboxylic acids in which two carboxyl groups are attached to one carbon atom of so an aliphatic hydrocarbon moiety having&) 1 to I error atoms or dicarboxylic acids in which one sar~oxyl group is attached to each of the Tao adjoining carton atoms of an aliphatic hydrocarbon moiety hygiene 2 to 20 carbon atoms; divesters, preferably di(Cl-C20)alkyl esters in which the two alkyd esters may be identical ox different, of dicarboxylic acids in which two earboxyl groups are attached to one carbon atom of an alicyelie hydrocarbon moiety having 3 to 20 carbon atoms or diearboxylie acids in which one earboxyl group is attached to each of the two adjoining carbon atoms of the aforesaid alicyclic hydrocarbon moiety; divesters, preferably di(Cl-C20)alkyl esters in which the two alkyd groups may be identical or different, of diearboxylie acids in which one carboxyl group is attached to each of the adjoining carbon atoms (at the ortho-position) of an aromatic hydrocarbon moiety having 6 to 20 carbon atoms; and divesters, preferably di(Cl-C20)alkyl esters, of diearboxylie acids in which one earboxyl group is attached to each of the two adjoining carbon atoms of a heteroeyclie compound moiety containing at least two carbon atoms and 1 to 10 hotter atoms selected from the group consisting of 0, N and S atoms.
Specific examples of the diearboxylie acids exemplified above include Masonic acid; substituted Malone acids such as methylmalonie acid, ethylmalonie acid, isopropylmalonie acid, allylmalonie acid, and phenylmalonic acid; succinic acid; substituted Suzanne acids such as methylsuceinie acid, dim ethyl-Sweeney acid, ethylsuee.inie acid, methylethylsueeinic acid and itaconie acid; rnaleic acid; substituted Molly acids such as eitraeonie acid and dimethylmaleie acid; fumier acid; substituted fumier acid such as rne~ylfw~ric acid and ethyl~rr~ric acid; alicyclic dicarboXylic acids such as eyelopentane-l~l diearboxylie acid, eyelopentane-1,2-diearboxylie acid, election-.. Jo _ 17 -dicarboxylic acid, cyclohex~ene~ -dicar-,o~.~lic acid, cyclohexene-2,3-dicarboxylic acid, cyclshexene-7,4-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, Nadir Acid, iilethylnadic Acid, and l-allylcyclone~ane-3,4-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,2-dicarboxylic acid and naphthalene-2,3-dicarboxylic acid; and heterocyclic dicarboxylic acids such as foreign-dicarboxylic acid, 4,5-dihydrofurane-2,3,-dicarboxylic acid, benzopyran-3,4-dicarboxylic acid, purl-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, and indwell-dicarboxylic acid.
Preferably, at least one of the alcohol components of the dicarboxylic acid divesters exemplified above has at least 2 carbon atoms, for example 2 to 20 carbon atoms, especially at least 3 carbon atoms It is above all preferred that both of the alcohol components have at least 2 carbon atoms, especially at least 3 carbon atoms. Examples include the deathly esters, diisopropyl esters, di-n-propyl esters, di-n-butyl esters diisobutyl esters, di-tert-butyl esters, dismal esters, di-n-hexyl esters, Dow-ethylhexyl esters, di-n-octyl esters, deciduously esters, and ethyl-n-butyl esters of the above-exemplified dicarboxylic acids.
A magnesium compound having no reducing ability can be utilized in the preparation of the solid highly active titanium catalyst component (A.
The magnesium compound includes, for example, magnesium halicies such as rna~nesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; Cluck alkoxyfnagnesium halides such as methoxymagnesium chloride, ethics magnesium chloride, isopropoxymagnesiurn chloride, bu~oxymagnesium chloride and octoxymagnesiurn chloride; C6-C20 aryloxymay~nesium halides such as phenoxyma~nesiurn chloride and methylphenox~magnesium chloride; C -C70 al~oxyrr~a7~nesi~ m-such as ethics magnesium, issuers r,lagnesiur-., buttocks rnagnesiuM, n-octoxy rnagnesiu,l7 and 2-ethylriexo~,y magnesium; C6-C20 aureole magnesium such as phonics magnesium and dimethylphenoxy magnesium; and carboxylic acid salts ox magnesium such as magnesium laureate and magnesium Stewart.
Preferred are halogen-containing magnesium compounds, particularly, magnesium chloride, alkoxy magnesium chlorides and aryloxyMagnesium chlorides are preferred.
Suitable titanium compounds used to prepare the titanium catalyst component (A are tetravalent titanium compounds represented by Ti(OR)gX4_g in which R is a hydrocarbon group, X is halogen and g is O to 4.
Examples of R are alkyd groups having l to 6 carbon atoms. Examples of X are Of, By and I.
Specific examples of such titanium compounds ; include titanium tetrahalides such as Tickle, Tuber and Tao; alkoxytitanium trihalides such as Ti~OCH3)C13, Ti(OC2H5)C13, Tao n-C4Hg)Cl3, Chokeberry and Tao iso-C4Hg)Br3; alkoxytitanium deludes such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Tao n-C4Hg)2Cl2 and Chokeberry trialkoxytitanium monohalides such as Ti(OCH3~3C1, Ti(OC2H5)3Cl, Tao n-C4Hg)3Cl and Chokeberry and tetraalkoxytitaniums such as Tush, Tokyo and Tao n-C4Hg)4. Among -them, the halo~en-containing titanium compounds, particularly titanium tetrahalides, especially preferably titanium tetrachloride, are preferred. These titanium compounds may be used singly or as a mixture. Or they may be used as diluted in hydrocarbons or halogenated hydrocarbons.
In the preparation of the titanium catalyst component (A), the amounts of the titanium compound, the magnesium compound the electron donor to be supported, and the other electron donors such as so alcohols, ?nenols, rnonocarboxylic acid ester s, true silicon compound and the aluminum compound Russia Roy used as required differ depending upon the method of preparation and cannot be defined in a general manner.
For example, about 0.1 to abut 10 moles of the electron donor to be supported and about 0.05 mole to about 1000 motes of the titanium compound may be used per mole of the magnesium compound.
The catalyst composed of (A) the titanium catalyst component that can be obtained as above, (B) a trialkyl aluminum compound and (C) an organosilicon compound selected from the group stated hereinabove can be utilized in producing the l-butene polymer in accordance with this invention.
Examples of preferred trialkyl aluminum compounds (B) are triethyl aluminum and triisobutyl aluminum.
The polymerization or copolymerization of 1-butane can be carried out in the liquid phase. An inert solvent such as hexane, Hutton and kerosene may be used as a reaction medium, but l-butene itself may be used as a reaction solvent. The amount of the catalyst used is preferably such that per liter of the volume of the reaction zone, the compound (A) is used in an amount of about 0.0001 to about 1.0 millimole calculated as titanium atom; the component (B) is used in such an amount that the proportion of the metal atom in component (By is about 1 to about 2000 moles, preferably about 5 to about S00 moles, per mole of the titanium atom in the component (A); and the component (C) is used in such an amount that the proportion of the So atom in component (C) is about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, especially preferably about 0.05 to about 1 mole, per mole of the Metal atom in component (B).
The catalyst components, By and I may be contacted dllring or before the polymerization. In I
contacting them boor the pol~rnerizatior" owl) two o'' them selected may be contacted, or portLGrLs OX to or three of them May be contacted. Tune contacting ox the components before the ~olyrnerization may 'De carried out in an inert gaseous atmosphere, or in an atmosphere of l-butene.
The polymerization temperature is preferably about 20 to about 200C, more preferably about 50 to about 180C, and the polymerization pressure is from atmospheric pressure to about 100 kg/cm , preferably about 2 to about 50 kg/cm2.
The intrinsic viscosity of the polymer can be controlled to some extent by changing the pullers-lion conditions such as the polymerization temperature and the proportions of the catalyst components. Most effectively this can be achieved by adding hydrogen to the polymerization system.
Pipes produced from the l-butene polymer of this invention have improved rigidity, creep resistance characteristics and impact strength than conventional pipes of l-butene resins. Furthermore, since the crystal transition speed of the l-butene polymer ox this invention is increased, shaped products immediately after shaping can be advantageously handled.
The following examples illustrate the present invention more specifically.
Example 1 Preparation of a titanium catalyst component PA) An hydrous magnesium chloride (4.76 g; 50 moles), 30 25 ml of decant and 23.4 ml (lS0 moles) of 2-ethylhexyl alcohol were heated at 130 C for 2 hours to form a uniform solution. To the solution was added 1.11 $
(7.5 moles) of phthalic android, and the mixture was ; stirred at 130C for 1 hour to dissolve polka android in the uniform solution. The resulting uniform solution was cooled to room temperature, and added drops over the course of 1 hour to 200 ml 5~3 (1.8 moles) of titanium tetracnloride kept at -20~.
After the addition, the temperature of tune inure "as raised to 110C over the course of 4 nouns. 'Nina i s temperature reached 110 C, 2.68 rnl (12.5 moles of diisobutyl phthalate was added, and the mixture was maintained at this temperature for 2 hours with stirring.
After the 2-hour reaction, the solid portion was collected by hot filtration. The solid portion "as again suspended in 200 ml of titanium tetrachloride, and again reacted at 110C for 2 hours. After the reaction, the solid portion was collected again by hot filtration, and fully washed with decant and hexane at 110 C until no free titanium compound was detected from the washings. The titanium catalyst component (A) prepared by the foregoing procedure was stored as a hexane slurry. A part of it, however, was dried for determining its composition. It was found that the titanium catalyst component (A) formed contained 3. lo by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of diisobutyl phthalate.
Polytnerization A 2-liter autoclave was cooled to below 50C, and 1 liter of liquid l-butene, 1 mole of triethyl aluminum, 0.05 mole of vinyltriethoxysilane and 2 ; liters of hydrogen were introduced into the autoclave.
The mixture was heated to 60C, and then 0.01 mole, calculated as titanium atom, of the titanium catalyst component (A) was added. The l-butene was polymerized at 60C for 1 hour. Then, methanol was added to step the polymerization, and the unrequited l-butene was removed. The results of the polymerization are summarized in Table 1.
An antioxidant was added to the resulting polymer, and the mixture was kneaded and granulated by a single screw extrude with a screw diameter of 30 mm at a rosin temperature of 230C, and press-formed at ~Z~5~
200C into a sleet havirl~, a thicken of i m.
The sheet alas tested for truly phyla properties. 2 Tensile stress at yield porn I on ~easurec] in accordance with Astral ~33 using an ASTM No. 4 dumbbell specimen.
Issued impact strength (kg-cm/c,n) A notch was provided in the sample, and its impact strength was measured in accordance Waterloo Acutely D 256.
Creep resistance (hours) Tensile creep was evaluated in accordance with ASTM D 2990. The sample was an ASSET No. 4 dumbf~el specimen. The testing temperature was 100 C, and tune load was 20 kg. The time which elapsed until the specimen was broken, or stretched 25% was measured.
50% Transition time (hours) By X-ray diffraction, the ratio of the (110) plane reflection peak intensity of the I-type crystals to the (200) plane reflection peak intensity of the II-type crystals was measured. The time required until the intensity ratio reached one-half of the saturated value of the intensity ratio with the lapse of time was measured.
Example 2 Example 1 was repeated except that the amount of hydrogen used in the polymerization was chanted to 1 liter. The results are summarized in Tables 1 and 2.
Example 3 Ex~nple 1 was repeated except that in the polymerizatiorl$ the mount of vinyltriethoxysilane was changed to Al mole, and tune amount of hydrogen, to 0.7 liter. The results are sum7nari~ec~ in Tables 1 and .
Example 4 Example 1 was repeated except that in the polymerization, the anoint Ott vinyl~rieth~xysilan~ was :' changed to l ml,iole. The results ire us prized if, Tables l an 2.
Comparative E~arr~ple l Example l was repeated except Tao -r. the polymerization, the amount of vinyltriethGxysilan~ "a_ changed to 0.1 mole, and the amount of hydrogen, to 0.5 liter. The results are summarized in assay l ; and 2.
Comparative Example 2 lo A 2-liter autoclave was cooled to below -50 C, and l liter of liquid l-butene, 2 moles of deathly aluminum chloride and 0.3 liter of hydrogen err added.
After heating the mixture to 50C, l mole of -titanium trichloride was added. The l-butene was polymerized at 50C for 1 hour. Then methanol was added to stop the polymerization, and the unrequited l-butene was removed. The polymer was shaped. and evaluated as in Example l. The results are summarized in Tables l and 2.
Comparative Example 3 Example l was repeated except that the amount of hydrogen used in the polymerization was changed to 8 liters. The results are summarized in Tables 1 and 2.
Comparative Example 4 Comparative Example 2 was repeated except that the amount of hydrogen was changed to 0.4 liter, and the polymerization was carried out at 60C. The results are summarized in Tables l and 2.
~9~5(~
Table 1 Example (En.) or Comparative [ n] *
Example (Rex.) dug Lomb Isotactivity (~) En. 1 _ 4.7 95.8 En. 2 3.0 4.0 96.2 En. 3 3.5 3.9 97.0 En. 4 2.4 4.2 99.0 .__ .. . - .. __ Rex. 1 4.3 5.1 96.g Rex. 2 4.4 8.0 93.7 Rex. 3 0.9 4.5 95.1 Rex. 4 2.8 7.5 91.2 * Measuring conditions Solvent: Decline Temperature: 135C
Table 2 Example (En.) Stress at yield Issued impact Creep 50%
or Compare- point (kg/cm2) strength resistance Transit live Example (kg-cm/cm) (hours) lion (Rex.) After 1 After time day 10 days (hours) .. . ._ . . . _.. Jo En. 1 151 215 6.5 4000 15 En. 2 141 207 7.3 4400 25 En. 3 135 20:L 7.5 4500 31 En. 4 153 208 6.2 4900 18 ..._.___ Rex. 1 100 163 7.6 4500 65 Rex. 2 116 172 6.2 4000 35 Rex . 3 155 220 4.0 3100 12 Rex. 4 95 l57 4200 53 I
with an electron donor and/or a reaction at' Ill us an organoaluminurn compound or a halogen-conta_riing silicon compound, treated with a halogen a halogen compound or an aromatic hydrocarbon. In tune argyle procedure, a divester of a dicarboxylic acid or a compound capable of forming the divester is used at least once as the electron donor.
Preferred among these methods are those in which a liquid titanium halide is used, or a halogenated hydrocarbon is used after or during the use of tune titanium compound.
The electron donor used in the above methods of preparation is not necessarily limited to the divester or diester-forming compound. There may be used other electron donors such as alcohols, phenols, aldehydes, kittens, ethers, carboxy~ic acids Cry yoke, carboxylic acid anhydrides,-c~r~sn c acid esters, - monstrous and amine. It is essential however that the divester of a dicarboxylic acid or the divester-forming compound be used at least once.
Preferred examples of the divester as an essential component of the solid highly active titanium catalyst component (A) used in this invention include divesters of dicarboxylic acids in which two carboxyl groups are attached to one carbon atom of the hydrocarbon moiety or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carton atoms of the hydrocarbon moiety, and divesters of dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of the heterocyclic compound moiety containing at least two carbon atoms.
More specific examples of the preferred divesters are divesters, preferably di(C1-C20)a1kyl esters in which the two alkyd groups may be identical or different, of dicarboxylic acids in which two carboxyl groups are attached to one carbon atom of so an aliphatic hydrocarbon moiety having&) 1 to I error atoms or dicarboxylic acids in which one sar~oxyl group is attached to each of the Tao adjoining carton atoms of an aliphatic hydrocarbon moiety hygiene 2 to 20 carbon atoms; divesters, preferably di(Cl-C20)alkyl esters in which the two alkyd esters may be identical ox different, of dicarboxylic acids in which two earboxyl groups are attached to one carbon atom of an alicyelie hydrocarbon moiety having 3 to 20 carbon atoms or diearboxylie acids in which one earboxyl group is attached to each of the two adjoining carbon atoms of the aforesaid alicyclic hydrocarbon moiety; divesters, preferably di(Cl-C20)alkyl esters in which the two alkyd groups may be identical or different, of diearboxylie acids in which one carboxyl group is attached to each of the adjoining carbon atoms (at the ortho-position) of an aromatic hydrocarbon moiety having 6 to 20 carbon atoms; and divesters, preferably di(Cl-C20)alkyl esters, of diearboxylie acids in which one earboxyl group is attached to each of the two adjoining carbon atoms of a heteroeyclie compound moiety containing at least two carbon atoms and 1 to 10 hotter atoms selected from the group consisting of 0, N and S atoms.
Specific examples of the diearboxylie acids exemplified above include Masonic acid; substituted Malone acids such as methylmalonie acid, ethylmalonie acid, isopropylmalonie acid, allylmalonie acid, and phenylmalonic acid; succinic acid; substituted Suzanne acids such as methylsuceinie acid, dim ethyl-Sweeney acid, ethylsuee.inie acid, methylethylsueeinic acid and itaconie acid; rnaleic acid; substituted Molly acids such as eitraeonie acid and dimethylmaleie acid; fumier acid; substituted fumier acid such as rne~ylfw~ric acid and ethyl~rr~ric acid; alicyclic dicarboXylic acids such as eyelopentane-l~l diearboxylie acid, eyelopentane-1,2-diearboxylie acid, election-.. Jo _ 17 -dicarboxylic acid, cyclohex~ene~ -dicar-,o~.~lic acid, cyclohexene-2,3-dicarboxylic acid, cyclshexene-7,4-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, Nadir Acid, iilethylnadic Acid, and l-allylcyclone~ane-3,4-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,2-dicarboxylic acid and naphthalene-2,3-dicarboxylic acid; and heterocyclic dicarboxylic acids such as foreign-dicarboxylic acid, 4,5-dihydrofurane-2,3,-dicarboxylic acid, benzopyran-3,4-dicarboxylic acid, purl-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, and indwell-dicarboxylic acid.
Preferably, at least one of the alcohol components of the dicarboxylic acid divesters exemplified above has at least 2 carbon atoms, for example 2 to 20 carbon atoms, especially at least 3 carbon atoms It is above all preferred that both of the alcohol components have at least 2 carbon atoms, especially at least 3 carbon atoms. Examples include the deathly esters, diisopropyl esters, di-n-propyl esters, di-n-butyl esters diisobutyl esters, di-tert-butyl esters, dismal esters, di-n-hexyl esters, Dow-ethylhexyl esters, di-n-octyl esters, deciduously esters, and ethyl-n-butyl esters of the above-exemplified dicarboxylic acids.
A magnesium compound having no reducing ability can be utilized in the preparation of the solid highly active titanium catalyst component (A.
The magnesium compound includes, for example, magnesium halicies such as rna~nesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; Cluck alkoxyfnagnesium halides such as methoxymagnesium chloride, ethics magnesium chloride, isopropoxymagnesiurn chloride, bu~oxymagnesium chloride and octoxymagnesiurn chloride; C6-C20 aryloxymay~nesium halides such as phenoxyma~nesiurn chloride and methylphenox~magnesium chloride; C -C70 al~oxyrr~a7~nesi~ m-such as ethics magnesium, issuers r,lagnesiur-., buttocks rnagnesiuM, n-octoxy rnagnesiu,l7 and 2-ethylriexo~,y magnesium; C6-C20 aureole magnesium such as phonics magnesium and dimethylphenoxy magnesium; and carboxylic acid salts ox magnesium such as magnesium laureate and magnesium Stewart.
Preferred are halogen-containing magnesium compounds, particularly, magnesium chloride, alkoxy magnesium chlorides and aryloxyMagnesium chlorides are preferred.
Suitable titanium compounds used to prepare the titanium catalyst component (A are tetravalent titanium compounds represented by Ti(OR)gX4_g in which R is a hydrocarbon group, X is halogen and g is O to 4.
Examples of R are alkyd groups having l to 6 carbon atoms. Examples of X are Of, By and I.
Specific examples of such titanium compounds ; include titanium tetrahalides such as Tickle, Tuber and Tao; alkoxytitanium trihalides such as Ti~OCH3)C13, Ti(OC2H5)C13, Tao n-C4Hg)Cl3, Chokeberry and Tao iso-C4Hg)Br3; alkoxytitanium deludes such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Tao n-C4Hg)2Cl2 and Chokeberry trialkoxytitanium monohalides such as Ti(OCH3~3C1, Ti(OC2H5)3Cl, Tao n-C4Hg)3Cl and Chokeberry and tetraalkoxytitaniums such as Tush, Tokyo and Tao n-C4Hg)4. Among -them, the halo~en-containing titanium compounds, particularly titanium tetrahalides, especially preferably titanium tetrachloride, are preferred. These titanium compounds may be used singly or as a mixture. Or they may be used as diluted in hydrocarbons or halogenated hydrocarbons.
In the preparation of the titanium catalyst component (A), the amounts of the titanium compound, the magnesium compound the electron donor to be supported, and the other electron donors such as so alcohols, ?nenols, rnonocarboxylic acid ester s, true silicon compound and the aluminum compound Russia Roy used as required differ depending upon the method of preparation and cannot be defined in a general manner.
For example, about 0.1 to abut 10 moles of the electron donor to be supported and about 0.05 mole to about 1000 motes of the titanium compound may be used per mole of the magnesium compound.
The catalyst composed of (A) the titanium catalyst component that can be obtained as above, (B) a trialkyl aluminum compound and (C) an organosilicon compound selected from the group stated hereinabove can be utilized in producing the l-butene polymer in accordance with this invention.
Examples of preferred trialkyl aluminum compounds (B) are triethyl aluminum and triisobutyl aluminum.
The polymerization or copolymerization of 1-butane can be carried out in the liquid phase. An inert solvent such as hexane, Hutton and kerosene may be used as a reaction medium, but l-butene itself may be used as a reaction solvent. The amount of the catalyst used is preferably such that per liter of the volume of the reaction zone, the compound (A) is used in an amount of about 0.0001 to about 1.0 millimole calculated as titanium atom; the component (B) is used in such an amount that the proportion of the metal atom in component (By is about 1 to about 2000 moles, preferably about 5 to about S00 moles, per mole of the titanium atom in the component (A); and the component (C) is used in such an amount that the proportion of the So atom in component (C) is about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, especially preferably about 0.05 to about 1 mole, per mole of the Metal atom in component (B).
The catalyst components, By and I may be contacted dllring or before the polymerization. In I
contacting them boor the pol~rnerizatior" owl) two o'' them selected may be contacted, or portLGrLs OX to or three of them May be contacted. Tune contacting ox the components before the ~olyrnerization may 'De carried out in an inert gaseous atmosphere, or in an atmosphere of l-butene.
The polymerization temperature is preferably about 20 to about 200C, more preferably about 50 to about 180C, and the polymerization pressure is from atmospheric pressure to about 100 kg/cm , preferably about 2 to about 50 kg/cm2.
The intrinsic viscosity of the polymer can be controlled to some extent by changing the pullers-lion conditions such as the polymerization temperature and the proportions of the catalyst components. Most effectively this can be achieved by adding hydrogen to the polymerization system.
Pipes produced from the l-butene polymer of this invention have improved rigidity, creep resistance characteristics and impact strength than conventional pipes of l-butene resins. Furthermore, since the crystal transition speed of the l-butene polymer ox this invention is increased, shaped products immediately after shaping can be advantageously handled.
The following examples illustrate the present invention more specifically.
Example 1 Preparation of a titanium catalyst component PA) An hydrous magnesium chloride (4.76 g; 50 moles), 30 25 ml of decant and 23.4 ml (lS0 moles) of 2-ethylhexyl alcohol were heated at 130 C for 2 hours to form a uniform solution. To the solution was added 1.11 $
(7.5 moles) of phthalic android, and the mixture was ; stirred at 130C for 1 hour to dissolve polka android in the uniform solution. The resulting uniform solution was cooled to room temperature, and added drops over the course of 1 hour to 200 ml 5~3 (1.8 moles) of titanium tetracnloride kept at -20~.
After the addition, the temperature of tune inure "as raised to 110C over the course of 4 nouns. 'Nina i s temperature reached 110 C, 2.68 rnl (12.5 moles of diisobutyl phthalate was added, and the mixture was maintained at this temperature for 2 hours with stirring.
After the 2-hour reaction, the solid portion was collected by hot filtration. The solid portion "as again suspended in 200 ml of titanium tetrachloride, and again reacted at 110C for 2 hours. After the reaction, the solid portion was collected again by hot filtration, and fully washed with decant and hexane at 110 C until no free titanium compound was detected from the washings. The titanium catalyst component (A) prepared by the foregoing procedure was stored as a hexane slurry. A part of it, however, was dried for determining its composition. It was found that the titanium catalyst component (A) formed contained 3. lo by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of diisobutyl phthalate.
Polytnerization A 2-liter autoclave was cooled to below 50C, and 1 liter of liquid l-butene, 1 mole of triethyl aluminum, 0.05 mole of vinyltriethoxysilane and 2 ; liters of hydrogen were introduced into the autoclave.
The mixture was heated to 60C, and then 0.01 mole, calculated as titanium atom, of the titanium catalyst component (A) was added. The l-butene was polymerized at 60C for 1 hour. Then, methanol was added to step the polymerization, and the unrequited l-butene was removed. The results of the polymerization are summarized in Table 1.
An antioxidant was added to the resulting polymer, and the mixture was kneaded and granulated by a single screw extrude with a screw diameter of 30 mm at a rosin temperature of 230C, and press-formed at ~Z~5~
200C into a sleet havirl~, a thicken of i m.
The sheet alas tested for truly phyla properties. 2 Tensile stress at yield porn I on ~easurec] in accordance with Astral ~33 using an ASTM No. 4 dumbbell specimen.
Issued impact strength (kg-cm/c,n) A notch was provided in the sample, and its impact strength was measured in accordance Waterloo Acutely D 256.
Creep resistance (hours) Tensile creep was evaluated in accordance with ASTM D 2990. The sample was an ASSET No. 4 dumbf~el specimen. The testing temperature was 100 C, and tune load was 20 kg. The time which elapsed until the specimen was broken, or stretched 25% was measured.
50% Transition time (hours) By X-ray diffraction, the ratio of the (110) plane reflection peak intensity of the I-type crystals to the (200) plane reflection peak intensity of the II-type crystals was measured. The time required until the intensity ratio reached one-half of the saturated value of the intensity ratio with the lapse of time was measured.
Example 2 Example 1 was repeated except that the amount of hydrogen used in the polymerization was chanted to 1 liter. The results are summarized in Tables 1 and 2.
Example 3 Ex~nple 1 was repeated except that in the polymerizatiorl$ the mount of vinyltriethoxysilane was changed to Al mole, and tune amount of hydrogen, to 0.7 liter. The results are sum7nari~ec~ in Tables 1 and .
Example 4 Example 1 was repeated except that in the polymerization, the anoint Ott vinyl~rieth~xysilan~ was :' changed to l ml,iole. The results ire us prized if, Tables l an 2.
Comparative E~arr~ple l Example l was repeated except Tao -r. the polymerization, the amount of vinyltriethGxysilan~ "a_ changed to 0.1 mole, and the amount of hydrogen, to 0.5 liter. The results are summarized in assay l ; and 2.
Comparative Example 2 lo A 2-liter autoclave was cooled to below -50 C, and l liter of liquid l-butene, 2 moles of deathly aluminum chloride and 0.3 liter of hydrogen err added.
After heating the mixture to 50C, l mole of -titanium trichloride was added. The l-butene was polymerized at 50C for 1 hour. Then methanol was added to stop the polymerization, and the unrequited l-butene was removed. The polymer was shaped. and evaluated as in Example l. The results are summarized in Tables l and 2.
Comparative Example 3 Example l was repeated except that the amount of hydrogen used in the polymerization was changed to 8 liters. The results are summarized in Tables 1 and 2.
Comparative Example 4 Comparative Example 2 was repeated except that the amount of hydrogen was changed to 0.4 liter, and the polymerization was carried out at 60C. The results are summarized in Tables l and 2.
~9~5(~
Table 1 Example (En.) or Comparative [ n] *
Example (Rex.) dug Lomb Isotactivity (~) En. 1 _ 4.7 95.8 En. 2 3.0 4.0 96.2 En. 3 3.5 3.9 97.0 En. 4 2.4 4.2 99.0 .__ .. . - .. __ Rex. 1 4.3 5.1 96.g Rex. 2 4.4 8.0 93.7 Rex. 3 0.9 4.5 95.1 Rex. 4 2.8 7.5 91.2 * Measuring conditions Solvent: Decline Temperature: 135C
Table 2 Example (En.) Stress at yield Issued impact Creep 50%
or Compare- point (kg/cm2) strength resistance Transit live Example (kg-cm/cm) (hours) lion (Rex.) After 1 After time day 10 days (hours) .. . ._ . . . _.. Jo En. 1 151 215 6.5 4000 15 En. 2 141 207 7.3 4400 25 En. 3 135 20:L 7.5 4500 31 En. 4 153 208 6.2 4900 18 ..._.___ Rex. 1 100 163 7.6 4500 65 Rex. 2 116 172 6.2 4000 35 Rex . 3 155 220 4.0 3100 12 Rex. 4 95 l57 4200 53 I
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A butene-1 polymer containing 0 to 1 mole % of an olefin with 2 to 20 carbon atoms other than 1-butene and having (1) an intrinsic viscosity [?] of from 1.5 to 4.0 dl/g, (2) a molecular weight distribution, expressed by the raito of its weight average molecular weight (?w) to its number average molecular weight (?n), of not more than 6, and 3) an isotacticity value of at least 95 %
2. The 1-butene polymer of claim 1 which has a molecular weight distribution of from 2 to 5.5.
3. The 1-butene polymer of claim 1 which has an isotact-icity value of at least 95.5.
4. The 1-butene polymer of claim 1 which is a shaped article in the form of a pipe structure.
5. A process for the production of a shaped article in the form of a pipe structure, characterized in that the article is composed of a 1-butene polymer as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP81,016/83 | 1983-05-11 | ||
| JP58081016A JPS59206417A (en) | 1983-05-11 | 1983-05-11 | Poly-1-butene resin pipe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229450A true CA1229450A (en) | 1987-11-17 |
Family
ID=13734697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000453997A Expired CA1229450A (en) | 1983-05-11 | 1984-05-10 | 1-butene polymer and its use |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS59206417A (en) |
| CA (1) | CA1229450A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6441428U (en) * | 1987-09-07 | 1989-03-13 | ||
| JPH03126706A (en) * | 1989-10-11 | 1991-05-29 | Idemitsu Petrochem Co Ltd | Butene-1-propylene random copolymer for pipe and resinous pipe |
| JPH0431019U (en) * | 1990-07-10 | 1992-03-12 | ||
| EP1308466B1 (en) * | 2000-07-03 | 2007-02-28 | Mitsui Chemicals, Inc. | Butene copolymer, resin composition comprising the copolymer and moldings of the composition |
| KR100472771B1 (en) * | 2003-08-30 | 2005-03-14 | 주식회사 일렘테크놀러지홀딩스 | high stereospecific polybutene-1 polymer and the highly active preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120646A (en) * | 1977-12-14 | 1982-03-23 | Charles M. Selman | Catalyst and process for the polymerization of butene-1 |
-
1983
- 1983-05-11 JP JP58081016A patent/JPS59206417A/en active Granted
-
1984
- 1984-05-10 CA CA000453997A patent/CA1229450A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59206417A (en) | 1984-11-22 |
| JPS619325B2 (en) | 1986-03-22 |
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