CA2015302A1 - Processes for preparing thermoplastic elastomers - Google Patents

Abstract

Abstract Proposed herein is a process for preparing thermoplas-tic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a crosslinking agent optionally in the presence of a crosslinking auxiliary and/or a mineral oil softening agent a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles. Also proposed herein is a process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a radical initiator and a graft modifier optionally in the presence of a crosslinking agent, a crosslinking auxiliary, a swelling solvent and/or a mineral oil softening agent at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer graft modified and crosslinked within the particles.

Description

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SPECIFICATION
;! PROCESSES FOR PREPARING THERMOPLASTIC ELASTOMERS

Field of the Invention The present invention relates to processes for prepar-ing thermoplastic elastomers and more particularly to pro-~ cesses for preparing thermoplastic elastomers which are ex-'d cellent in heat resistance, tensile strength, weatherabil-ity, flexibility, elasticity and impact strength at low temperatures and, at the same time, excellent in surface smoothness and coating properties.

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Background of the Invention ~eretofore, thermoplastic elastomers have been widely J; 1 5 used as materials for the manufacture of automotive parts such as bumper. The thermoplastic elastomers have charac-teristics of both thermoplasticity and elasticity, and are l capable of being formed by injection or extrusion molding i into molded articles which are excellent in heat resis-~, 20 tance, tensile properties, weatherability, flexibility and ` elasticity.
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For example, Japanese Patent Publication No. 53-34210 `~ discloses thermoplastic elastomers prepared by partially - 25 curing a blend of from 60 to 80 parts by weight of a monoolefin copolymer rubber and from 40 to 20 parts by weight of a polyolefin plastics under dynamical conditions.

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3 Japanese Patent Publication No. 53-21021 discloses thermo-plastic elastomers comprising (a) a partially crosslinked copolymer rubber comprising a ethylene/propylene/non-con~u-gated polyene copolymer rubber having a gel content of from ^ 5 30 to 90 % by weight and (b) a polyolefin resin. Further, .j Japanese Patent Publication No. 55-18448 discloses thermo-plastic elastomers prepared by partially or fully curing a blend of an ethylene/propylene copolymer rubber and a poly-~, olefin resin under dynamical conditions.

Japanese Patent Laid-open Publication No. 58-187412 discloses a crosslinked block copolymer derived from an olefinic copolymer comprising from 50 to 70 parts by weight , '~ of one or more blocks [A] selected from homopolymer blocks ; 15 of propylene and binary random copolymer blocks of propy-lene and ethylene of a C4-12 a-olefin and having a propy-lene content of from 100 to 60 % by weight, and from 30 to 50 parts by weigh~ of one or more blocks [B] selected from ' binary random copolymer blocks of ethylene and propylene 20 and having an ethylene content of from 30 to 85 % by weight, said crosslinked block copolymer having a specified :- . . .
;~' content of hot xylene insoluble components and a specified '~` fluidity.

~ 25 Japanese Patent Laid-open Publications Nos. 63-165914, - 63-165415 and 63-415416, and US Patent no. 4,454,306 dis-,~ close a process for preparation of a crosslinked olefinic '-~

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- block copolymer which comprises melt kneading an olefinic block copolymer comprising one or more homopolymer blocks of propylene [A], one or more first binary random copolymer blocks of propylene and ethylene [B] and one or more second 5 binary random copolymer blocks of propylene and ethylene [C] and prepared using a specific Tiegler's catalyst, to-gether with an organic peroxide, a divinyl compound and an antioxidant, at a temperature of not higher than 230 C.

~ 10Japanese Patent Laid-open Publication No. 48-21731 .~ discloses a method for improving a processability of block ,j .
copolymers wherein a block copolymer comprising from 3 to ~1 30 % by weight of copolymer segments primarily comprised of J ethylene and containing up to 70 % by weight of at least one other a-olefin and from 97 to 70 % by weight of polymer segments primarily comprised of propylene is admixed with . an organic peroxide and the admixture is heat treated at a ~ temperature of from 180 to 270 C.

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20We have carried out extensive researches on the prepa-` ration of thermoplastic elastomers by direct dynamic heat treatment of polymer particles, and found that if polymer particles having a specific morphology are so treated, there can be economically prepared thermoplastic elastomers ~~ 25 which are very smooth, excellent in strength and elasticity `; even though they have a reduced rubber content, and capable of being molded into articles having good appearance, in .~.:
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-4- 72932-69 particular, good appearance after painted. The invention is based on the findings.

Thus, an object of the invention is to provide processes for the preparation of thermoplastic elastomers which have excellent elasticity even with a reduced rubber content and excellent strength, and are capable of being molded to articles which are very uniform, and excellent in strength properties such as tensile strength, heat resistance, weatherability, flexibility, elasticity, surface smoothness, properties of being painted and economy.

Description of the Invention The process for preparing thermoplastic elastomers according to the invention comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a crosslinking agent at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles.
In a first (i.e. broad) embodiment, a crosslinking agent is used. Upon bringing the polymer particles in contact with the crosslinking agent to prepare the thermoplastic elastomers, a swelling solvent or a mineral oil softening agent may be -- coexistent with the polymer particles and the crosslinking agent.
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-5- 72932-69 In a second (i.e. narrower) embodiment, a combination of a radical initiator (namely a radical-initiating crosslinking agent) and a graft modifier is used. Upon bringing the polymer particles in contact with the radical initiator and graft modifier to -prepare the thermoplastic elastomers, a swelling solvent or a mineral oil softening agent may be coexistent with the polymer particles and the radical-generating crosslinking agent, such as an organic peroxide.

By the processes according to the invention there can be prepared granular particles of a thermoplastic elastomer cross-linked within the particles. Some of the thermoplastic elastomers are novel. Such thermoplastic elastomer is primarily comprised of polymerized units of at least one ~-olefin having at least 3 carbon atoms, each of the particles composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin ,1 :' ':

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6 2~53~2 polymer, ~ particles having an average particle diameter of from 100 to 5000 ~m with a geometric standard deviation of from 1.0 to 2.0, an apparent bulk density of from 0.25 to 0.70, an aspect ratio of from 1.0 to 3.0 and containing 5 not more than 20 % by weight of fine particles having a particle diameter of not more than 100 ~m and at least 10 %

by weight of gel insoluble in cyclohexane.
t Best Mode~ of Carrying out the Invention 0 The processes for preparing thermoplastic elastomers according to the invention are illustrated below in detail.
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In the processes according to the invention, polymer particles, each composed of a portion or comprising a crystalline olefin polymer and portions comprising an amor-- phous olefin polymer, are used.
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The polymer particles used herein have an avera~e par-ticle diameter of usually at least 10 ~m, preferably from 10 to 5000 ~m,more preferably from 100 to 4000 ~m, and most preferably from 300 to 3000 ~m. A geometrical standard de-viation by which a particle size distribution of the poly-mer particles is designated is usually from 1.0 to 3.0, preferably from 1.0 to 2.0, more preferably from 1.0 to 1.5, and most preferably from 1.30 to-l1.3. An apparent bulk density of the polymer particles used herein, as mea-sured by spontaneous falling, is usually at least 0.2 g/ml, ' preferably from 0.2 to 0.7 g/ml, more preferably from 0.3 to 0.7 g/ml, and most preferably from 0.35 to 0.60 g/ml.
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The polymer particles used herein contain particles ~;5 passing through a sieve of 150 mesh in an amount of prefer-ably not more than 30 % by weight, more preferably not more than 10 % by weight, and most preferably not more than 2 %
~by weight. Furthermore, the polymer particles used herein jexhibit a falling time of preferably from 5 to 25 seconds, `~.10 more preferably from 5 to 25 seconds, and most preferably from 5 to 15 seconds, as measured by the falling test noted below.

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The average particle diameter, apparent bulk density and falling time of the polymer particles are determineed as follows.

Average particle diameter At the top of a stainless sieve assembly supplied by Nippon Science Instrument Co. Ltd.tcomprising 7 sieves hav-ing openings of 7, 10, 14, 20, 42, 80 and 150 mesh, respec-tively, stacked in this order from the top,and equipped with a receiving dish at the bottom) and having diameter of ~ .
~200 mm and a depth of 45 mm, there was added 300 g of poly-- 25 mer particles. The sieve assembly was stoppered, set on a -sieve shaker (supplied by IIDA Works Co. Ltd., and shaken for a period of 20 minutes. At the end of the period, '', , ..~ .

polymer particles remaining on the respective sieves and received on the receiving dish were weighed respectively.
The weight (% by weight) of the polymer particles was plot-ted against the opening (particle diameter in ~m) on a log-arithmico-normal probability paper. Based on the curve so obtained, a particle diameter at a point where an inte-~ grated weight is 50 % by weight (D50) was determined, and ¦ was taken as the average particle diameter.

0 Further, a particle diameter at a point where an inte-grated weight is 16 ~ by weight (D16) Iwas determined,and the geometric standard deviation = D50/Dl6 was calculated.

Apparent bulk density ~ 15 The apparent bulk density was determined in accordance !, with JIS K 6721-1977, using a funnel having an inlet inner `~ diameter of 92.9 mm and an outlet inner diameter of 9.5 mm.and equipped with a damper at the outlet.

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Falling time ; The apparatus used in the measurement of the apparent - bulk density was used as such. Polymer particles were al-lowed to fall from the funnel in a 100 ml vessel, and ex-cess polymer particles standing up above the vessel were swept with a glass rod thereby sampling 100 ml in bulk of the polymer particles. The 100 ml of the sample was trans-ferred to the funnel having the damper inserted thereinto, , .:~

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, and the damper was drawn to allow the particles fall. The falling time (in second) taken Eor all the sample to fall from the funnel was measured.
;' SIncidentally, the measurement of the falling time was ~ carried out on polymer particles from which large particles '~7' having a diameter 1.5 to i.6 or more times the average par-~ ticle diameter had been removed by sieving. Further, upon ., ~ measurement of the falling time, the funnel was securely : !
fixed to a vibrating plate of a powder tester (Type PT-D, Ser. No. 71190) supplied by Hosokawa Micro Co. Ltd., and the sample was allowed to fall under vibration. A voltage of an electric power for vibrating the plate was adjusted by means of a rheostat so that the amplitude of the vibra-lS tion might be 1 mm.

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Each of the polymer particles used herein is composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, and has a so-called sea-and-islands structure in which the amorphous ~` olefin portions constitute the islands. The islands, com-prising the amorphous olefin polymer (and a part of the crystalline olefin polymer in some cases) desirably have an ,.j average particle diameter of not exceeding 0.5 ~m, preferably not exceeding 0.1 ~m, and more preferably not exceeding 0.05 ~m. ;

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1 o 20~.~3~2 The average particle diameter of the islands of the 3 polymer particles used herein is determined as follows.

A polymer particle is sliced at a temperature of about 5 - 140 C., with an ultramicrotome to obtain a specimen hav-~ ing a thickness of from 500 to 1000 A. The sliced specimens is then placed in a vapor phase of a sealed one liter ves-sel containing 200 ml of a 0.5 % aqueous solution of Ru04 for a period of 30 minutes, thereby dying the amorphous 10 olefin polymer portions (islands) of the specimen, and the so dyed specimen is reinforced with carbon. At least 50 dyed islands of the specimen are measured for their parti-cle diameters by observation with an electron transmission . microscope, and the mean value of the so measured particle 15 diameters is taken as the average particle diameter of the islands.

~:~ The polymer particles used herein are preferably those having such characteristics as mentioned above, and they :l 20 are preferably prepared by the processes as will be men-tioned hereinafter, though no particular limitation is placed on the processes for the preparation thereof. In .~ the polymer particles thus obtained, the ash content ~ thereof contains a transition metal component in an amount f't~l ' 25 of usually not more than 100 ppm, preferably not more than . 10 ppm, and more preferably not more than 5 ppm, and a .~
.~ halogen component in an amount of usually not more than 300 ~.

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ppm, preferably not more than 100 ppm, and more preferably not more than 50 ppm.
~ , The term polymer used herein is intended to include ¦ 5 both polymer and copolymer.

; The polymer particles having such characteristics as ¦ mentioned above may be obtained, for example, by polymer-ization or copolymerization of a-olefins having from 2 to 3 1 0 20 carbon atoms.

Examples of such a-olefins include, for example, ethy-lene, propylene, butene-1, 2-methylbutene--1, 3-methyl-~, butene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 15 3,3-dimethylbutene-1, heptene-1, methylhexene-l, dimethylpentene-l, trimethylbutene-l, ethylpentene-l, octene-1, methylpentene-1, dimethylhexene-l, trimethylpen-tene-1, ethylhexene-l, methylethylpentene-l, diethylbutene-1, propylpentene-1, decene-l, methylnonene-l, dimethy-20 loctene-1, trimethylheptene-1, ethyloctene-1, methylethyl-he)~ad~¢~ne~l.
~ ~ butene-1, diethylhexene-1, dodecene-1 and hr~ n~-1=
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~. Of these a-olefins exemplified above, preferred are tJ a-olefins having from 2 to 8 carbon atoms used either singly or in combination.

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The polymer particles used herein contain recurrinq :~ .
units derived from the above-mentioned a-olefin in an amount of usually at least 50 mol %, preferably at least 80 ~mol %, more preferably at least 90 mol %, and most prefer-`~5 ably 100 mol %.

Other compounds usable together with the above-men-.tioned a-olefins in the preparation of the starting polymer ~yparticles used herein include, for example, chain polyene ~j10 compounds and cyclic polyene compounds. The polyene com-pounds useful herein have at least two conjugated or non-conjugated olefinic double bonds, and include chain polyene compounds such as 1,4-hexadiene, 1,5-hexadiene, 1,7-octadi-~-~ene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, lS 1,5,9-decatriene and divinylbenzene,as well as cyclic polyene compounds such as 1,3-cyclopentadiene, 1,3-cyclo-hexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-nor-bonene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-~-~20 isopropylidene-2-norbornene, methylhydroindene, 2,3-diiso-propylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,5-norbonadiene.

In the preparation of the starting polymer particles used herein, together with the above-mentioned a-olefins, there may also be used polyene compounds obtained by con-densation of cyclopentadienes such as cyclopentadiene with .

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: ~ , . , a-olefins such as ethylene, propylene and butene-1 by uti-~ lizing Diels-Alder reaction.

-~ Further, cyclomonoenes may also be used together with the above-mentioned a-olefins and optionally above-men-tioned polyenes in the preparation of the starting polymer.
Examples of such cyclomonoenes include, for example, mono-cycloalkenes such as cyclopropene, cyclobutene, cyclopen-tene, cyclohexene, 3-methylcyclohexene, cycloheptene, cy-0 clooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene and cycloeicosene; bicycloalkenes such as norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-I isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-~ trimethyl-2-norbornene and 2-bornene; tricycloalkenes such 15 as 2,3,3a,7a-tetrahydro-4,7-methano-lH-indene and 3a,5,6,7a-tetrahydro-4,7-methano-lH-indene; and, in addi-' tion thereto, tetracycloalkenes such as 2-methyl-1,4,5,8-I dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-;~ 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, `~ 20 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaph-thalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-oc-tahydronaphthalene, 2-stearyl-1,4,5,8,8a-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, : 25 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,qa,5,8,8a-oc-tahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-~,. .
,.-: ~` ~ ................... . ' ' ,' , ' " ' ' ' '' ' ' . dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-i 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-oc-tahydronaphthalene; and polycycloalkenes such as hexacy-3 5 c10[6 6 1 13 6 110~l3,0Z~7,09~l4]heptadecene-4, pentacy-c10[8 8 l29,14,7,11l,l8,0,03~8,0l2~l7]heneicosene-5, and octa-cyclo[8,8,12~9,14,7,lll,l8,ll3,16,o,o3,8,0l2,l7]dOcOsene_5 3, . Styrene and substituted styrenes may also be used as 31 0 an optional monomer in the preparation of the starting ~polymer particles ~, ¦The polymer particles which can be used in the process according to the invention may be obtained by polymeriza-`~15 tion or copolymerization of at least the aforementioned a-.olefin in the presence of a catalyst as noted below, and this polymerization or copolymerizatlon reaction may be !carried out either in a vapor phase (vapor phase process) `i ~:~or in a liquid phase (liquid phase process).
' 20 .The polymerization or copolymerization according to .`the liquid process is carried out Dreferably in a suspen-sion state so that the resulting polymer particles are ob-`tained in a solid state. In this case, inert hydrocarbons ~ ; :
25 can be used as the solvent. Alternatively, at least one a-olefins being polymerized may serve as the polymerization solvent. i~

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J 15 20~:i302 The polymerization or copolymerization of the prepara-tion of the polymer particles used herein is preferably carried out by a combined process comprising a first vapor phase process or a liquid phase process using an a-olefin as the solvent, followed by a second vapor phase process.

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In preparing the polymer partlcles used in the process according to the invention, there may be employed a process which comprises fcrming simultaneously crystalline olefin polymer and amorphous olefin polymer by feeding at least two kinds of monomers to a polymerization vessel, or a pro-cess which comprises forming crystalline olefin polymer and amorphous olefin polymer separately but in series by using at least two polymerization vessels. Of the two processes, ~lS preferred is the latter one from a standpoint that the ~molecular weight, composition and amount of the resulting ~amorphous olefin polymer can be freely adjusted at will.
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Of the latter process mentioned above, most preferred ~-20 is a process which comprises forming a crystalline olefin ;-~
,polymer portion by a first vapor phase polymerization, fol-:, : .. :
lowed by formation of amorphous olefin polymer portions by `~a second vapor phase polymerization, or a process which ~;comprises forming a crystalline olefin polymer portion by ;25 using the monomer as a solvent, followedjby formation of an amorphous olefin polymer portion by a vapor phase polymer-ization. `
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In the above-mentioned polymerization or copolymeriza-tion reaction, there is employed a catalyst normally com-posed of a catalyst component [A] containing at least one transition metal and a catalyst component [B] containing at 5 least one organometallic compound of a metal selected from metals belonging to Groups I, II and III of the periodic table.

The above-mentioned catalyst components [A] used are preferably those containing transition metal atoms of Groups IVB and VB of the periodic table, and are further preferably those containing at least one atom selected from the group consisting of titanium, zirconium, hafnium and vanadium.

Besides the above-mentioned catalyst components [A], other useful catalyst component.s ~A] are preferably those containing halogen and magnesium atoms in addition to the aforementioned transition metal atoms, and those containing ; 20 compounds in which a group having conjugated ~ electrons has been coordinated to the transition metal of Group IVB

or VB of the periodic table.
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It is desirable that the catalyst components [A] used are prepared so that at the time of carrying out the above-mentioned polymerization or copolymerization reaction, they may be present in a solid state in the reaction system or .~

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they are supported on solid carriers so as to be present in ~ a solid state in the reaction system.

'~ Solid catalyst components [A] containing halogen and magnesium atoms in addition to the transition metal atoms, will be further illustrated in detail.
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The solid catalyst components [A] as mentioned above have an average particle diameter of preferably from 1 to 200 ~m, more preferably from 5 to 100 ~m, and most prefer-. ably from 10 to 80 ~m. Such solid catalyst components [A]
have a geometrical standard deviation (~g), as a barometer of particle size distribution, of preferably from 1.0 to 3.0, more preferably from 1.0 to 2.1, and most preferably from 1.0 to 1.7.
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An average particle diameter and particle size distri-. bution of the catalyst components [A] may be determined by a light transmission method. Specifically, a dispersion is prepared by pouring a specimen of the catalyst component [A] into decalin so that the concentration (content) of said specimen becomes 0.1 % by weight, the dispersion is put into a measuring cell, and the cell is exposed to a slit lighting, and changes of the intensity of the light passing through the liquid in a state where the particles are settling are continuously measured, whereby the parti-cle size distribution of the specimen is measured. A stan-, . . .
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201S3~32 dard deviation (~g) is obtained from a logarithmic-normal distribution function as a (~50/~16) ratio of an average I particle diameter (~50) to a particle size diameter (~16) of smaller particles amounting to 16% by weight. The average 5 particle diameter as termed herein is a weight average par-ticle diameter.

The catalyst components [A] are preferably spherical, ~ ellipsoidal or granular in shape, and an aspect ratio of 3 10 the particle thereof is preferably not more than 3, more preferably not more than 2 and most preferably not more ~, than 1.5. The aspect ratio can be determined by optical microscopic observation of particles of the catalyst compo-nent [A], measurement of major and minor axes on 50 parti-15 cles and calculation.

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When the catalyst components [A] contain magnesium, titanium and halogen atoms and an electron donor, magne-` sium/titanium ~atomic ratio) is preferably greater than 1, 20 and this value is usually from 2 to 50, preferably from 6 to 30, halogen/titanium (atomic ratio) is usually from 4 to 100, preferably from 6 to 40, and electron donor/titanium (molar ratio) is usually from 0.1 to 10, preferably from 0.2 to 6. The specific surface area of the catalyst compo-25 nents [A] is usually at least 3 m2/g, preferably at least 40 m2/g and more preferably from 100 to 800 m2/g.

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Generally, the catalyst components [A] will not re-lease the titanium compound contained therein by such a mild operation as rinsing with hexane at room temperature.

In addition to the above-mentioned components, the catalyst components [A] used herein may contain other atoms and metals, and may be incorporated with appropriate func-tional groups. Further, the catalyst components [A] may be diluted with organic or inorganic diluents.
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The catalyst components [A] as illustrated above may be prepared, for example, by a process in which the magne-sium compound having the average particle diameter, parti-cle size distribution and shape as defined above is pre-pared, followed by deposition of a transition metal com-I pound thereon , or a process in which a liquid magnesium compound and a liquid titanium compound are brought into contact with each other and thereby to form a solid cata-lyst having such properties of their particles as defined ~ 20 above.
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The catalyst components [A] thus prepared may be used, as they are, or there may also be used those prepared by supporting the magnesium and titanium compounds, if neces-sary, the electron donor, on carriers uniform in shape, orthose prepared by granulating a particu!late catalyst pre-. ' :
:' 2O~.~;302 t pared in advance into such a desirable shape as mentloned i above.
'2 Such catalyst components [A] as illustrated above are5 disclosed in Japanese Patent Laid-open Publications. Nos.
55-135102, 55-135103, 56-811 and 56-67311, and specifica-tions attached to Japanese Patent Applications. Nos. 56-181019 and 61-21109.

For reference, some processes for the preparation of the catalyst components [A] disclosed in the above-cited patent publications or specification are as in the follow-ing.
(1) A solid magnesium compound/electron donor complex hav-.
ing an average particle diameter of from 1 to 200 ~m and a geometrical standard deviation (~g) of particle size dis-tributicn of not more than 3.0 is pretreated, or not pre-~ treated, with an electron donor and/or a reaction assistant ; such as organoaluminum compound or a halogen-containing -~ 20 silicon compound, and the complex is caused to react under reaction conditions with a liquid halogenated titanium com-pound, preferably titanium tetrachloride.

(2) A liquid magnesium compound having no reducing ability is caused to react with a liquid titanium compound, prefer-ably in the presence of an electron donor, to deposit a solid component having an average particle diameter of from '-' ~"`' ' 2 1 20~5302 1 to 200 ~m and a geometrical standard deviation (~g) of particle size distribution of not more than 3Ø If de-sired, the solid component thus obtained is caused to react twith a liquid titanium compound, preferably titanium tetra-5 chloride, or with a liquid titanium compound and an elec-tron donor.
-(3) A liquid magnesium compound having a reducing ability is preliminarily brought into contact with a reaction as-10 sistant, such as polysiloxane or halogen-containing silicon compound, capable of disappearance of the reducing ability of the magnesium compound to deposit a solid component hav-s~ing an average particle diameter of from 1 to 200 ~m and a }geometrical standard deviation (~g) of particle size dis-15 tribution of not more than 3.0, followed by causing the ¦solid component to react with a liquid titanium compound, preferably titanium tetrachloride, or with a titanium com-pound and an electron donor.

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(9) A magnesium compound having a reducing ability is : brought into contact with an inorganic carrier such as sil-. l :
:ica or with an organic carrier, the carrier is then brought ~into contact, or not in contact, with a halogen-containing .. . .
compound, and brought into contact with a liquid titanium . 25 compound, preferably titanium tetrachloride, or with a ti--`tanium compound and an electron donor, thereby causing the . :

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magnesium compound supported on the carrier with the tita-nium compound.

(5) The first half of the process (2) above or the first 5 half of the process (3) above, is carried out in the pres-Yrence of an inorganic carrier such as silica or alumina of an organic carrier such as polyethylene, polypropylene or .polystylene, thereby preparing the Mg compound supported by the carrier, followed by the second half of the process (2) ;~10 or (3) above.
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iThe solid catalyst components [A~ thus prepared have such a performance that they are capable of preparing poly-mers having high stereo-regularity at high catalytic effi-5 ciency. For example, when homopolymerization of propylene is carried out under the same conditions by using the solid catalyst component [A], it is found that this catalyst com-ponent has an ability to give polypropylene having an iso-tacticity index (insoluble in boiling n-heptane) of at least 92%, preferably at least 96% in an amount, based on 1 ,mmole of titanium, of usually at least 3000 g, preferably at least 5000 g and more preferably -at least 10000 g.

qExamples of the magnesium compound, halogen-containing 25 silicon compound, titanium compound and electron donor ;which can be used at the time of preparing the above-men-.. .
;tioned catalyst components [A] are shown hereinafter. The ' ~ .

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aluminum co~,ponents which can be used in the preparation of the catalyst componemt [A] includes compounds illustrated , hereinafter on the organometallic compound catalyst compo-nents [B].
; S
. Examples of the magnesium compound include inorganic magnesium compounds such as magnesium oxide, magnesium hy-droxide, and hydrotalcite, and organic magnesium compounds ~`~' such as magnesium carboxylates, alkoxymagnesium compounds, aryloxymagnesium compounds, alkoxymagnesium halides, ary-loxymagnesium halides, magnesium dihalides, dialkylmagne-sium compounds, Grignard reagents and diarylmagnesium com-pounds.

` lSExamples of the titanium compound include titanium -; halides such as titanium tetrachloride and titanium trichloride, alkoxytitanium halides, aryloxytitanium ~'~ halides, alkoxytitanium compounds and aryloxytitanium com-pounds. Of these, preferred are titanium tetrahalides, in ' 20 particular, titanium tetrachloride.
,,,,, ~"

Examples of the electron donor include oxygen-contain-ing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic ; 25 acid, ethers, acid amides, acid anhydrides and alkoxysi-lane; and nitrogen-containing electron donors such as ammo-nia, amines, nitriles and isocyanates.

, ~ :

24 2 O ~ 53 02 More specifically, examples of the compounds useful as the electron donor include~
alcohols having from 1 to 18 carbon atoms such as jmethanol, ethanol, propanol, pentanol, hexanol, octanol, !s dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alco-Ihol, phenylethyl alcohol, isopropyl alcohol, cumyl alcohol and isopropylbenzyl alcohol;

:phenols having from 6 to 20 carbon atoms which may 0 have lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol;

....
ketones having from 3 to 15 carbon atoms such as ace-~lS tone, methyl ethyl ketone, methyl isobutyl ketone, ace--~tophenone, benzophenone and benzoquinones;

~aldehydes having from 2 to 15 carbon atoms such as ac- I ~:
,~etaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, .
tolualdehydes and naphthoaldehydes;

1 .
organic acid esters having from 2 to 30 carbon atoms ~:

-such as methyl formate, methyl acetate, ethyl acetate, `vinyl acetate, propyl acetate, octyl acetate, cyclohexyl .25 acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl .methacrylate, ethyl crotonate, ethyl cyclohexanecarboxy- ~

.
. -. : '.~,'.'." -: ' ' ' ~ . : . , , :
~ f ,t,~

; -- 20~5302 ;. 25 ,~ , !;
late, methyl benzoate, ethyl benzoate, propyl benzoate, ~ butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl ~ benzoate, benzyl benzoate, methyl toluylate, ethyl toluy-late, amyl toluylate, ethyl ethylbenzoate, methyl anisy-5 late, n-butyl maleate, diisobutyl methylmalonate, di-n-.~I hexyl cyclohexenecarboxylate, diethyl nadylate, diisopropyl tertahydrophthalate, diethyl phthalate, diisobutyl phtha-. late, di-n-butyl phthalate, di-2-ethylhexyl phthalate, ~-butyrolactone, ~-valerolactone, coumarin, phthalide and ethylene carbonate;
/

halides having from 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chlorldes and anisic acid chlorides;

'I 15 ethers of having from 2 to 20 carbon atoms such as ~ ~
s methyl ether, ethyl ether, isopropyl ether, butyl ether, -~ amyl ether, tetrahydrofuran, anisole and diphenyl ether;
.i and in particular diethers;
: 20 ~ :
acid amides such as acetamide, benzamide and tolu-amide;
.

amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyri-dine, picoline and tetramethylenediamine;

... , ~.. . . . , . . :

-organic phosphorous compounds having P-O-C bond such as trimethyl phosphite and triethyl phosphite; and t alkoxysilanes such as ethyl silicate and diphenyl dimethoxysilane. These electron donors may be used either singly or in combination.

Of the electron donors as exemplified above, preferred are compounds having no active hydrogen, for example, esters of organic or inorganic acid, alkoxy (or ary-'~ loxy)silane compounds, ethers, ketones, tertiary amines, ~acid halides and acid anhydrides, and organic acid esters , . :
~and alkoxy (or aryloxy) silane compounds are particularly ;~preferred. Above all, particularly preferred are esters of ;15 an aromatic carboxyllc acid with an alcohol having from 1 to 8 carbon atoms; esters of a dicarboxylic acid such as malonic acid, substituted malonic acids, substituted suc-cinic acids, maleic acid, substituted maleic acids, 1,2-cy-clohexanedicarboxylic acid and phthalic acids with an alco-`20 hol having at least 2 carbon atoms; and diethers. Needless -to say, it is not always necessary that these electron donors are added as starting materials to the reaction sys-;tem at the time of preparing the catalyst components [A].
For instance, it is also possible that compounds convert-ible into these electron donors are first added to the re-action system and then converted into said electron donors ~ ' : ~.

~ , .

. :,i,............ . , ., -2 7 ;2(;)~53(~2 .

in the course of preparation of the catalyst components [A].

The catalyst components [A] as obtained in the manner mentioned above may be purified by thoroughly rinsing with liquid inert hydrocarbon compounds. Examples of the hydro-carbons usable in the above case include:
aliphatic hydrocarbon compounds such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosine and liquid paraf-fin;

alicyclic hydrocarbon compounds such as cyclopentane, .;
~ methyl cyclopentane, cyclohexane and methyl cyclohexane; ~-aromatic hydrocarbon compounds such as benzene, s toluene, xylene and thymene; and halogenated hydrocarbon compounds such as chloroben- ;
:~ 20 zene and dichloroethane.

These inert hydrocarbon compounds may be used either :

singly or in combination.
:, ' - 25 The organometallic compound catal.yst components [B]

used in the present invention are preferably organoaluminum :`

. ~:

'. ,~ . , .

~ !
rl ,j, -, .. 2 8 2015302 ,, . ,.
i~ compounds having in the molecule at least one Al-carbon : bond.

h Examples of the organoaluminum compounds mentioned above include:
~A~
~-~; (i) those represented by the formula:
.``~ RlmAl ~oR2) nHpXq (i) wherein Rl and R2, which may be the same or different, and each represents a hydrocarbon group having usually from 1 ~ 10 to 15 carbon atoms, preferably from 1 to 4 carbon atoms, X
y is a halogen atom, m is O<m~3, n is O~n<3, p is O~p<3, q is O~q<3, and m+n+p+q = 3; and (ii) complex alkylated compounds of a metal of Group ~; I of the periodic table with aluminum represented by the ~l 15 formula MlAlRl 4 ( i i ) ~i wherein M1 is Li, Na or K, and Rl is as defined above.
. -, .
':'~ ':
The organoaluminum compounds of the formula (i) in-20 clude concretely such compounds as will be mentioned here-inbelow.
Compounds represented by the formula:
RlmAl(OR2)3-m .,~ :
wherein Rl and R2 are as defined above, and m is preferably 1.5<m<3.
,................................... ;, Compounds represented by the formula:

. .

~; - : -20~5302 RlmAlX3-m wherein R1 is as defined above, X is a halogen atom, and m is preferably O<m<3.
' Compounds represented by the formula,:
RlmAlH3-m wherein Rl is as defined above and m is preferably 2~m<3.
~::

Compounds represented by the formula: -~
1 0 RlmAl ~oR2) nXq wherein Rl and R2 are as defined above, X is a halogen atom, m is O<mS3, n is O<n<3, q is O<q<3, and m+n+q=3.

~oncrete examples of the organoaluminum compounds rep-resented by the above-mentioned formula ~i) include:
trialkylaluminum compounds such as triethylaluminum, tributylaluminum and triisopropylaluminum;
'~' , .
trialkenylaluminum compounds such as triisoprenylalu-20 minum;
~ :
partially alkoxylated alkylaluminum compounds, includ-ing, for example, dialkylaluminum alkoxides such as diethy-- laluminum ethoxide and dibutylaluminum butoxide; alkylalu-minum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; and other partially alkoxylated alkylaluminum compounds having an average com-~ . '': ' , ' - :sr;~. ~

Z~3~2 . .
position, for example,represented by the formula R12,5Al (oR2) 0.5 wherein R1 and R2 are as defined above;

!
partially halogenated alkylaluminum compounds, includ-ing, for example, dialkylaluminum halides such as diethyla-luminum chloride, dibutylaluminum chloride and diethylalu-minum bromide; alkylaluminum sesquihalides such as ethyla-luminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; alkylaluminum dihalides such ., .
0 as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dichloride;

partially hydrogenated alkylaluminum compounds, in- :~
cluding, for example, alkylaluminum hydrides such as di-15 ethylaluminum hydride and dibutylaluminum hydride, alkyla-luminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; and -~
i, .

:~ partially alkoxylated and halogenated alkylaluminum t 20 compounds such as ethylaluminum ethoxychloride, butylalu-/ minum butoxychloride and ethylaluminum ethoxybromide.
:~ , : The organoaluminum compounds may be, for example, those having at least two aluminum atoms linked together 25 through oxygen or nitrogen atom, which are analogous to the compounds represented by the aforementioned formula (i).
Concrete examples of such organoaluminum compounds as men-, 'i ' :.j ,. - -: ~ : :

-. :~, , . - .

3 ~ 15302 , .

~; tioned above include (C2H5)2AlOAl~C2Hs)2, (C4Hg)2AlOAl(C4H9)2 and (C2H5)2AlN(C6Hs)Al(C2Hs) 2 -: .
~xamples of the organoaluminum compounds of the afore-mentioned formula (ii) include, for example, LiAl(C2H5) 9 andLiAl(C7Hl5) 4-Of the organoaluminum compounds illustrated above, itis particularly desirable to use a trialkylaluminum, a mix-ture of a trialkylaluminum and an alkylaluminum halide, and a mixture of a trialkylaluminum and an aluminum halide as the catalyst component [B].

The polymerization or copolymerization for the prepa-ration of the polymer particles used herein, is carried outin the presence of the catalyst component [A] and organometallic compound catalyst component [B]. In this ~ case, an electron donor [C~ is preferably used in combina-:~ tion with the components [A] and [B].
~ 20 . Examples of the electron donor [C] usable herein in-clude amines, amides, ethers, ketones, nitriles, phos-phines, stibines, arsines, phosphoamides, esters, thioethers, thioesters, acid anhydrides, acid halides, . 25 aldehydes, alcoholates, alkoxy(or aryloxy)silanes, organic acids and amides of metals belonging to Groups I, II, III
and IV of the periodic table and acceptable salts thereof.

''.~;-~-' ~ :

.
3 2 Z01~;302 The above-mentioned salts may also be formed in the reac-tion system by a reaction of organic acids with the organometallic compounds used as the catalyst components [B]-Concrete examples of the above-mentioned electron donors may be the compounds exemplified in the case of the catalysts components [A]. Of these electron donors, par-ticularly preferred are organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid an-hydrides and amides. In particular, when the electron donor in the catalyst component [A] is a monocarboxylic ~ acid ester, the electron donors [C] are preferably an alkyl ¦ ester of an aromatic carboxylic acid.

i When the electron donor in the catalyst component [A]
is an ester of a dicarboxylic acid with an alcohol having at least two carbon atoms, the electron donors [C] used herein are preferably alkoxy(aryloxy)silane compounds rep-resented by the formula RnSi(OR1) 4-n wherein R and R1 each represent a hydrocarbon group and n is 0~n<4, and amines large in steric hindrance.

:
Concrete examples of the alkoxy(aryloxy)silane com-pounds mentioned above include trimethylmethoxysilane,trimethoxyethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, diisopropyldimethoxysilane, t-butyl-.

t 33 ~

methyldimethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, ` diphenyldiethoxysilane, bis-o-tolyldimethylsilane, bis-m-tolyldimethoxysilane, bis-p-tolylmethoxysilane, bis-p-5 tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicy-! clohexyldimethoxysilane, cyclohexylmethylmethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxysilane, decyl-methoxysilane, decyltriethoxysilane, phenyltrimethoxysi-lane, ~-chloropropyltrimethoxysilane, methyltrimethoxysi-~ lane, vinyltriethoxysilane, t-butyltriethoxysilane, n-d, butyltriethoxysilane, iso--butyltriethoxysilane, phenyltri-ethoxysilane, ~-aminopropyltriethoxysilane, chlorotri-ethoxysilane, ethyltriisopropoxysilane, vinyltributoxysi-lane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysi-lane, 2-norbonanetrimethoxysilane, 2-norbor-nanedimethyldimethoxysilane, ethyl silicate, butyl sili-i cate, trimethylphenoxysilane, methyltriallyloxysilane, :1 vinyltris(~-methoxysilane) and dimethyltetraethoxydisilox-ane. Of there, preferred are ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltri-ethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolylmethoxysilane, p-tolylmethyldimethoxysilane, dicy-clohexyldimethoxysilane, dichlorohexylmethyldimethoxysi-lane, 2-norbornanetriethoxysilane, 2-norbor-, ,.

.

20~5302 nanemethyldimethoxysilane, diphenyldiethoxysilane and ethyl silicate.

Particularly suitable as the aforementivned amines large in steric hindrance are 2,2,6,6-tetramethylpiperi-dine, 2,2,5,5-tetramethylpyrrolidine and derivatives of these compounds, and tetramethylmethylenediamine. Of these compounds mentioned above, particularly preferable electron donors used as catalyst component are alkoxy(aryloxy)silane compounds and diethers.

,' .

In the polymerization or copolymerzation for preparing the starting polymer particles used herein, there may be preferably used catalysts composed of a catalyst component lS [i] containing a compound of a transition metal atom of I Groups IVB and VB of the periodic table which has a group `~ containing conjugated ~ electrons as a ligand, and an organometallic compound catalyst component [ii].

1 20 The transition metals belonging to Groups IVB and VB
i of the periodic table include metals of zirconium, tita-nium, hafnium chromium and vanadium.
'' :

:- j Examples of the group as the ligand having conjugated : .
~ electrons include, for example, cyclopentadienyl, alkyl-substituted cyclopentadienyl groups such as mthylcyclopen-` tadienyl, ethylcyclopentadienyl, t-butylcyclopentadienyl, ' :

,-. : , . . .
. ~ . . : .
: ~

3 s ~;~;3~

dimethylcyclopentadienyl and pentamethylcyclopentadienyl, and indenyl and fluorenyl.

Also suitable as the above-mentioned group are those containing at least two such ligands having a cycloalkadi-! enyl skeleton linked together through a lower alkylene group or a group containing silicon, phosphorus, oxygen or nitrogen. Such groups as mentioned above include ethylenebisindenyl and isopropyl(cyclopentadienyl-1-fluo-renyl).

At least one, preferably two ligands having the cy-cloalkadienyl skeleton are coordinated to the transition metal.

Ligands other than those having the cycloalkadienyl skeleton may be hydrocarbon groups having from 1 to 12 car-bon atoms, alkoxy groups, aryloxy groups, halogen or hydro-gen.

! !
; The hydrocarbon groups having from 1 to 12 carbon atoms may be alkyl, cycloalkyl, aryl and aralkyl, and con-cretely the alkyl group includes methyl, ethyl, propyl, isopropyl and butyl, the cycloalkyl group includes cy-clopentyl and cyclohexyl, the aryl group includes phenyl and tolyl, the aralkyl group includes benzyl and neophyl.
The alkoxy group includes methoxy, ethoxy and butoxy, the :~ ' - ' . , , ' .~ . :
:;~.,., . . . . . ' 201~302 ... .
`~aryloxy group includes phenoxy, and the halogen includes '~fluorine, chlorine, bromine and iodine.

:~The transition metal compounds containing at least one S ligand having a cycloalkadienyl skeleton may be repre-sented, when the valency of the transition metal contained d,iS four, by the formula:
~,R2kR31R4mR5nM
wherein M is zirconium, titanium, hafnium or vanadium, R2 `3~1 0 iS a group having a cycloalkadienyl skeleton, R3, R4 and R5, each is a group having a cycloakadienyl skeleton, an alkyl, cycloalkyl, aryl, aralkyl alkoxy or aryloxy group, or a .halogen or hydrogen atom, k is an integer of at least 1, and k+l+m+n = 9.
,'j 15 Particularly preferable compounds of the above-men-~-~tioned formula are those in which R2 and R3 are the groups .having a cycloalkadienyl skeleton, said two groups being linked to each other through a lower alkylene group or a ~\20 group containing silicon, phosphoryl, oxygen or nitrogen.

... . .
Concrete examples of the transition metal compounds `containing ligands having a cycloalkadidenyl skeleton rep-resented by the above-mentioned formula in which M is zir- ~ `~
conium are exemplified below.
~Bis(cyclopentadienyl)zirconium monochloride monohy-:: dride, bis(cyclopentadienyl)zirconium monobromide monohy-dride, bis~cyclopentadlenyl)methyl zirconium hydride, bis(cyclopentadienyl)ethyl zirconium hydride, bis(cyclopentadienyl)phenyl zirconium hydride, bis(cyclopentadienyl)benzyl zirconium hydride, bis(cyclopentadienyl)neopentyl zirconium hydride, bis(methylcyclopentadienyl)zirconium monochloride hy-dride, ,, 10 bis(indenyl)zirconium monochloride monohydride, bis(cyclopentadienyl)zirconium dichloride, bis~cyclopentadienyl)zirconium dibromide, : bis(cyclopentadienyl)methyl zirconium monochloride, bis~cyclopentadienyl)ethyl zirconium monochloride, ~ lS bis~cyclopentadienyl)cyclohexyl zirconium monochlo--~, ride, bis~cyclopentadienyl)phenyl zirconium monochloride, bis(cyclopentadienyl)benzyl zirconium monochloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(t-butylcyclopentadienyl)zirconium dichloride, ;~ bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, .` bis(cyclopentadienyl)zirconium dimethyl, .` bis(cyclopentadienyl)zirconium diphenyl, bis~cyclopentadienyl)zirconium dibenzyl, ` bis~cyclopentadienyl)zirconium methoxychloride, : bis~cyclopentadienyl)zirconium ethoxychloride, ,~ r . - : ' ' ' ~,''Vf~

.~,~:- ' :
: :,r C

3 8 20~5302 ~, :. bis(methylcyclopentadienyl)zirconium ethoxychloride, bis(cyclopentadienyl)zirconium phenoxychloride bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)diethyl zirconium, S ethylenebis(indenyl)diphenyl zirconium, ethylenebis~indenyl)methyl zirconium, ethylenebis(indenyl)ethyl zirconium monochloride, ~ ethylenebis(indenyl)zirconium dichloride, ,!q isopropylbisindenyl zirconium dichlor.ide, isopropyl(cyclopentadienyl)-1-fluorenyl zirconium ~ chloride, .~ ethylenebis(indenyl)zirconium dibromide, ethylenebis(indenyl)zirconium methoxymonochloride, .j ethylenebis(indenyl)zirconium ethoxymonochloride, -.~ lS ethylenebis(indenyl)zirconium phenoxymonochloride, ethylenebis(cyclopentadienyl)zirconium dichloride, .~
propylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(t-butylcyclopentadienyl)zirconium dichlo-ride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethyl zir-conium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methyl zirco- ;
:~ nium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, : ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium di-bromide, .'' ~ .

~ j~ " : . .

ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, i ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichlo-ride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichlo-ride, and ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichlo-ride.

i The same transition metal compounds as the above-men-tioned zirconium compounds except that the zirconium metal is replaced with a metal of titanium, hafnium, chromium or ~ vanadium are also usable as the catalyst component [i].

;. The organometallic compound catalyst components [ii]
, used in combination with the catalyst components [i] are preferably known aluminoxane compounds and aluminumoxy com-pounds. the aluminumoxy compounds may be formed, for exam-ple, by reaction of an organoaluminum compound with water or by reaction of a solution of aluminoxane in a hydrocar-bon solvent with an active hydrogen-containing compound.
- 25 The aluminumoxy compounds are insoluble or sparingly solu-ble in benzene at 60 C.

::;
. .

.

4 201~;3~2 In the preparation of the polymer particles used herein, the amount of the catalyst used varies according to the kind of the catalyst used. For example, when a combi-nation of the aforementioned catalyst component [A], organometallic compound catalyst component [B] and electron donor [C], or a combination of the above-mentioned catalyst component [i] and catalyst component [ii] is are used, the the component [A] or [i] is used in an amount, based on 1 liter of the polymerization volume, of usually from 0.001 to 0.5 mmol, preferably from 0.005 to 0.5 mmol in terms of the transition metal, and the organometallic compound cata-lyst component [B] or [ii] is used in an amount, based on 1 mole of the transition metal atom of the component ~A] or ~ [i] in the polymerization system, of usually from 1 to i lS 10000 moles, preferably from 5 to 500 moles in terms of the metal. Further, the electron donor [C], if any, is used in an amount, based on 1 mole of the transition metal atom of the component [A] in the polymerization system, of not more ~.
than 100 moles, preferably from 1 to 50 moles, and more ~i20 preferably from 3 to 20 moles.
,` -:
When polymerization or copolymerization may be carried -~
out in the presence of the above-mentioned catalyst, at a :~
temperature of usually from 20 to 200 C., preferably from 50 to 100 C., and under a pressure of from normal pressure to 100 kg/cm2, preferably from 2 to 50 kg~cm2.
~ ' '' 4 1 X~5302 ., In the preparation of the polymer particles used herein, preliminary polymerization is preferably carried out prior to main polymerization. In carrying out the pre-~liminary polymerization, there is used as the catalyst at ¦S least the catalyst component [A] in combination with the organometallic compound catalyst component [B], or a combi-nation of the catalyst components [i] and [ii].

!
In the preliminary polymerization, the amount of poly-merization, when titanium is used as the transition metal, $is usually from 1 to 2000 g, preferably from 3 to 1000 g, and more preferably from 10 to 500 g of polymer/g of the ~titanium component.
.~

15The preliminary polymerization is preferably carried out in the presence of inert hydrocarbon solvents, and ex-amples of the inert hydrocarbon solvents used in this case include aliphatic hydrocarbons such as propane, butane, n-pentane, i-pentane, n-hexane, i-hexane, n-pentane, n-oc-tane, i-octane, n-decane, n-dodecane and kerosine; ali-cyclic hydrocarbons such as cyclopentane, methylcyclopen-tane, cyclohexane and methylcyclohexane; aromatic nydrocar-bons such as benzene, toluene and xylene; and halogenated hydrocarbons such as methylene chloride, ethyl chloride, :'.25 ethylene chloride and chlorobenzene. Of the inert hydro-carbon solvents mentioned above, particularly preferred are aliphatic hydrocarbons, especially those having from 4 to :~
-~.

42 2 0 1~ 30Z
,, .

10 carbon atoms. It is also possible to use as the sol-vents the starting monomers used in the reaction.

Examples of a-olefins suitably used in the preliminary polymerization are those of not more than 10 carbon atoms such as ethylene, propylene, 1-butene, 1 pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. Of these a-olefins, preferred are those having from 3 to 6 carbon atoms, and especially propylene. These ~-olefins may be used singly or in combination of two or more so far as an appropriate proportion of the crystalline ~ polymer may be prepared. For example, in order to prepare `~ polymer particles containing portions of an amorphous olefin polymer in a relatively large proportion, e. g. not less than 30 ~ by weight, and having good morphology, the prepolymerization may be carried out using a mixed gas of '~ from 70 to 98 mol ~ of propylene and from 30 to 2 mol ~ of ethylene, thereby effecting copolymerization of propylene with ethylene.

The polymerization temperature employed in the prelim-inary polymerization varies according to the kind of a-olefin and inert solvent used and so cannot be defined ` indiscriminately, but generally is from -40 to 80 C., preferably from -20 to 40 C. and more preferably from -10 to 30 C. For example, the polymerization temperature is from -40 to 70 C. when propylene is used as the a-olefin, ' . .; . ,, .. -. , . , ~ .. ., , . , , . . ~ .

i from -40 to 40 C. when 1-butene is used, and from -40 to 70 C when 4-methyl-1-pentene and/or 3-methyl-1-pentene is used. In the reaction system of this preliminary polymer-¦ ization, hydrogen gas may also be allowed to coexist there-S with.

I After carrying out or not carrying out the above-men-tioned preliminary polymerization, the aforesaid monomer is then introduced into the reaction system to carry out poly-0 merization reaction (main polymerization~, whereby the polymer particles can be prepared.

The monomer or monomers used in the main polymeriza-tion may be the same or different from the monomer or monomers used in the preliminary polymerization.

., .
The polymerization temperature employed in this main polymerization is usually from -50 to 200 C., preferably from 0 to 150 C. The polymerization pressure employed is usually from normal pressure to 100 kg/cm2, preferably from normal pressure to 50 kg/cm2, and the polymerization reac-tion may be carried out by any of the batchwise, semi-con-tinuous and continuous methods.
', The molecular weight of the olefin polymer may be reg-ulated by the addition of hydrogen and/or by adjusting the polymerization temperature.

r~

4 4 ~015302 , The polymer particles thus obtained, each is composed of a portion or portions comprising a crystalline olefin polymer and portions comprising an amorphous olefin poly-mer. In the polymer particles used herein, the proportion of the amorphous olefin polymer present therein is usually from 20 to 80 % by weight, preferably from 25 to 70 % by weight, more preferably from 30 to 60 % by weight, and most preferably from 33 to 55 % by weight. The content of the ti amorphous olefin polymer of the polymer particles can be :`.i 0 determined by measuring an amount of a component which is soluble in n-decane at 23 C.

, à, It is desirable to use such polymer particles which i have not been heated even once to a temperature higher than both the melting point of the crystalline olefin polymer ~' and the glass transition point of the amorphous olefin polymer. In such polymer particles which have not been ~! heated even once to a temperature higher than both the melting point of the crystalline olefin polymer and the glass transition point of the amorphous olefin polymer, the islands constituted by the amorphous olefin polymer have an average particle diameter of not exceeding 0.5 ~m, prefer-ably not exceeding 0.1 ~m, and more preferably from 0.00001 to 0.05 ~m.

The term "amorphous olefin polymer" as used herein is intended to designate that part of polymer particles which ' !

dissolves in n-decane at 23 C, and specifically is ob-tained by solvent separation in such a manner that a mix-ture of n-decane (500 ml) and the polymer particles (3 g) is stirred at a temperature of lg0-145 C to dissolve that part of the polymer particles in the solvent as far as pos-sible; after the stirring is suspended, the resulting sus-pension is cooled to 80 C in 3 hours and to 23 C in 5 hours, and kept at 23 C for 5 hours and then filtered through a G-4 glass filter; and the n-decane is removed from the resulting filtrate to obtain the amorphous poly-mer.

~ r ~ er.~bool;r~n~
A In the first proces-according to the inventlon, the ~ thermoplastic elastomer crosslinked within the particles is A' 15 prepared in such a manner that the above-mentioned polymer particles are brought ln contact with a crosslinking agent , at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer.
` 20 The crosslinking agents which can be used herein are organic peroxides, sulfur, phenol type vulcanizers, oximes and polyamines, and from the standpoint of properties of - the resulting thermoplastic elastomers, organic peroxides - 25 and phenol type vulcanizers, in particular crganic perox- ~-ides are preferred.

:: :
' :~
' ~

. .

t Usable phenol type vulcanlzers include alkylphenol- -formaldehyde resins, triazine-formaldehyde resins and me-lamine-formaldehyde resins.

~' :
Usable organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5 bis(tert-butylper-oxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, l,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-9,9-bis(tert-butylperoxy)valerate, dibenzoyl peroxide and tert-butylperoxybenzoate. Of the organic peroxides mentioned above, preferred are dibenzoyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene from the standpoint of crosslinking reaction time, odor and scorch stability.

~ 15 ¦ In order to realize uniform and mild crosslinking re-action, crosslinking auxiliaries are used preferably.
; Crosslinking auxiliaries usable herein include sulfur, p-, quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N-'`20 4-dinitroisoaniline, nitrobenzene, diphenyl guanidine, ~, .
trimethylolpropane-N,N-m-phenylene dimaleimide, divinylben-zene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol ~``A dimethacrylate, trimethylolpropane trimethacrylate, a~
methacrylate, vinylbutyrate and vinyl stearate. By the use of such compounds as exemplified above, the uniform and mild crosslinking reaction can be expected. Particularly, . :

~ ~j~ ' : ' ' ' ' `x 4 7 20~s~02 ) ~'the use of divinylbenzene in the process according to the -sinventicn is most preferable, because this divinylbenzene is easy to handle and has a good compatibility to the poly-mer particles and, moreover, has an organic peroxide solu-- .
5 bilizing action and acts as a dispersion assistant of per-oxide and accordingly provides a uniform and mild `l!
lcrosslinking reaction, whereby a thermoplastic elastomer which is well balanced between flowability and physical :~properties is obtained. In the present invention, such 1O crosslinking auxiliaries are used in an amount, based on 100 parts by weight of the polymer particles, of from 0.1 ~.to 2 % by weight, preferably from 0.3 to 1 % by weight, 3whereby a thermoplastic elastomer excellent in flowability, which does not bring about change in physical properties by lS a heat history at the time of molding said elastomer, is obtained.

In the process according to the invention, it is also possible to carry out the crosslinking reaction of the 20 polymer particles and the crosslinking agent, and option-ally the crosslinking auxiliary by adding thereto a mineral oil softening agent.

,~, .
The mineral oil softening agent is a high boiling ~`25 petroleum fraction which is usually used for the purposes of weakening intermolecular force of rubber when the rubber `is rolled, and facilitating the processing and, at the same .,.
`'` : ;~
:`` ~'';

j. - ~ , . ~ ,. , . . .. . - -i time, assisting dispersion of carbon black, white carbon and the like, or of reducing the vulcanized rubber in hard-ness to increase flexibility or elasticity, and such min-eral oil softening agent includes paraffinic, naphthenic 5 and aromatic mineral oils.

The mineral oil sof~ening agents are used for further improving flow characteristics, i.e. moldability of the thermoplastic elastomer, in an amount, based on 100 parts 10 by weight of the polymer particles, of usually from 1 to 100 parts by weight, preferably from 3 to 90 parts by weight and more preferably from S to 80 parts by weight.

The crosslinking agent, and the crosslinking auxiliary ~ 15 and mineral oil softening agent, if any, may be used in a 3 condition diluted with a swelling solvent. The swelling ~ solvent dilutes the crosslinking agent, and the crosslink-` ing auxiliary, if any, to promote their dispersion onto the surfaces of the polymer particles, and swells the polymer v 20 particles thereby facilitating carriage of the crosslinking agent and auxiliary into the polymer particles.
Accordingly, it is possible by the use of the swelling sol-vent to effect the crosslinking reaction uniformly even in ~; locations inside of the particles. If a swelling solvent 25 which is a poor solvent for the polymer-particles is used, the crosslinking reaction may be effected selectively in the vicinity of the surfaces of the polymer particles. The '': ~ ' - .. . .. .

4 9 2015302 ~s . .

particular swelling solvent used may be selected depending x upon the nature of the polymer particles. Needless to say, . use of the swelling agent is not absolutely essential for the crosslinking reaction.
.~ Examples of usable swelling solvents include, for ex- ample, aromatic hydrocarbons such as benzene, toluene and 3 xylene; aliphatic hydrocarbons such as pentane, hexane, . heptane, octane, nonane and decane; alicyclic hydrocarbons .,f 1 0 such as cyclohexane, methylcyclohexane and decahydronaph-~'~ thalene; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chlorofolm, carbon tetrachloride, tetrachloroethane, dichloroethane and trichroloethylene; alcohols such as .~, I ~ -, 15 methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec.-butanol and tert.-butanol; ketones such as acetone, , methyl ethyl ketone and methyl isobutyl ketone; esters such , ' as ethyl acetate and dimethyl phthalate; and ethers such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydro-1 20 furan, dioxane and anisole.
,~j Such a swelling solvent may be used in an amount of from 1 to 100 parts by weight, preferably from 5 to 60 parts by weight, and more preferably from 10 to 40 parts by , 25 weight, per 100 parts by weight of the polymer particles.
'-' ': -,: , :
' .. ~ ... :

~ 50 20~5302 .. .
When brought in contact with the polymer particles, the swelling solvent illustrated above swells the polymer particles, in particular the amorphous olefin polymer por-tions of the particles, thereby serving to facilitate en-5 trance of the crosslinking agent and auxiliary into the polymer particles.

The amount of the swelling agent used in the process according to the invention does not exceed 200 parts by ~'; 10 weight per 100 parts by weight of the polymer particles.
and thus, the crosslinking reaction involved is different from suspension reactions in which a great excessive amount 3 of a solvent is used.

~A ~ sIn the second proccs~ according to the invention, the crosslinking reaction of the above-mentioned polymer parti-!, cles is carried out by bringing the polymer particles in . contact with a radical initiator and a graft modifier at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer. Upon crosslinking of the polymer particles a crosslinking agent other than the radical initiator may be coexistent.

25Suitable graft modifiers which can be used herein in-clude glycidyl group-containing ethylenically unsaturated compounds,carboxyl group-containing ethylenically unsatu-'' rated compounds and acid anhydrides and derivatives thereof, hydroxy group-containing ethylenically unsaturated compounds,and amino group-containing ethylenically unsatu-n rated compounds.
S
~ Examples of the glycidyl group-containing ethyleni-. cally unsaturated compounds include, for example, glycidyl ~ (meth)acrylate, allyl glycidyl ether,2-methylallyl glycidyl .~
ether and vinyl glycidyl ether, ~:~
~ 10 glycidyl esters of unsaturated dicarboxylic acids such ;~ as diglycidyl maleate, glycidylmethyl maleate, isopropyl-glycidyl maleate, glycidyl-t-butyl maleate, diglycidyl fu-marate, glycidylmethyl fumarate, isopropylglycidyl fu-:J marate, diglycidyl itaconate, methylglycidyl itaconate, isopropylglycidyl itaconate, diglycidyl 2-methylenegul-tarate, glycidylmethyl 2-methyleneglutarate and monogly-` cidyl ester of butenedicarboxylic acid, and other glycidyl compounds such as 3,4-epoxybutene, 3,4-;~ epoxy-3-methyl-l-butene, vinylcyclohexene monoxide p-gly-cidylstyrene.

Examples of the carboxyl group-containing ethyleni-cally unsaturated compounds and~acid anhydrides and deriva-. tives thereof include, for example, acrylic acid, maleic : :
acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,crotonic acid and Nadic~ acid (endocis-bi-cyclo[2,2,1]hept-5-ene-2,3~di-carboxylic acid, acid anhy-: :" ' . :

;!'J
,.,j ;~. 5 2 20~$~2 ~i ~drides thereof and their derivatives, for example, acid ,~ , .
halides, amides, imides and esters, including, for example, ~malenyl chloride, malenylimide, maleic anhydried, citra-,~
~conic anhydride, monomethyl maleate,and dimethyl maleate.
:~5 Of these, unsaturated dicarboxylic acids and anhydrides ,~thereof, in particular maleic acid and Nadic~ acid and an-;~hydride thereof are preferred.

~Examples of the hydroxy group-containing ethylenically ;~10 unsaturated compounds include, for example, acrylates and ~methacrylates such as hydroxyethyl (meth)acrylate,2-hydrox-.dypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydrox-ypropyl (meth)acrylate, glycerine mono(meth)acrylate, pen-taerithritol mono(meth)acrylate, trimethylolpropanemono(meth)acrylate, tetramethylolethane mono(meth)acrylate, butenediol mono(meth)acrylate, polyethylene glycol .~mono(meth)acrylate and 2-t6-hydroxyhexanoyloxy)ethyl acry-late, and other hydroxy group-containing ethylenically unsatu-rated compound including, for example, 10-undecene-1-ol, 1-octene-3-ol, 2-methanol-norbornene, hydroxystyrene, hydrox-~ yethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol-:~ acrylamide, 2-(meth)acryloyloxyethyl acid phosphate, glyc-erine monoallyl ether, allyl alcohol, allyloxyethanol and : 2-butene-1,9-diol.

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.i 53 Z O 1 5 ~02 r The amino group-containing ethylenically unsaturated ~ compounds which can be used herein may be vinyl monomers ?' having at least one amino group of the formula : -N R1R2 wherein R1 represents a hydrogen atom or a methyl or ethyl group, R2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms or a cycloalkyl group having from 6 to 12 carbon atoms, preferably from 6 to 7 carbon atoms, and the alkyl ~-and cycloalkyl groups may have one or more substituents.

Examples of such amino group-containing ethylenically unsaturated compounds include, for example, amino group-containing alkyl esters of acrylic and methacrylic acids such as aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, ~ phenylaminoethyl methacrylate, cyclohexylaminoethyl ;; methacrylate and methacryloyloxyethyl acid phosphate mo-noethanolamino half salt ; vinylamines such as N-vinyldiethylamine and N-acetylvinylamine; allylamines such , 20 as allylamine, methallylamine, and N-methylallylamine;
acrylamides such as acrylamide, methacrylamine, N-methy-lacrylamide, N.N-dimethylacrylamide and N,N-dimethylamino-propylacrylamide; and aminostyrenes such as p-aminostyrene.
; These compounds may be used alone or in combination. Of these, particularly preferred are allylamine, aminoethyl ~ methacrylate, aminopropyl meth~crylate and aminostyrenes.

': :
.' :'.

The above-illustrated polar group-containing ethyleni-cally unsaturated compounds may be used alone or in combi- ,, nation The above-illustrated polar group-containing ethyleni-cally unsaturated compounds are used in an amount of usu-ally from 0.01 to 50 parts by weight, preferably from 0.1 to 90 parts by weight per 100 parts by weight of the poly-mer particles. When two ore more polar group-containing 0 ethylenically unsaturated compounds (graft modifiers) are used in combination, they may be used in any proportions.

When the graft modifier is used, the crosslinking re-action of the polymer particles must be carried out in the presence of a radical initiator. The radical initiator i5 used in an amount of usually at least 0.02 part by weight, preferably from 0.05 to 10 parts by weight, and more ' preferably from 0.1 to 5 parts by weight per 100 parts by weight of the polymer particles.

... ~
Suitable radical initiators which can be used herein are organic peroxides illustrated hereinabove as the crosslinking agent. The radical initiators may be used - alone or in combination.

~.

~ In addition to the graft modifier and radical initia-. .
~ tor, crosslinking agents other than the radical initiator, ::
j ,~
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; ;-.~,,~.

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i for example, sulfur and phenolic vulcanizing agents may also be used in the second process according to the inven-tion.

3~ 5 The crosslinking reaction according to the invention is carried out at a temperature where the polymer particles are not molten and do no~ adhere to one another.
Generally, the reaction is carried out at a temperature of not lower than 0 C. and below the higher one of the melt-:71 0 ing point of the crystalline olefin polymer and the glass ..~
transition temperature of the amorphous olefin polymer.

For example, in cases wherein the higher melting olefin polymer is polypropylene, high density polyethylene or low ;~density polyethylene,the upper limit of the reaction tem- ;

perature will be about 150 C., about 120 C. and about 90 C., respectively.
6~

,The crosslinking reaction is carried out for a period of from 1 to 30 times, preferably from 2 to 10 times, and more preferably from 3 to 7 times the half-life of the jcrosslinking agent at the reaction temperature, and under a pressure of from 0 to 50 kg/cm2, preferably from 1 to 20 `~~kg/cm2 , and more preferably from 1 to 5 kg/cm2. The reac-tion may be carried out either batchwise or continuously.
~m b~dl m~t~
In the first process according-to the invention, while it is preferred to carry out the crosslinking reaction by , 5 6 ZOlS30Z

~ bringing the polymer particles in contact with the ;3~ crosslinking agent, and optionally crosslinking auxiliary ~ and mineral oil softening agent, simultaneously, the poly-,:t mer particles may be brought in contact with the crosslink-. 5 ing agent, and optionally crosslinking auxiliary and min-3 eral oil softening agent in sequence to effect the crosslinking.
~bod~
In the second p~Y~X~r according to the invention, . 10 while it is preferred to carry out the crosslinking reac-` tion and graft modification by bringing the polymer parti-~ cles in contact with the graft modifier and radical initia-tor, and optionally crosslinking agent other than the radi-cal initiator, crosslinking auxiliary and mineral oil soft-lS ening agent, simultaneously, the polymer particles may be brought in contact with the graft modifier and radical ini-tiator, and optionally crosslinking agent other than the radical initiator, crosslinking auxiliary and mineral oil softening agent, in sequence to effect the crosslinking and 20 graft modification.
. :.

`~. When polymer particles polymer, each composed of a :: portion or portions comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, :~`
- 25 crosslinked by the processes according- to the invention, - the crosslinking takes place within the particles, particu-larly in the amorphous olefin portions in the particles, ., .
~ , h ~

": `~"` . :
" ~ ' ' ~ ' ' ' " ;"~,' i . ~ ' ' ~ 57 Z01530Z

2 whereby the amorphous olefin polymer portions (rubber com-~,,'J, ponent) are fixed at a molecular segment level in the poly-mer particles.

5Reactors for carrying out the reaction according to the invention may be either vertical of horizontal so far as it is capable of mixing the polymer particles. When the reaction is to be carried out under heating, reactors ca-pable of mixing and heating the polymer particles are used.
;, 10 Suitable reactors which can be used herein include flu-idized bed reactors, moving bed reactors, loop reactors, horizontal reactors equipped with agitating blades, rotat-ing drums and vertical reactors equipped with agitating ; blades.

The particles of the thermoplastic elastomer crosslinked within the particles thus obtained desirably contain an insoluble gel content which is not extracted in cyclohexane, as measured by the following procedure, in an amount of at least 10 % by weight, preferably from ~0 to 100 % by weight, more preferably from 60 -to 99 % by weight " and most preferably from 80 to 98 % by weight.
. .

~ . ., ~ When the gel content as measured above is 100 % by ; 25 weight~ this shows that the resulting thermoplastic elas- ;
tomer has been perfectly crosslinked.
'.:

I :
..

v~

s 8 ~(~ `02 .
:!
The cyclohexane-insoluble gel content is measured in the following manner. About 100 g of pellets (1 mm x 1 mm x 0.5 mm) as specimen of the thermoplastic elastomer was ~, immersed in 30 cc of cyclohexane in a closed container at ; 5 23 C for 48 hours, the specimen was taken out therefrom ., .
and then dried. When the thermoplastic elastomer contains i cyclohexane-insoluble fillers, pigments or the like, the weight of the dried specimen from which the total weight of such insolubles as mentioned above has been subtracted is 10 taken as a corrected final weight ~Y) after drying. On one s hand, the weight of the pellets as the specimen from which the total weight of components insoluble in cyclohexane other than the ethylene/a-olefin copolymer, for example, plastlcizer and cyclohexane-insoluble rubber component, and 15 from which the total weight of cyclohexane-insoluble 3 fillers, pigments and the like other than the polyolefin resin contained in the thermoplastic elastomer has been ~` subtracted when such insolubles are contained in said ther-moplastic elastomer, is taken as a corrected initial weight 20 (X).

From the values of above-mentioned weights, the cyclo-hexane-insoluble gel content is determined according to the r~' following equation, ` 25 Corrected final weight (Y) Gel content (~) = ... ! x 100 ColTected mltlal weight (X) ,.
:
! . , ' '~',t'.,,'.,,, ~ ', ' ' ~3~
~... . . . .
~" . . . , :
.... .. . . ... . .
`:~ : : . . .

The partlcles of the thermoplaatlc elastomer prepared by the proce3ses accordlng to the lnventlon have an average partlcle dlameter of from 100 to 5000 ~m, preferably from 200 to 4000 ~m, more preferably from 300 to 3000 ~m wlth a geometrlc standard devlatlon of from 1.0 to 2.0, preferably from 1.0 to 1.5 more preferably from 1.0 to 1.3, an apparent bulk denslty of from 0.25 to 0.70, preferably from 0.30 to 0.60, more preferably from 0.35 to 0.50, an aspact ratio of from 1.0 10to 3.0, preferably from 1.0 to 2.0, more preferably from l.0 to 1.5, and contaln not more than 20 % by welght, preferably from 0 to 10 % by weight, more preferably from 0 ~! to 2 % by weight of fine particles having a partlcle diame-ter of not more than 100 ~m.
!
{ 15 Stablllzers lncluding phenolic, phosphorus, sulfur, ~ hlndered am~ne and higher fatty acid stablllzers may be ln-j corporated lnto the polymer particles used ln or into the thermoplastlc elastomer partlcles prepared by the processes accordlng to the lnventlon. The amount of the stablllzer used may be from 0.01 to 10 parts by welght, preferably from 0,05 to 5 parts by weight, based on 100 parts by welght o f the polymer partlcles.

; 25The thermoplastlc elastomers prepared by the procesRes accordlng to the lnventlon, may be lncorporated wlth fillers such as calclum carbonate, calcium silicate, clay, ' - :

: .

: ~, .
. ~ . . . .
~,~'. ''' : .' .: , .

6 o Z015302 caoline, talc, silica, diatomaeceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, cal-cium sulfate, basic magnesium carbonate, molibdenum disul-fide, graphite, glass fiber, glass bead, Shirasu balloon 3 5 and carbon fiber; and coloring agents such as carbon black, titanium oxide, zinc flower, red iron oxide, ultramarine, prussian blue,azo dyes, nitoso dyes, lake pigments and ph-., ~` thalocyanine pigments.

~J 10 Effect of the In~ention By the processes according to the invention in which the polymer particles are crosslinked at a relatively low ` temperature, undesirable thermal decompo$ition of the poly-mer particles can be controlled and there are obtained at 15 low production costs thermoplastic elastomers which have excellent elasticity even with a reduced rubber content and excellent strength, and are capable of being molded to ar-ticles which are very uniform, and excellent in strength properties such as impact strength and tensile strength, ~ 20 toughness, heat resistance, flexibility at low temperature, ~. surface smoothness, and properties of being painted.
,~

In particular, the thermoplastic elastomers in which the amorphous olefin polymer portions (rubber component) ; 25 are fixed at a molecular segment level in the polymer par-.~ ticles, are capable of being molded to articles which are ~ excellent by far in flexibility at low temperature, surface . . , :.. ,.............. :

~ ;t~

,, t smoothness and propertles of being painted, in particular, in appearance after painted.

I The thermoplastic elastomers obtained by the process `r 5 according to the present invention can be molded by using molding apparatus used for common thermoplastic polymers, and are suitable for extrusion molding, calender molding and particularly for injection molding.
~, 0 Such thermoplastic elastomers are used for the manu-facture of automotive parts such as body panel, bumper j part, side shield and steering wheel, footwears such as ^~ sole of a shoe and sandals, electrical parts such as cover-ing of electric wire, connector, cap plug and packings, leisure goods such as golf club grip, baseball bat grip, :3, fin for swimming and hydroscope, gasket, waterproof cloth, garden hose and belt.
.i .
The invention is illustrated below with reference to ` 20 examples, but it should be construed that the invention is no way limited to the examples.

Example [Preparation of catalyst component [A]~
A thorouqhly nitrogen-purged high speed stirring appa-ratus having an ~nternal volume of 2 liters (manufactured and sold by Tokushukika Kogyo K.K.~ was charged with 700 ml :~: .... . . . . .
: ~ " ' ' ~ - '. . .. ..

~1 of purified kerosine, 10 g of commercially available MgCl2, 24.2 g of ethanol and 3 g of sorbitan distearate (sold un-~e~ rk der a tradc namc Emasole 320 by Kao Atlas K.K.), and the system was elevated in temperature with stirring and S stirred at 120 C for 30 minutes at 800 rpm. Using a Teflon tube having an inside diameter of 5 mm, the contents of the stirring apparatus was transferred with high speed stirring to a 2-liter glass flask ~equipped with a stirrer) having been charged with 1 liter of purified kerosine pre-t 1 0 viously cooled to -10 C. The resulting solids were col-~ lected by filtration and thoroughly rinsed with hexane to obtain carriers.

To a suspension of 7.5 g of the carrier in 150 ml of lS titanium tetrachloride at room temperature was added 1.3 ml ~ of diisobutyl phthalate, and the system was then elevated in temperature to 120 C. After 2-hour stirring at 120 C, the solids were collected by filtration and suspended again rl in 150 ml of titanium tetrachloride, followed by stirring 20 again at 130 C. for 2 hours. The reacted solids were col-lected by filtration from the reaction product and thor-oughly rinsed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. This catalyst component was composed of 2.2 % by weight of titanium, 63 ~
25 by weight of chlorine and 20 % by weight of magnesium, in terms of atom, and 5.5 % by weight of diisobutyl phthalate.
Thus, there was obtained a spherical catalyst having an av-.:

r' ," ~:

~, .. . ..

` 6 3 20153~2 :.
erage particle size of 64 ~m and a geometrical standard de-i viation (~g) of 1.5 of particle size distribution.

., [Preliminary polymerization]
5The catalyst component [A] was subjected to the fol-lowing preliminary polymerization.

A 400 ml nitrogen-purged glass reactor charged previ-ously with 200 ml of purified hexane was then charged with 0 20 mmoles of triethylaluminum, 4 mmoles of diphenyl dimethoxysilane and 2 mmoles, in terms of titanium atom, of the above-mentioned Ti catalyst component [A], and propy-.~
lene was fed at a rate of 5.9 N1/hr over a period of 1 hour ~ to polymerize 2.8 g of propylene per 1 g of the Ti catalyst ;~ 15 component [A]. After the completion of the preliminary ~ polymerization, the liquid portion was removed, and the `, solids portion separated was suspended aqain in decane.
I :
[Polymerization]
-I 20 Preparation of Copolymer ~
A 17-liter polymerization vessel charged with 2.0 kg of propylene and 11 N liter of hydrogen at room temperature was elevated in temperature, and then charged at 50 C with lS mmoles of triethylaluminum, 1.5 mmoles of cyclohexyl~

methyldimethoxysilane and 0.05 mmole, in terms of titanium atom, of the catalyst component [A] which had been sub-jected to the preliminary polymerization, and the tempera-:

6 4 Z0~5302 ture inside the polymerization vessel was maintained at 70C. In the lapse of 30 minutes thereafter, a vent valve was opened to purge the propylene until normal pressure in-side the polymerization vessel was attained. After the purge, copolymerization was successively carried out. That is, to the polymerization vessel were fed ethylene at a rate of 480 Nl/hr, propylene at a rate of 720 Nl/hr and hy-drogen at a rate of 12 Nl/hr. The divergence of the vent of the polymerization vessel was controlled so that the pressure inside the vessel became 10 kg/cmZ G. The temper-ature of the polymerization vessel was maintained at 70 C.
The copolymerization was carried for 120 minutes, and the pressure inside the polymerization vessel was released to obtain 2.6 kg of a polymer having MI of 2.5 g/10 min at 230 IS C under a load of 2 kg, the ethylene content of 29 mol%
and an apparent bulk gravity of 0.45. The amount of the component soluble in n-decane at 23 C was 36 % by weight, ` and the ethylene content in said soluble component was 49 mol%.

The particles of the copolymer (I) so prepared had an average particle diameter of 2100 ~m with a geometric stan-dard deviation of 1.4, contained fine particles passing through 150 mesh in an amount of 0~2 % by weight and exhib-~ 25 ited a falling time of 13.2 seconds.
.:
~ Preparation of Copolymer (II) -, - . . . ~ ~ ".

,,,.,_ .~ ' ' ~
. ~'" ~ ', ,' , ' "', , ~ 6 s 2015302 .

A 17-liter polymerization vessel charged with 2.0 kg of propylene and 19 N liter of hydrogen at room temperature was elevated in temperature, and then charged at 50 C with 3 15 mmoles of triethylaluminum, 1.5 mmoles of cyclohexyl-5 methyldimethoxysilane and 0.05 mmole, in terms of titanium atom, of the catalyst component [A~ which had been sub-~ jected to the preliminary polymerization, and the tempera-`~ ture inside the polymerization vessel was maintained at 70 `.9 C. In the lapse of 30 minutes thereafter, a vent valve ' 10 was opened to purge the propylene until normal pressure in-side the polymerization vessel was attained. After the ~, purge, copolymerization was successively carried out. That is, to the polymerization vessel were fed ethylene at a rate of 480 Nl/hr, propylene at a rate of 720 Nl/hr and hy-15 drogen at a rate of 12 Nl/hr. The divergence of the vent of the polymerization vessel was controlled so that the pressure inside the vessel became 10 kg/cm2 G. The temper-ature of the polymerization vessel was maintained at 70 C.
The copolymerization was carried for 150 minutes, and the 20 pressure inside the polymerization vessel was released to obtain 2.5 kg of a polymer having MI of 3.9 g/10 min at 230 C under a load of 2 k~, the ethylene content of 28 mol%
and an apparent bulk gravity of 0.47. The amount of the component soluble in n-decane at 23 C was 28 % by weight, 25 and the ethylene content in said soluble component was 47 mol%.

.. '` .

~ .

6 6 ;~015302 ,, he particles of the copolymer ~II) so prepared had an average particle diameter of 2200 ~m with a geometric stan-dard deviation of 1.5, contained fine particles passing 3 through 150 mesh in an amount of 0.1 % by weight and exhib-5 ited a falling time of 8.5 seconds.

~xamples 1 to 3 A 15-liter stainless steel autoclave equipped with an agitating element having helical type double ribbons is 0 charged with 3 kg of particles the copolymer (copolymer I
.~
~' in Examples 1 and 2, and copolymer II in Example 3) and completely purged with nitrogen. Thereafter, a mixed liquid having a composition as shown in Table 1 is added dropwise at room temperature over a period of 10 minutes to 15 the autoclave, while stirring the polymer particles, and the stirring is conducted for additional 30 minutes to im-` pregnate the polymer particles with the reagents contained in the mixed liquid. Subsequently, the temperature of the system is raised to 100 C., and maintained at that temper-20 ature for a period of 4 hours. At the end of the period the temperature is lowered to 80 C., and the content of the autoclave is dried under reduced pressure.

. , .
The thermoplastic elastomer obtained was measured for ~ 25 MFR and gel content.

'~:

6 7 20~5302 The thermoplastic elastomer was injection molded to a square plate having a thickness of 3 mm under the condi-tions noted below.

5 Conditions of in~ection moldina A~ Molding machine : Dinamelter ~supplied by MEIKI Works K. X.) Molding temperature : 200 C.
Injection pressure : Primary pressure 1300 kg/cm2 0 Secondary pressure 700 kg/cm2 Injection speed : Ma~imum ~-~ Molding rate : 90 seconds/cycle i Gate : Direct gate (with a gate land of 10 mm in length, 10 mm in width and 3 mm in depth) ~, ' Specimens were cut out from the injection molded plate - and tested for tensile properties, initial flexual modulus ~ and Izod impact strength. Tensile strength at break (Tb in : 20 kg/cm2) was determined in accordance with JIS K-6031.
Initial flexual modulus ~FM in kg/m2) was determined in ac-cordance with ASTM D 790. Notched Izod impact strength (Izod in kgcm/cm) was determined in accordance with ASTM D
~` 256.

A test piece having a length of 120 mm, a width of 20 mm and a thickness of 3 mm was cut out from the injection : :~
~ Tr~_~Q~k Z01530;~

. . .
molded plate tested for heat sag at a temperature of 100 C. as a measure of heat resistance as noted below. That is, the test piece was horizontally fixed with clips along its width at a distance of 20 mm from one end, and aged for 5 1 hour at 100 C. The sag in mm of the other end was mea-sured.

1 Results are shown in Table 1.

Comparative E~ample A mixture of 39 parts by weight of EPDM having a Mooney viscosity, ML1+4(100 C), of 10, an ethylene content of 75 mol%, an iodine value, as a measure of ethylidenenor-bornene, of 10, 55 parts by weight of homopolypropylene 15 having MFR (230 C., 2.16 kg) of 7 g/10 min and 6 parts by weight of paraffinic process oil was kneaded in a Banbury's mixer, rolled to a sheet and plletized by means of a square ~-~ pelletizer.

A mixture of 100 parts by weight of the pellets, 0.14 ; part by weight of di-1-t-butylperoxydi-isopropylbenzene and ; 0.21 part of divinylbenzene was blended in a Henschl's mixer and extruded through an extruder at an extrusion tem-perature of 250 C. to provide a thermoplastic elastomer.

The thermoplastic elastomer so prepared was tested as in Examples 1 to 3.

; :`' . ~.. .

" Z015302 P~esults are shown in Table 1.
:
Table 1 Ex. 1 Ex. 2 Ex. 3 Comp. Ex. 1 l ..
Composition of cross-linking mixed liquid m BPO (wt %) 0.15 0.25 0.15 ___ DVB (wt %) 0.15 0.15 0.15 ___ toluene (ml) 5G0 500 500 ___ oil (wt %) 0 6 6 ___ . . .

lS Properties of thermo-elastomer MFR, 230 C.,2.16 kg : .
(g/lO min) 7 17 16 13 FM (kg/cm2) 4300 4200 4500 4400 Tb ~kg/cm2) 234 225 228 190 heat sag (mm) 3 2 2 3 .
Izod (-30 C.) N. B. N. B. N. B. N. B.
.
BPD : Benzoyl peroxide ~ -DVB : Divinylbenzene ~le 4 [Polymerization] ~ ~ ;

7 o 2~;3~)Z

Preparation of Copolymer (III) A 17-liter polymerization vessel charged with 2.5 kg of propylene and 9 N liter of hydrogen at room temperature was elevated in temperature, and then charged at 50 C with 5 15 mmoles of triethylaluminum, 1.5 mmoles of diphenyldimethoxysilane and 0.05 mmole, in terms of tita-nium atom, of the catalyst component [A] which had been subjected to the preliminary polymerization, and the tem-perature inside the polymerization vessel was maintained at 0 70 C. In the lapse of 10 minutes thereafter, a vent valve was opened to purge the propylene until normal pressure in-side the polymerization vessel was attained. After the purge, copolymerization was successively carried out. That is, to the polymerization vessel were fed ethylene at a rate of 480 Nl/hr, propylene at a rate of 720 Nl/hr and hy-drogen at a rate of 12 Nl/hr. The divergence of the vent of the polymerization vessel was controlled so that the pressure inside the vessel became 10 kg~cm2. The tempera-ture of the polymerization vessel was maintained at 70 C.
The copolymerization was carried for 85 minutes, and the pressure inside the polymerization vessel was released to obtain 3.1 kg of a polymer having MI of 3.9 g/10 min at 230 C under a load of 2 kg, the ethylene content of 28 mol%
and an apparent bulk gravity of 0.39. The amount of the component soluble in n-decane at 23 C was 37% by weight, and the ethylene content in said soluble component was 99 mol%.

A .
'1"'.' -: - ., ' . .. ' ~' ' ' `: ' . .

-7 1 21~S~
.

'~ The particles of the copolymer (III) so prepared had an average particle diameter of 1900 ~m with a geometric standard deviation of 1.3, contained fine particles passing through 150 mesh in an amount of 0.0 % by weight and exhib-1 5 ited a falling time of 13.1 seconds.

r A 15-liter stainless steel autoclave equipped with an agitating element having helical type double ribbons is charged with 3 kg of particles the copolymer (III) and com-10 pletely purged with nitrogen. Thereafter, a mixed liquid ` having a composition as shown in Table 2 is added dropwise at room temperature over a period of 10 minutes to the au-~j toclave, while stirring the polymer particles, and the stirring is conducted for additional 30 minutes to impreg-15 nate the polymer particles with the reagents contained in 3 the mixed liquid. Subsequently, the temperature of the system is raised to 100 C., and maintained at that temper-ature for a period of 4 hours. At the end of the period the temperature is lowered to 80 C., and 7.5 kg of acetone 20 is added to the system, which is stirred for 1 hour at 80 C. The content of the autoclave is drawn out, filtered to collect the polymer, which is then washed three times with 9 kg of acetone and dried under reduced pressure.
'., ~:~'~:
The thermoplastic elastomer obtained is measured for MFR and gel content. ~'his thermoplastic elastomer is in-jection molded into a sheet, and the sheet is evaluated for appearance and physical properties. Results are shown in .~.
Table 2.

Table 2 Polymer particles 3 kg of copolymer (III) _ Mixed liquid Benzoyl peroxide 6 g 0 Divinylbenzene 9 g toluene ___ paraffinic oil ___ Propertie~
MIR 230 C.,2.16 kg 12 g/10 min.
Gel content 80 wt% :~ :
Tensile strength 210 kg/cm Elongation 650 ~ :
Smoothness of sheet qood ` ~.
Example 5 A 15-liter stainless steel autoclave equipped with an agitating element having helical type double ribbons is charged with 3 kg of particles the copolymer (III) and com-pletely purged with nitrogen. Thereafter, a mixed liquid having a composition as shown in Table 3 is added dropwise at room temperature over a period of 10 minutes to the au-;," . ~ : .
" .

73 ~ ~ ~

toclave, while stirring the polymer particles, and thestirring is conducted for additional 30 minutes to impreg-nate the polymer particles with the reagents contained in the mixed liquid. Subsequently, the temperature of the system is raised to 100 C., and maintained at that temper-ature for a period of 4 hours. At the end of the period the temperature is lowered to 80 C., and 7.5 kg of acetone is added to the system, which is stirred for 1 hour at 80 C. The content of the autoclave is drawn out, filtered to collect the polymer, which is then washed three times with 9 kg of acetone and dried under reduced pressure.

The thermoplastic elastomer obtained is measured for MFR and gel content. This thermoplastic elastomer is in-jection molded into a sheet, and the sheet is evaluated forappearance and physical properties. Results are shown in Table 3.

~; :
'~

. . .

7 4 ~153{jZ

~Q~

Polymer particles 3 kg of copolymer (III) S
Mixed liquid Benzoyl peroxide6 g Divinylbenzene 9 g toluene 600 g .
paraffinic oil ___ . .
Propertie~ :
MIR 230 C.,2.16 kg 8 g/10 min.
Gel content 85 wt% -Tensile strength230 kg/cm2 Elongation 600 % :~
Smoothness of sheet qood I

A 15-liter stainless steel autoclave equipped with an agitating element having helical type double ribbons is :~
; charged with 3 kg of particles the copolymer (III) and com~
pletely purged with nitrogen. Thereafter, a mixed liquid having a composition as shown in Table 4 is added dropwise at room temperature over a period of lO minutes to the au-toclave, while stirring the polymer particles, and the stirring i9 conducted for additional 30 minutes to impreg- -nate the polymer particles with the reagents contained in the mixed liquid. Subsequently, the temperature of the system is raised to 100 C., and maintained at that temper-ature for a period of 9 hours. At the end of the period the temperature is lowered to 80 C., and 7.5 kg of acetone is added to the system, which is stirred for 1 hour at 80 C. The content of the autoclave is drawn out, filtered to collect the polymer, which is then washed three times with 9 kg of acetone and dried under reduced pressure.

~:' The thermoplastic elastomer obtained is measured for MFR and gel content. This thermoplastic elastomer is in-jection molded into a sheet, and the sheet is evaluated for appearance and physical properties. Results are shown in Table 9.

, . . ' ' ~
: .. ~,. . : . :

Table 4 I _ Polymer particles 3 kg of copolymer (III) :-S __ .
Mixed liquid Benzoyl peroxide 6 g ~:
Divinylbenzene 9 g : :
toluene ___ paraffinic oil 950 g ~ :
.._.
Propertie~
MIR 230 C.,2.16 kg 20 g/10 min.
Gel content 83 wt%
Tensile strength 180 kg/cm2 Elongation 630 %
Smoothness of sheet qood : :

Exam~le 7 20A 15-liter stainless steel autoclave equipped with an agitating element having helical type double ribbons is charged with 3 kg of particles the copolymer (III) and com-pletely purged with nitrogen. Thereafter, a mixed liquid :
having a composition as shown in Table 5 is added dropwise at room temperature over a period of 10 minutes to the au-toclave, while stirring the polymer particles, and the stirring is conducted for additional 30 minutes to impreg~

;; .

7 7 2~ Z

nate the polymer particles wlth the reagents contained in the mixed liquid. Subsequently, the temperature of the system is raised to 100 C., and maintained at that temper-ature for a period of 4 hours. At the end of the period the temperature is lowered to 80 C., and 7.5 kg of acetone is added to the system, which is stirred for 1 hour at 80 C. The content of the autoclave is drawn out, filtered to collect the polymer, which is then washed three times with 9 kg of acetone and dried under reduced pressure.

The thermoplastic elastomer obtained is measured for MFR and gel content. Physical properties of the product lre shown in Table 5.

, . . .. .

7 8 ~0153~2 Table 5 P
: ' Polymer particles 3 kg of copolymer ~III) ~
S , _ ~ -:
Mixed liquid Modifier: maleic anhydride68 g :
Crosslinking agent:1,1-di-t-butylper oxy-3,3,5-trimethylcyclohexane 6 g 10 Crosslinking auxiliary: divinyl-benzene 9 g Radical initiator: benzoyl peroxide 2 g Swelling solvent: toluene600 g _ . , .
15 2ropertie~
MIR 230 C.,2.16 kg7 g/10 min.
Content of grafted maleic anhydride 0.39 wt%
Gel content 85 wt %
Particle shape Sa~e as before modifi-cation and qraftinq ~ .~
A 15-liter stainless steel autoclave equipped with an agitating element having helical type double ribbons is ~-:
charged with 3 kg of particles the copolymer (III) and com-pletely purged with nitrogen. Thereafter, a mlxed liquid comprising 8 g of dibenzoyl peroxide, 11 g of divinylben-' ~ .

zene and 400 g of toluene is added dropwise at room temper-ature over a period of 10 minutes to the autoclave, while stirring the polymer particles, and the stirring is con-ducted for additional 30 minutes to impregnate the polymer particles with the reagents contained in the mixed liquid.
Subsequently, the temperature of the system is raised to 100 C., and maintained at that temperature for a period of 4 hours. At the end of the period the temperature is low-ered to 80 C., and 7.5 kg of acetone is added to the sys-0 tem, which is stirred for 1 hour at 80 C. The content ofthe autoclave is drawn out, filtered to collect the poly-mer, which is then washed three times with 9 kg of acetone and dried under reduced pressure.

The thermoplastic elastomer obtained is measured for MFR and gel content. This thermoplastic elastomer is in-jection molded into a sheet, and the sheet is evaluated for appearance and physical properties. Results are shown in T~ble 6.

Z 0 lS 3 02 ~able 6 Polymer particles 3 kg of copolymer (III) Mixed liquid Dibenzoyl peroxide 8 g : :
Divinylbenzene 11 g toluene 400 g .
0 paraffinic oil ___ Propertie~
MIR 230 C.,2.16 kg 15 g/10 min.
Gel content 85 wt%
Tensile strength215 kg/cm2 Elongation 630 %
Smoothness of sheet good Particle shapeSame as before modifi- :~
cation and qraftinq .

Claims (31)

Claims

1. A process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a crosslinking agent at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles.

2. A process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a crosslinking agent and a crosslinking auxiliary at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles.

3. A process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a crosslinking agent and a mineral oil softening agent at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles.

4. A process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a crosslinking agent and a swelling solvent at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles.

5. A process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a radical initiator and a graft modifier at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer crosslinked within the particles.

6. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 5 wherein each of said polymer particles is composed of from 80 to 20 parts by weight of a portion comprising a crystalline olefin polymer and from 20 to 80 parts by weight of portions comprising an amorphous olefin polymer.

7. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 5 wherein said crystalline olefin polymer is a crystalline propylene polymer.

8. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 5 wherein said amorphous olefin polymer is an amorphous ethylene-.alpha.-olefin copolymer.

9. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 5 wherein said polymer particles have an average particle diameter of from 10 to 5000 µm.

10. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 5 wherein said polymer particles have an average particle diameter of from 10 to 5000 µm with a geometric standard deviation of from 1.0 to 3Ø

11. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 5 wherein said polymer particles have an apparent bulk density of from 0.2 to 0.7 g/ml.

12. The process for preparing thermoplastic elas-tomers in accordance with claim 11 wherein said polymer particles have an apparent bulk density of from 0.3 to 0.7 g/ml.

13. The process for preparing thermoplastic elas-tomers in accordance with any one of claims 1 to 4 wherein said crosslinking agent is used in an amount of from 0.01 to 2 parts by weight based on 100 parts by weight of said polymer particles.

19. The process for preparing thermoplastic elas-tomers in accordance with claim 2 wherein the crosslinking auxiliary is used in an amount of from 0.1 to 2 parts by weight based on 100 parts by weight of the polymer parti-cles.

15. The process for preparing thermoplastic elas-tomers in accordance with claim 3 wherein said mineral oil softening agent is used in an amount of from 1 to 100 parts by weight based on 100 parts by weight of the polymer par-ticles.

16. The process for preparing thermoplastic elas-tomers in accordance with claim 4 wherein said swelling solvent is used in an amount of from 1 to 100 parts by weight based on 100 parts by weight of the polymer parti-cles.

17. The process for preparing thermoplastic elas-tomers in accordance with claim 5 wherein said graft modi-fier is used in an amount of from 0.01 to 50 parts by weight based on 100 parts by weight of the polymer parti-cles.

18. Granular particles of a thermoplastic elastomer crosslinked within the particles, said thermoplastic elas-tomer primarily comprised of polymerized units of at least one .alpha.-olefin having at least 3 carbon atoms,each of said particles composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, said particles having an average particle diameter of from 100 to 5000 µm with a geometric standard deviation of from 1.0 to 2.0, an apparent bulk density of from 0.25 to 0.70, an aspect ratio of from 1.0 to 3.0 and containing not more than 20 % by weight of fine particles having a particle diameter of not more than 100 µm and at least 10 %
by weight of gel insoluble in cyclohexane.

19. A process for preparing thermoplastic elastomers, which comprises bringing polymer particles, each composed of a portion comprising a crystalline olefin polymer and portions comprising an amorphous olefin polymer, in contact with a radical initiator and a graft modifier in the presence of at least one substance selected from the group consisting of crosslinking agents other than the radical initiator, crosslinking auxiliaries, swelling solvents and mineral oil softening agents at a temperature below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer to obtain a thermoplastic elastomer graft modified and crosslinked within the parti-cles.

20. A process for preparing a thermoplastic elastomer from polymer particles having an average particle diameter of 10 to 5,000 µm, a geometrical standard deviation indicating a polymer particle size distribution of 1.0 to 3.0 and an apparent bulk density of 0.2 to 0.7 g/ml, each of the polymer particles having a sea-and-islands structure consisting of a sea portion and a plurality of islands portions surrounded or embedded in the sea portion, where the sea portion is composed essentially of a crystalline olefin polymer and the islands portions are composed essentially of an amorphous olefin polymer, which process comprises:
bringing the polymer particles into contact with a crosslinking agent at a temperature sufficient to facilitate crosslinking but below the higher one of the melting point of the crystalline olefin polymer and the glass transition temperature of the amorphous olefin polymer, thereby obtaining granular particles of a thermoplastic elastomer crosslinked within the particles and not among the particles.

21. The process in accordance with claim 20, wherein each of the polymer particles is composed of 80 to 20 % by weight of the crystalline olefin polymer and 20 to 80 % by weight of the amorphous olefin polymer, both based on the polymer particle.

22. The process in accordance with claim 21, wherein the crystalline olefin polymer is crystalline polypropylene and the amorphous olefin polymer is a copolymer rubber of ethylene and at least one member selected from the group consisting of a C3-C20 .alpha.-olefin, a chain or cyclic di- or triene and a cyclomonoene.

23. The process in accordance with claim 22, wherein the amorphous olefin polymer is a copolymer rubber of ethylene and a C2-C8 .alpha.-olefin.

24. The process in accordance with claim 23, wherein the .alpha.-olefin is propylene.

25. The process in accordance with any one of claims 20 to 24, wherein an organic peroxide is used as the crosslinking agent.

26. The process in accordance with claim 25, wherein a crosslinking auxiliary is also employed in the crosslinking reaction, the said crosslinking auxiliary being a member selected from the group consisting of trimethylolpropane-N,N-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethylacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinylbutyrate and vinyl stearate.

27. The process in accordance with claim 25, wherein a graft modifier is also used in the crosslinking reaction, the graft modifier being selected from the group consisting of:
(a) an ethylenically unsaturated compound containing a glycidyl or epoxy group, (b) an ethylenically unsaturated compound containing a carboxyl group or acid anhydride, halide, amide, imide or ester thereof, (c) an ethylenically unsaturated compound containing a hydroxyl group, and (d) an ethylenically unsaturated compound containing an amino group.

28. The elastomer in accordance with claim 18, wherein each of the particles has a sea-and-islands structure consisting of a sea portion made of the crystalline olefin polymer and a plurality of islands portions made of the amorphous olefin polymer and each of the polymer particles is composed of 80 to 20 % by weight of the crystalline olefin polymer and 20 to 80 % by weight of the amorphous olefin polymer, both based on the polymer particle.

29. The elastomer in accordance with claim 28, wherein the crystalline olefin polymer is crystalline polypropylene and the amorphous olefin polymer is a copolymer rubber of the ethylene and at least one member selected from the group consisting of a C3-C20 .alpha.-olefin, a chain or cyclic di- or triene and a cyclomonoene.

30. The elastomer in accordance with claim 29, wherein the amorphous olefin polymer is a copolymer rubber of ethylene and a C2-C8 .alpha.-olefin.

31. The elastomer in accordance with claim 30, wherein the .alpha.-olefin is propylene.