CN104736629A - Propylene-based polymer composition and injection-molded body using same - Google Patents

Abstract

To provide: a propylene-based polymer composition that exhibits an excellent balance of rigidity and impact resistance, that has good molding characteristics, and that exhibits little warpage in a thin-walled molded body thereof; and an injection-molded body using same. [Solution] A propylene-based polymer composition containing a propylene-based polymer that simultaneously satisifies the predetermined conditions [1]-[4] and a nucleating agent that is an organic metal salt possessing anisotropic properties. A propylene-based polymer composition containing 150-3000 ppm of the nucleating agent relative to the propylene-based polymer solves the abovementioned problem, and it is preferable that the melt flow rate (230 DEG C, ASTM1238) of the propylene-based polymer be 30 g/10 minutes or higher.

Description

Propylene polymer composition and use the injection molded article of this propylene polymer composition

Technical field

The present invention relates to propylene polymer composition and use the injection molded article of this propylene polymer composition.

Background technology

Acrylic polymer has excellent rigidity, hardness and thermotolerance, so in the exterior purposes of automobile being widely used in beater or beat-up, collision bumper, side filler rod, mud guard, car lens cover etc. by injection molding or automobile inside purposes, various container application etc.

In recent years, be strongly required to reduce carrying capacity of environment, in a variety of applications where, wish to realize lightweight by the thin-walled property of products formed, in order to this demand accomplished there is the products formed of sufficient intensity, wish to develop high workability, rigidity-shock-resistance balance improves the acrylic polymer of (that is, any characteristic of rigidity and shock-resistance is all excellent) or the composition containing this polymkeric substance further.In addition, it is desirable to shorten shaping cycle when manufacturing the formed body using acrylic polymer.

A kind of rigidity and excellent impact resistance is proposed in patent documentation 1, and the propylene based block copolymer that current mark outward appearance is also excellent.This propylene based block copolymer is made up of the part (Dinsol) 20 ~ 95 % by weight being insoluble to n-decane under dissolving in the part (Dsol) 5 ~ 80 % by weight of n-decane and room temperature under room temperature, meets defined terms.In addition, the large container etc. that the composition proposing a kind of propylene system block polymer all excellent by any characteristic containing high workability, rigidity and shock-resistance in non-patent literature 1 obtains.

In patent documentation 2 and patent documentation 3, as the solution of the warpage of the not wide acrylic resin of molecular weight distribution, propose the scheme using specific nucleator.

Prior art document

Patent documentation

Patent documentation 1: No. 2010/032793rd, International Publication

Patent documentation 2: Japanese Unexamined Patent Publication 2010-248438 publication

Patent documentation 3: Japanese Unexamined Patent Publication 11-349776 publication

Non-patent literature

Non-patent literature 1: open skill and technique 2011-504369

Summary of the invention

Invent problem to be solved

But, newly judge that the propylene based block copolymer recorded in patent documentation 1 and non-patent literature 1 is when products formed is thin in injection molding, and the buckling deformation of products formed easily occurs.Although can predict that warpage can be improved to a certain extent by improvement condition of molding, the problem there is the stenosis of condition of molding scope, making productivity reduce.In addition, the reason of warpage is considered to the anisotropy of molding shrinkage.

In addition, in the propylene polymer composition recorded in the propylene system products formed recorded in patent documentation 2 and patent documentation 3, the modification method of buckling deformation when using the polypropylene for the molecular weight distribution of giving high workability is wide in order to the shaping of thin-walled pressure vessel is not yet resolved.Particularly, as in patent documentation 2 use organophosphate system nucleator time, occur shaping after the different phenomenon of shrinking percentage, namely occur that anisotropic report is such, as the modification method of the buckling deformation of acrylic polymer, application organophosphate system nucleator is not general method.

The balance of molded appearance, rigidity-shock-resistance, injection molding mobility will be asked like this, suppress the further improvement of the propylene resin composition of the warpage that thin molded article occurs.The present invention completes to solve above-mentioned problem, its object is to provide a kind of balancing good of rigidity-shock-resistance, molding processibility good and the propylene polymer composition that the warpage of thin-walled molding body is few and use the injection molded article of this propylene polymer composition.

For solving the method for problem

The present inventor is studied for the modification method of the buckling deformation of acrylic polymer.In this process, find that the warpage of thin-walled molding body is few, the propylene polymer composition of the balancing good of rigidity-shock-resistance and use the injection molded article of this propylene polymer composition, thus completed the present invention.

The feature of the propylene polymer composition related to for the present invention solving above-mentioned problem is, containing the acrylic polymer and the nucleator that meet following condition [1] ~ [4] simultaneously, above-mentioned nucleator has anisotropic organic metal salt, in this propylene polymer composition, contain the above-mentioned nucleator of more than 150ppm below 3000ppm relative to aforesaid propylene based polymer.

[1] part (Dsol) dissolving in n-decane under room temperature is less than more than 0 % by weight 80 % by weight, the part (Dinsol) being insoluble to n-decane under room temperature is less than more than 20 % by weight 100 % by weight (wherein, the total amount of Dsol and Dinsol is 100 % by weight)

[2] molecular weight distribution (Mw/Mn) recorded by gel permeation chromatography of Dinsol is less than more than 7.0 30, and Mz/Mw is less than more than 6.0 25,

[3] the five-tuple mark (mmmm) of Dinsol is more than 93%,

[4] fusing point (Tm) recorded by differential scanning calorimeter of Dinsol is more than 140 DEG C.

The melt flow rate (MFR) (230 DEG C, 2.16kg load) of the preferred aforesaid propylene based polymer of the propylene polymer composition that the present invention relates to is more than 30g/10 minute.

The preferred above-mentioned nucleator of the propylene polymer composition that the present invention relates to is organophosphate.Feature for the injection molded article solving above-mentioned problem is, the propylene polymer composition comprising above-mentioned record forms.The injection molded article that the present invention relates to is preferably thin-walled molding body.Invention effect

According to the present invention, molding processibility when can obtain shaping is good, the products formed of the balancing good of excellent appearance, rigidity-shock-resistance.Further, when making thin-walled molding body, the generation of warpage can be suppressed, and shorten shaping cycle.

Embodiment

Below, the propylene polymer composition that the present invention relates to and the injection molded article containing this propylene polymer composition are described in detail.

The invention is not restricted to following embodiment, various distortion can be carried out implement in the scope of its main points.

The propylene polymer composition related to of the present invention contains the acrylic polymer and nucleator that meet prescribed condition [1] ~ [4] simultaneously, and wherein, this nucleator has anisotropic organic metal salt.

(propylene polymer composition)

Propylene polymer composition is containing meeting the acrylic polymer of prescribed condition and the composition of nucleator simultaneously, this nucleator has anisotropic organic metal salt, in this propylene polymer composition, contain the nucleator of more than 150ppm below 3000ppm relative to acrylic polymer.The lower value of the concentration of nucleator is preferably 200ppm, is more preferably 400ppm, and higher limit is preferably 2500ppm, is more preferably 2000ppm.

When the concentration of nucleator is in above-mentioned scope, suppress the excellent effect of warpage, the rigidity of products formed, excellent impact resistance, and both balances are also excellent.In addition, the good and excellent appearance of molding processibility, and also favourable in cost.

[acrylic polymer]

Condition [1] ~ [4] that should simultaneously meet for acrylic polymer are described.

Condition [1] is the part (Dsol) dissolving in n-decane under room temperature is less than more than 0 % by weight 80 % by weight, the part (Dinsol) being insoluble to n-decane under room temperature is less than more than 20 % by weight 100 % by weight (wherein, the total amount of Dsol and Dinsol is 100 % by weight).

The lower value of Dsol is preferably 10 % by weight, and higher limit is preferably 50 % by weight, is more preferably 30 % by weight.The lower value of Dinsol is preferably 50 % by weight, is more preferably 70 % by weight, and higher limit is preferably 90 % by weight.By containing Dsol more than lower value, the excellent impact resistance of acrylic polymer, by containing the Dsol below higher limit, the rigidity of acrylic polymer, excellent heat resistance.

" under room temperature, dissolve in the part (Dsol) of n-decane " and represent: as set forth in an embodiment below, among acrylic polymer, the part of dissolving in n-decane solution cool to 23 DEG C with 150 DEG C of heating for dissolving after 2 hours in n-decane after.In addition, in the following description, sometimes by " dissolving in the part of n-decane under room temperature " referred to as " n-decane soluble part ".

The part (Dsol) dissolving in n-decane under room temperature with by propylene be selected from propylene series copolymer rubber that more than one the alkene in the alpha-olefin of ethene and carbonatoms 4 ~ 20 formed for main component and (be greater than 50 % by weight, be preferably 80 ~ 100 % by weight, be more preferably 90 ~ 100 % by weight).The content being selected from more than one the alkene in the alpha-olefin of ethene and carbonatoms 4 ~ 20 contained by this propylene series copolymer rubber is higher than the content of this alkene contained by acrylic polymer described later.

" under room temperature, be insoluble to the part (Dinsol) of n-decane " and represent: as set forth in an embodiment below, among acrylic polymer, the part of not dissolving in n-decane solution cool to 23 DEG C with 150 DEG C of heating for dissolving after 2 hours in n-decane after.In addition, in the following description, sometimes by " being insoluble to the part of n-decane under room temperature " referred to as " the insoluble part of n-decane ".

The part (Dinsol) being insoluble to n-decane under room temperature is main component (be greater than 50 % by weight, be preferably 80 ~ 100 % by weight, be more preferably 90 ~ 100 % by weight) with crystalline propylene system (being total to) polymkeric substance.This crystalline propylene system (being total to) polymkeric substance represents crystalline propylene's homopolymer or contains the crystalline propylene's based copolymer being selected from more than one the alkene in the alpha-olefin of ethene and carbonatoms 4 ~ 20 of propylene and below 1.5mol%.

As the alpha-olefin of carbonatoms 4 ~ 20,1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc. can be enumerated.As the alkene being derived from the skeleton of more than one the alkene in the alpha-olefin being selected from ethene and carbonatoms 4 ~ 20 formed in multipolymer, the alpha-olefin of optimal ethylene or carbonatoms 4 ~ 10, be more preferably ethene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, more preferably use more than a kind.

Condition [2] is the molecular weight distribution (Mw/Mn) recorded by gel permeation chromatography of Dinsol be less than more than 7.0 30, Mz/Mw is less than more than 6.0 25.

About Mw/Mn, from the view point of the high rigidization of maintenance and shock-resistance, lower value is preferably 8.0, and higher limit is preferably 25, is more preferably 20, is particularly preferably 15.About Mz/Mw, from the view point of high molecular weight components containing ratio, lower value is preferably 6.5, is more preferably 7, and higher limit is preferably 23, is more preferably 20.

The insoluble part of n-decane (Dinsol) of the propylene based block copolymer that the present invention relates to is because Mw/Mn value is in above-mentioned scope, so the molecular weight distribution that display is fully wide, formability is excellent, and rigidity is also excellent.In addition, propylene based block copolymer is owing to showing high Mz/Mw value as mentioned above, so the composition containing a large amount of high molecular, melting tension force (MT) is high and formability is excellent.

The insoluble part of n-decane (Dinsol) of propylene based block copolymer also can be manufactured by multistage polymerization or multiple polyacrylic mixing, but obtains preferably by the polymerization in 1 stage.When the insoluble part of the decane of propylene based block copolymer (Dinsol) is obtained by the polymerization in 1 stage, polymers manufacturing device can be made more simple, comparatively economical, and the high molecular weight components in propylene based block copolymer can not be condensed and form microdispersed state, therefore preferably.

The insoluble part of n-decane (Dinsol) of propylene based block copolymer, due to and high molecular weight components that Mz/Mw value high high containing a large amount of Mw/Mn values, so the high molecular weight components when shaping in propylene based block copolymer plays the effect as nucleator, even if the nucleator such as absorb fillers powder or toner, can not obtain the high formed body of degree of crystallinity yet.Particularly when this high molecular body differential falls apart, the trend that the effect with nucleator etc. improves, so preferably.

Wherein, propylene 98.5 ~ 100mol% by under the existence of catalyst for olefines polymerizing described later, can be polymerized with more than one the alkene 0 ~ 1.5mol% (being total to) in the alpha-olefin being selected from ethene and carbonatoms 4 ~ 20 and obtain by condition [2].

Condition [3] is the five-tuple mark (mmmm) of Dinsol is more than 93%.The lower value of five-tuple mark (mmmm) is preferably more than 94%, is more preferably more than 95%.Higher limit is preferably less than 100%, is more preferably less than 99.8%, and more preferably less than 99.5%.

When five-tuple mark (mmmm) is less than 93%, rigidity reduces, or in the arts of film etc., there is the field that thermotolerance cannot guarantee requirement characteristic, therefore not preferred.Such as, utilizing titanium trichloride catalyst to be polymerized the acrylic polymer obtained is recorded in Japanese Laid-Open Patent Publication 47-34478 publication, there is the effect that wide molecular weight distribution is brought, but the five-tuple mark due to the insoluble part of decane is extremely low reaches about 91 ~ 92%, so the middle uses such as the injection molding purposes of high rigidity cannot be needed at automotive material etc.

Wherein, satisfy condition [3] be because comprise cyclic ester compounds (a) and cyclic ester compounds (b) as electron donor in catalyst for olefines polymerizing described later.Condition [4] is the fusing point (Tm) recorded by differential scanning calorimeter of Dinsol is more than 140 DEG C.The lower value of fusing point (Tm) is preferably more than 145 DEG C.Higher limit is preferably less than 150 DEG C, is more preferably less than 170 DEG C.When fusing point (Tm) is within the scope of this, thermotolerance, excellent rigidity.

In order to make the fusing point of Dinsol (Tm) in above-mentioned scope, by the manufacture method of acrylic polymer described later, copolymer rubber portion manufacture can be regulated, regulates the molecular weight during manufacture of crystalline propylene's based polymer to realize.

The melt flow rate (MFR) (ASTM1238,230 DEG C, 2.16kg load) of acrylic polymer is preferably more than 30g/10 minute.Be more preferably 30 ~ 100g/10 minute.When melt flow rate (MFR) is within the scope of this, satisfactory from the viewpoint of mobility.

The acrylic polymer that the present invention relates to, preferably except meeting above-mentioned condition [1] ~ [4], also meets condition [5] ~ [7] below.

Condition [5]: the n-decane soluble part (Dsol) of the acrylic polymer that the present invention relates to be 6.0 ~ 30 by the ratio Mw/Mn value of the weight-average molecular weight (Mw) utilizing the measured value of gel permeation chromatography (GPC) to obtain and number-average molecular weight (Mn).From the view point of having both high workability and high melting tension force, Mw/Mn value is preferably 6.5 ~ 20, is more preferably 7.0 ~ 18.

The acrylic polymer that the present invention relates to due to the Mw/Mn of n-decane soluble part (Dsol) high, so have the feature of the copolymer rubber composition containing a large amount of high molecular.By this feature, in acrylic polymer of the present invention, even if the MFR of wide molecular weight distribution acrylic polymer is high, also can improve melting elasticity by high molecular weight copolymer rubber constituent, be therefore favourable realizing in the having both of high workability and high melting tension force.

When the mobility height of acrylic polymer, injection molding and the cripetura in injection molding cycle of massive article can be realized.In addition, when the melting elasticity height of propylene based block copolymer, the outward appearance of injection-molded article is good, and blow moldability, foaming are good, can give molding processibility.

In addition, condition [5] can by under the existence of catalyst for olefines polymerizing described later, is obtained with being selected from more than one the olefin-copolymerization in the alpha-olefin of ethene and carbonatoms 4 ~ 20 by propylene.

Wherein, for condition [5], even existing catalyst for olefines polymerizing, also can realize by polymerization hop count is set to multistage, but in the present invention, by using catalyst for olefines polymerizing described later, even if be the polymerization in 1 stage, the multipolymer of desired condition also can be met.Thus, the copolymer rubber composition obtained has and can not condense and the advantage of easier differential dispersion in propylene based block copolymer.In addition, polymers manufacturing device can be made more simple, also favourable in the viewpoint of economic aspect, energy-saving.Wherein, " polymerization in 1 stage " refers to that the operation manufacturing copolymer rubber is made up of 1 section of reactor, and does not change the state of polymerizing condition completely in this reactor.

Condition [6]:

Limiting viscosity [η] (dl/g) of the decane soluble part (Dsol) of the acrylic polymer that the present invention relates to is 1.5 ~ 10.0.From making shock-resistance, high workability, the optimized viewpoint of the elastic balance of high melting, limiting viscosity [η] (dl/g) is preferably 2.0 ~ 7.0, is more preferably 2.5 ~ 4.0.When limiting viscosity [η] (dl/g) is lower than 1.5dl/g, the shock-resistance of acrylic polymer may reduce, so not preferred.In addition, when limiting viscosity [η] (dl/g) is higher than 10dl/g, easily there is reduction or the flake of mobility, be therefore sometimes difficult to apply in large-scale injection product or film.

In addition, by the propylene series copolymer rubber that limiting viscosity [η] (dl/g) of rear interpolation decane soluble part (Dsol) is high, the effect of shock-resistance, high workability, high melting elasticity etc. can be showed.But, now, the problem easily producing flake can be there is, the viewpoint that appearance of molded articles worsens is difficult to realize industrialization.On the other hand, propylene based block copolymer by (Dsol) successive polymerization of decane soluble part is obtained as the present invention, because copolymer rubber differential in multipolymer entirety falls apart, so unfavorable condition as described above can not be there is, except the effects such as shock-resistance, high workability, high melting elasticity can be obtained, the products formed of the generation of the flake that can also be inhibited.

Condition [7]:

The Mz/Mn value of the insoluble part of decane (Dinsol) of the acrylic polymer that the present invention relates to is 70 ~ 300.Mz/Mn value is preferably 80 ~ 250, is more preferably 100 ~ 200.In the polypropylene that Mz/Mn value is high, represent the high containing ratio of the high composition of molecular weight, can expect that melting tension force is high, the possibility of formability and excellent rigidity is high.

About Mz/Mn value, titanium trichloride catalyst is such as utilized to be polymerized the acrylic polymer obtained, described in Japanese Laid-Open Patent Publication 47-34478 publication, there is the effect that wide molecular weight distribution is brought, but wide molecular weight distributionization is because low-molecular-weight polymkeric substance increases mostly, therefore utilize titanium trichloride catalyst be polymerized the Mz/Mn value of the acrylic polymer obtained maximum be also only about 40 numerical value.Therefore, and be not suitable for as the present invention by the polymkeric substance of high molecular many bring effect, namely, automotive material etc. needs the injection molding purposes etc. of high rigidity.

The acrylic polymer simultaneously meeting above-mentioned condition [1] ~ [4] preferably uses following catalyst for olefines polymerizing manufacture.

(catalyst for olefines polymerizing)

The acrylic polymer that the present invention relates to preferably carries out being polymerized and obtains under the existence comprising solid titanium catalyst component (I), catalyst for olefines polymerizing containing the organometallic compound (II) of atoms metal be selected from the 1st race of the periodic table of elements, the 2nd race and the 13rd race and electron donor as required (III).

Specifically, the catalyzer described in International Publication No. 2010/032793 brochure can be illustrated.Below, each composition related to for catalyst for olefines polymerizing is described.

solid titanium catalyst component (I)

The above-mentioned solid titanium catalyst component (I) that the present invention relates to comprises the cyclic ester compounds (a) of titanium, magnesium, halogen and following formula (1) defined and the cyclic ester compounds (b) of following formula (2) defined.

Among these, about the cyclic ester compounds (a) of wide molecular weight distribution and the cyclic ester compounds (b) that are believed to be helpful in propylene based block copolymer, enumerate the preferred compound of following concrete use.Wherein, about each composition of titanium, magnesium, halogen, comprise above-mentioned publication, obtained by known method.

(cyclic ester compounds (a))

Cyclic ester compounds (a) has multiple carboxylic acid ester groups, is represented by following formula (1).

In formula (1), n is the integer of 5 ~ 10, is preferably the integer of 5 ~ 7, is more preferably 6.In addition, C ^aand C ^brepresent carbon atom.

R ²and R ³be separately COOR ¹or R, R ²and R ³in at least 1 be COOR ¹.Between the carbon atom in cyclic skeleton, key is all preferably singly-bound, but in cyclic skeleton except C ^a-C ^akey and R ³for C during R ^a-C ^barbitrary singly-bound beyond key can be replaced by double bond.That is, the C-C in cyclic skeleton ^bkey, R ³for COOR ¹time C ^a-C ^bkey and C-C key (when n is 6 ~ 10) can be replaced by double bond.

Existing multiple R ¹the alkyl be separately carbonatoms 1 ~ 20, being preferably 1 ~ 10, being more preferably 2 ~ 8, being particularly preferably 1 valency of 4 ~ 8, more preferably 4 ~ 6.As this alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, hexyl, heptyl, octyl group, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl etc. can be enumerated, wherein, preferred normal-butyl, isobutyl-, hexyl, octyl group, normal-butyl, isobutyl-are owing to can manufacture the wide propylene based block copolymer of molecular weight distribution and more preferred furthermore.

Existing multiple R are not separately for being selected from hydrogen atom, the alkyl of carbonatoms 1 ~ 20, halogen atom, nitrogenous base, containing oxygen base, phosphorous-containigroups groups, containing halogen with containing the atom in silica-based or group, but at least 1 R is hydrogen atom.

As the R beyond hydrogen atom, the alkyl of preferred carbonatoms 1 ~ 20, as the alkyl of this carbonatoms 1 ~ 20, aliphatic alkyl, alicyclic alkyl, the aromatic hydrocarbyl of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, vinyl, phenyl, octyl group etc. can be enumerated.Wherein, preferred aliphat alkyl, specifically more preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl.

In addition, R can be combined with each other formation ring, and R is combined with each other in the skeleton of formed ring can contain double bond, comprises more than 2 and be combined with COOR in the skeleton of this ring ¹c ^atime, the carbonatoms forming the skeleton of this ring is 5 ~ 10.

As the skeleton of such ring, norbornane skeleton, tetracyclododecane skeleton etc. can be enumerated.Multiple R existing in addition can be the group containing carbonyl structure of carboxylic acid ester groups, alkoxyl group, siloxy-, aldehyde radical or ethanoyl etc., and these substituting groups preferably contain the alkyl of the carbonatoms 1 ~ 20 of more than 1.

As such cyclic ester compounds (a), on the books in International Publication No. 2006/077945 brochure.Above-mentioned have like that in the compound of two ester structures exist be derived from multiple COOR in formula (1) ¹the cis of base, trans etc. isomer, which kind of structure all has the effect meeting the object of the invention, but more preferably the containing ratio of trans-isomer(ide) is high.During the containing ratio height of trans-isomer(ide), not only there is the effect that molecular weight distribution is broadened, and there is the trend making the stereospecific of polymkeric substance that is active and that obtain higher.

As cyclic ester compounds (a), the compound shown in preferred following formula (1-1) ~ (1-6).

(the R in above-mentioned formula (1-1) ~ (1-6) ¹identical with the definition in formula (1) with R.

In above-mentioned formula (1-1) ~ (1-3), the singly-bound in cyclic skeleton is (wherein except C ^a-C ^akey and C ^a-C ^bin addition) double bond can be replaced by.In above-mentioned formula (1-4) ~ (1-6), the singly-bound in cyclic skeleton is (wherein except C ^a-C ^abeyond key) can double bond be replaced by.In addition, above-mentioned formula (1-3) and (1-6) middle n are the integer of 7 ~ 10.〕

As cyclic ester compounds (a), the particularly preferably compound shown in following formula (1a).

(n, R in formula (1a) ¹identical with the definition in formula (1) with R, the singly-bound in cyclic skeleton is (wherein except C ^a-C ^akey and C ^a-C ^bbeyond key) can double bond be replaced by.That is, the C-C key (when n is 6 ~ 10) in cyclic skeleton, C ^a-C key and C ^b-C key can be replaced by double bond.〕

As the compound shown in above-mentioned formula (1a), specifically, can enumerate as preferred illustration: 3, 6-dimethyl cyclohexane-1, 2-diisobutyl dicarboxylate, 3, 6-dimethyl cyclohexane-1, the just own ester of 2-dicarboxylic acid two, 3, 6-dimethyl cyclohexane-1, 2-dicarboxylic acid di-n-octyl, 3-methyl-6-ethylcyclohexane-1, 2-diisobutyl dicarboxylate, 3-methyl-6-ethylcyclohexane-1, the just own ester of 2-dicarboxylic acid two, 3-methyl-6-ethylcyclohexane-1, 2-dicarboxylic acid di-n-octyl, 3-methyl-6-n-propyl hexanaphthene-1, 2-diisobutyl dicarboxylate, 3-methyl-6-n-propyl hexanaphthene-1, the just own ester of 2-dicarboxylic acid two, 3-methyl-6-n-propyl hexanaphthene-1, 2-dicarboxylic acid di-n-octyl, 3, 6-diethyl cyclohexane-1, 2-diisobutyl dicarboxylate, 3, 6-diethyl cyclohexane-1, the just own ester of 2-dicarboxylic acid two, 3, 6-diethyl cyclohexane-1, 2-dicarboxylic acid di-n-octyl.These compounds can utilize Diels Alder to react and manufacture.

In the cyclic ester compounds (a) as above with two ester structures, there is cis, trans etc. isomer, although which kind of structure all has the effect meeting the object of the invention, but during the containing ratio height of trans-isomer(ide), not only there is the effect that molecular weight distribution is broadened, and there is the trend making the stereospecific of polymkeric substance that is active and that obtain higher, therefore particularly preferably.The ratio of the trans-isomer(ide) in preferred cis-isomeride and trans-isomer(ide) is preferably more than 51%.Preferred lower value is 55%, more preferably 60%, be particularly preferably 65%.On the other hand, preferred higher limit is 100%, is more preferably 90%, more preferably 85%, be particularly preferably 79%.

(cyclic ester compounds (b))

Cyclic ester compounds (b) has multiple carboxylic acid ester groups, is represented by following formula (2).

In formula (2), n is the integer of 5 ~ 10, is preferably the integer of 5 ~ 7, is particularly preferably 6.In addition, C ^aand C ^brepresent carbon atom.

Between the carbon atom in cyclic skeleton, key is all preferably singly-bound, but in cyclic skeleton except C ^a-C ^akey and R ⁵for C during hydrogen atom ^a-C ^barbitrary singly-bound beyond key can be replaced by double bond.That is, the C-C in cyclic skeleton ^bkey, R ⁵for COOR ¹time C ^a-C ^bkey and C-C key (when n is 6 ~ 10) can be replaced by double bond.

In addition, R ⁴and R ⁵be separately COOR ¹or hydrogen atom, R ⁴and R ⁵in at least 1 be COOR ¹, R ¹it is separately the alkyl of 1 valency of carbonatoms 1 ~ 20.

Existing multiple R ¹separately for carbonatoms 1 ~ 20, be preferably 1 ~ 10, be more preferably 2 ~ 8, more preferably 4 ~ 8, be particularly preferably the alkyl of 1 valency of 4 ~ 6.As this alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, hexyl, heptyl, octyl group, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl etc. can be enumerated, wherein, preferred normal-butyl, isobutyl-, hexyl, octyl group, normal-butyl, isobutyl-are owing to can manufacture the wide propylene based block copolymer of molecular weight distribution furthermore, so particularly preferably.

Have as above in the compound of two ester structures, there is cis, trans etc. isomer, but which kind of structure all has the effect meeting the object of the invention.The ratio of the trans-isomer(ide) in cis-isomeride and trans-isomer(ide) is preferably more than 51%.Preferred lower value is 55%, more preferably 60%, be particularly preferably 65%.On the other hand, preferred higher limit is 100%, is more preferably 90%, more preferably 85%, be particularly preferably 79%.Although its reason is still not clear, can infer because the change (Variation) of steric isomer described later is in the region being suitable for wide molecular weight distribution.

In above-mentioned formula (2), the trans purity of hexanaphthene-1, the 2-dicarboxylic diester of n=6 is in above-mentioned scope.When trans purity lower than 51% time, the effect, activity, stereospecificity etc. of wide molecular weight distribution are insufficient sometimes.In addition, when trans purity is more than 79%, the effect of wide molecular weight distribution is insufficient sometimes.That is, if trans purity is in above-mentioned scope, be conducive under most cases with high level have both the molecular weight distribution of obtained polymkeric substance is broadened effect, with the activity of catalyzer and the high stereospecific of polymkeric substance that obtains.

As cyclic ester compounds (b), the compound with naphthenic hydrocarbon-1,2-dicarboxylic diester structure or cycloolefin-1,2-dicarboxylic diester structure shown in preferred following formula (2a).

(n, R in formula (2a) ¹the same (that is, identical with the definition in formula (2)), the singly-bound in cyclic skeleton is (wherein except C ^a-C ^akey and C ^a-C ^bbeyond key.That is, C-C ^akey, C-C ^bkey and C-C key (when n is 6 ~ 10)) can double bond be replaced by.〕

As the compound shown in above-mentioned formula (2a), specifically, can enumerate as preferred illustration: hexanaphthene-1,2-diisobutyl dicarboxylate, hexanaphthene-1,2-dicarboxylic acid dihexyl ester A, hexanaphthene-1,2-dicarboxylic acid two heptyl ester, hexanaphthene-1,2-dicarboxylic acid dioctyl ester, hexanaphthene-1,2-dicarboxylic acid two-2-ethylhexyl.Its reason is not only catalyst performance, is also that these compounds can utilize Diels Alder to react and manufacture less expensively.

Cyclic ester compounds (a) and (b) both can individually use, and also can combine two or more use each.The combination mol ratio (cyclic ester compounds (a)/(cyclic ester compounds (a)+cyclic ester compounds (b)) × 100 (% by mole)) of cyclic ester compounds (a) and cyclic ester compounds (b) is preferably more than 10 % by mole.Be more preferably more than 30 % by mole, more preferably more than 40 % by mole, be particularly preferably 50 % by mole.Preferred higher limit is 99 % by mole, is preferably 90 % by mole.Be more preferably 85 % by mole, more preferably 80 % by mole.

Solid titanium catalyst component of the present invention (I), even if under the condition of the combination mol ratio of the cyclic ester compounds (a) of wide region, namely, even if the content of the cyclic ester compounds (a) of solid titanium catalyst component (I) is low, the olefin polymer that molecular weight distribution is extremely wide also can be provided.The reason of this effect is still not clear, but the present inventor is presumed as follows.

The change of the three-dimensional arrangement that apparent cyclic ester compounds (a) can be formed compared with cyclic ester compounds (b) due to the existence of substituent R is extremely many.Therefore can think, for molecular weight distribution, the impact of cyclic ester compounds (a) accounts for leading, even if the low olefin polymer that also can provide pole wide molecular weight distribution of combination mol ratio.

On the other hand, cyclic ester compounds (a) and cyclic ester compounds (b) due to structure comparison similar, so in the fundamental propertys such as activity, stereospecific, be difficult to impact (when using the different compound of structure, there are a lot of activity, stereospecifics etc. and sharply changing or the example of predominant effect of a compound) the effect of compound each other.

Therefore, the solid titanium catalyst component (I) used in the present invention, even if the containing ratio of cyclic ester compounds (a) is low, also can provides pole wide molecular weight distribution with high activity and have the olefin polymer of high stereospecific.

The propylene based block copolymer that the present invention relates to is the wide polymkeric substance of molecular weight distribution.Its reason is still not clear at present, but can be speculated as following reason.

Known cyclic hydrocarbon structures forms the diversified three-dimensional arrangement such as chair form, boat form.Further, if ring texture has substituting group, then the change of the three-dimensional arrangement that can adopt increases further.In addition, if formed cyclic ester compounds cyclic skeleton carbon atom in, be combined with ester group (COOR ¹base) carbon atom be combined with ester group (COOR ¹base) other carbon atoms between key be singly-bound, then the change of the three-dimensional arrangement that can adopt increases.Diversified like this three-dimensional arrangement can be adopted to be related at the diversified spike of the upper formation of solid titanium catalyst component (I).Its result, when using solid titanium catalyst component (I) to carry out the polymerization of alkene, once can manufacture the olefin polymer of various molecular weights, namely, can manufacture the propylene based block copolymer that molecular weight distribution is wide.

In the present invention, cyclic ester compounds (a) and (b) can be formed in the process preparing solid titanium catalyst component (I).Such as, when preparing solid titanium catalyst component (I), by arranging the carboxylic acid anhydride or carboxylic acid dihalide and the operation of corresponding alcohol substantial contact that correspond to cyclic ester compounds (a) and (b), also can make in solid titanium catalyst component containing cyclic ester compounds (a) and (b).

When preparing solid titanium catalyst component (I) used in the present invention, except above-mentioned cyclic ester compounds (a) and (b), magnesium compound and titanium compound can also be used.In addition, only otherwise damage object of the present invention, catalyst component (d) described later use can also be combined.

(magnesium compound)

As the magnesium compound prepared solid titanium catalyst component (I) and use, specifically, the magnesium compound preferably containing halogen, preferably uses magnesium halide, particularly preferably uses magnesium chloride.

(titanium compound)

As the titanium compound prepared solid titanium catalyst component (I) and use, the titanium compound of 4 valencys such as shown in following general formula can be enumerated.

Ti(OR) _gX _4-g

(R is alkyl, and X is halogen atom, and g is 0≤g≤4.)。More specifically, TiCl can be enumerated ₄, TiBr ₄deng titanium tetrahalide; Ti (OCH ₃) Cl ₃, Ti (OC ₂h ₅) Cl ₃, Ti (O-n-C ₄h ₉) Cl ₃, Ti (OC ₂h ₅) Br ₃, Ti (O-isoC ₄h ₉) Br ₃deng three halogenated alkoxy titaniums; Ti (OCH ₃) ₂cl ₂, Ti (OC ₂h ₅) ₂cl ₂deng dihalogenated alkoxytitanium; Ti (OCH ₃) ₃cl, Ti (O-n-C ₄h ₉) ₃cl, Ti (OC ₂h ₅) ₃single halogenated alkoxy titanium such as Br; Ti (OCH ₃) ₄, Ti (OC ₂h ₅) ₄, Ti (OC ₄h ₉) ₄, Ti (O-2-ethylhexyl) ₄deng four titan-alkoxides etc.

Preferably titanium tetrahalide among these, particularly preferably uses titanium tetrachloride.These titanium compounds both can be used alone and also can combine two or more use.

As magnesium compound as described above and titanium compound, the compound recorded in detail in such as Japanese Unexamined Patent Publication 5-170843 publication, Japanese Unexamined Patent Publication 3-7703 publication etc. can also be enumerated.

When preparing solid titanium catalyst component (I), except using cyclic ester compounds (a) and (b), can unrestrictedly use known method.Specifically, the method recorded in detail in such as International Publication No. 2010/032793 brochure can be adopted.

(aromatic carboxylic acid esters and/or there is across multiple carbon atom the chemical combination of more than 2 ehter bonds thing)

Solid titanium catalyst component (I) can also containing aromatic carboxylic acid esters and/or the compound (hereinafter also referred to as " catalyst component (d) ") across multiple carbon atom with more than 2 ehter bonds.When solid titanium catalyst component (I) is containing catalyst component (d), sometimes can improve catalyst activity, or improve stereospecific, molecular weight distribution is broadened further.

As catalyst component (d), the known aromatic carboxylic acid esters that preferably uses in catalyst for olefines polymerizing in the past or the described compound such as polyether compound, such as Japanese Unexamined Patent Publication 5-170843 publication or Japanese Unexamined Patent Publication 2001-354714 publication unrestrictedly can be used.

As aromatic carboxylic acid esters, optimization aromatic multi-carboxylate, more preferably phthalate.This phthalate, the alkyl phthalates such as preferred ethyl phthalate(DEP), n-butyl phthalate, phthalic acid isobutyl ester, the own ester of phthalic acid, O-phthalic heptyl heptylate, particularly preferably diisobutyl phthalate.

In addition, as the particular compound of polyether compound, preferably 1,3-bis-ethers, particularly preferably 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2,2-diisobutyls-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetals, 2,2-two (cyclohexyl methyl)-1,3-Propanal dimethyl acetal.

These compounds both can be used alone a kind, also can combine two or more and use.In solid titanium catalyst component of the present invention (I), halogen/titanium (atomic ratio) (that is, the mole number of the mole number/titanium atom of halogen atom) is 2 ~ 100, is preferably 4 ~ 90.

Cyclic ester compounds (a)/titanium (mol ratio) (namely, the mole number of the mole number/titanium atom of cyclic ester compounds (a)) and cyclic ester compounds (b)/titanium (mol ratio) is (namely, the mole number of the mole number/titanium atom of cyclic ester compounds (b)) be 0.01 ~ 100, be preferably 0.2 ~ 10.

At this, as the preferred ratio of cyclic ester compounds (a) with cyclic ester compounds (b), the lower value of the value (% by mole) of 100 × cyclic ester compounds (a)/(cyclic ester compounds (a)+cyclic ester compounds (b)) is 5 % by mole, be preferably 25 % by mole, be more preferably 40 % by mole, be particularly preferably 50 % by mole.Higher limit is 99 % by mole, is preferably 90 % by mole, is more preferably 85 % by mole, is particularly preferably 80 % by mole.

Magnesium/titanium (atomic ratio) (that is, the mole number of the mole number/titanium atom of magnesium atom) is 2 ~ 100, is preferably 4 ~ 50.In addition, the content of the composition that can contain beyond above-mentioned cyclic ester compounds (a) and (b), such as catalyst component (c) and catalyst component (d) preferably relative to cyclic ester compounds (a) and (b) 100 % by weight below 20 % by weight, more preferably below 10 % by weight.

As the preparation condition specifically of solid titanium catalyst component (I), except using cyclic ester compounds (a) and (b), preferably can use the condition recorded in such as EP585869A1 (European Patent application discloses No. 0585869 specification sheets) or Japanese Unexamined Patent Publication 3-7703 publication etc.

organometal compound catalyst composition (II)

As Organometal compound catalyst composition (II), the organometallic compound containing the atoms metal in the 1st race being selected from the periodic table of elements, the 2nd race and the 13rd race can be enumerated.Specifically, the compound containing the 13rd race's metal can be used, such as organo-aluminium compound, the 1st race's metal and the complexing alkylide of aluminium, the organometallic compound etc. of group II metal.Among these, preferably have machine aluminium compound.As Organometal compound catalyst composition (II), specifically, as preferred example, the Organometal compound catalyst composition described in known document such as above-mentioned EP585869A1 can be enumerated.

electron donor (III)

Catalyst for olefines polymerizing containing above-mentioned Organometal compound catalyst composition (II), can contain electron donor (III) simultaneously as required.As electron donor (III), preferably there are organic silicon compound.As these silicoorganic compound, preferably use vinyltriethoxysilane, dimethoxydiphenylsilane, Dicyclohexyldimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane.

The alkoxysilane compound containing trialkylsilyl group in molecular structure of No. 2004/016662nd, International Publication described in brochure is also the preferred example of above-mentioned silicoorganic compound.As the concrete example of compound, can enumerate: the amino triethoxyl silane of dimethylamino triethoxyl silane, diethylin triethoxyl silane, dimethylamino Trimethoxy silane, diethylin Trimethoxy silane, diethylin three positive propoxy silane, two n-propylamine ethyl triethoxy silicane alkane, methyl n-propylamine ethyl triethoxy silicane alkane, tertiary fourth, ethyl n-propylamine ethyl triethoxy silicane alkane, ethylisopropyl amino triethoxyl silane, methyl-ethylamino triethoxyl silane.

As other examples of above-mentioned silicoorganic compound, specifically can enumerate: (perhydro quino-) triethoxyl silane, (perhydro isoquino) triethoxyl silane, (1,2,3,4-tetrahydroquinoline is also) triethoxyl silane, (1,2,3,4-tetrahydroisoquinoline is also) triethoxyl silane, eight methylene radical imino-triethoxyl silanes etc.

These silicoorganic compound can combine two or more and use.In addition, as other useful compounds of electron donor (III), can also enumerate be defined as above-mentioned catalyst component (d), aromatic carboxylic acid esters and/or there are across multiple carbon atom more than 2 the compound (polyether compound) of ehter bond as preferred example.

In addition, catalyst for olefines polymerizing, except containing except each composition as above, can also contain other useful in olefin polymerization composition as required.As other composition, can enumerate such as: the carrier, static inhibitor etc., particle aggregation agent, preserving stabilizer etc. of silicon-dioxide etc.As particle aggregation agent, such as, when using magnesium chloride and ethanol to generate particle, sorbitan SUNSOFT Q-182S etc. can be used as preferred compound.

(manufacture method of acrylic polymer)

[1] ~ [4] as long as the acrylic polymer that the present invention relates to satisfies condition simultaneously, manufacture method is restriction not.

In the manufacture method of the acrylic polymer that the present invention relates to, alkene prepolymerization (prepolymerization) can be made under the existence of above-mentioned catalyst for olefines polymerizing, and under the existence of the pre-polymerized catalyst obtained thus, carry out main polymerization (polymerization).About the detailed content of this manufacture method, the method described in International Publication No. 2010/032793 brochure can be used.Prepolymerization by making 0.1 ~ 1000g with every 1g catalyst for olefines polymerizing, be preferably 0.3 ~ 500g, be particularly preferably that the alkene pre-polymerization of the amount of 1 ~ 200g is incompatible to be carried out.In prepolymerization, the catalyzer of the concentration higher than the catalyst concn in the system of main polymerization can be used.

The concentration of the solid titanium catalyst component (I) in prepolymerization, in every 1 liter of liquid medium, converts in titanium atom, is generally 0.001 ~ 200 mmole, be preferably 0.01 ~ 50 mmole, be more preferably the scope of 0.1 ~ 20 mmole.

Organometal compound catalyst composition (II) in prepolymerization if amount be that every 1g solid titanium catalyst component (I) generates 0.1 ~ 1000g, is preferably the such amount of 0.3 ~ 500g polymkeric substance, relative to the every 1 mole of titanium atom in solid titanium catalyst component (I), be generally about 0.1 ~ 300 mole, be preferably 0.5 ~ 100 mole, be more preferably 1 ~ 50 mole.

In prepolymerization, also above-mentioned electron donor (III) etc. can be used as required, now these compositions, relative to the every 1 mole of titanium atom in above-mentioned solid titanium catalyst component (I), with 0.1 ~ 50 mole, be preferably 0.5 ~ 30 mole, be more preferably 1 ~ 10 mole amount use.

Prepolymerization, by adding alkene and above-mentioned catalyst component in nonactive hydrocarbon medium, is carried out under mild conditions.Now, as used nonactive hydrocarbon medium, specifically the aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene can be enumerated; The clicyclic hydrocarbons such as pentamethylene, methylcyclopentane, hexanaphthene, suberane, methylcycloheptane, cyclooctane; The aromatic hydrocarbonss such as benzene,toluene,xylene; The halohydrocarbon such as ethylene dichloride, chlorobenzene; Or their mixture etc.

Among these nonactive hydrocarbon media, particularly preferably use aliphatic hydrocarbon.Like this, when using nonactive hydrocarbon medium, prepolymerization is preferably carried out with batch-type.

On the other hand, alkene itself can be carried out prepolymerization as solvent, prepolymerization can also be carried out with solvent-free in fact state.Now, preferably prepolymerization is carried out continuously.

The alkene used in prepolymerization both can identical with the alkene used in main polymerization described later also can not be identical, but be preferably propylene.Temperature during prepolymerization is generally-20 ~+100 DEG C, is preferably-20 ~+80 DEG C, is more preferably the scope of 0 ~+40 DEG C.

Then, be described in the main polymerization (polymerization) implemented after prepolymerization or without prepolymerization.Main polymerization (polymerization) is divided into the operation manufacturing crystalline propylene system (being total to) polymkeric substance and the operation manufacturing copolymer rubber, as use in this any operation (namely, be polymerized) alkene, propylene can be enumerated and be selected from more than one the alkene in the alpha-olefin of ethene and carbonatoms 4 ~ 20.As the concrete example of the alpha-olefin of carbonatoms 4 ~ 20, can enumerate: the branched alkene of the straight-chain alkene such as 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene or 4-methyl-1-pentene, 3-Methyl-1-pentene, 3-methyl-1-butene etc., among these, preferred 1-butylene, 1-amylene, 4-methyl-1-pentene.Thus, as the combination of preferred alkene, can enumerate: propylene-ethylene, propylene-1-butylene, propylene-1-amylene, propylene-4-methyl-1-pentene, propylene-ethylene-1-butylene, propylene-ethylene-1-amylene, propylene-ethylene-4-methyl-1-pentene etc.In addition, be easy to performance from the view point of the distribute advantage of wide polymkeric substance of the resin middle-molecular-weihydroxyethyl high in rigidity, particularly preferably comprise 1-butylene, 4-methyl-1-pentene as the formation of multipolymer.

Also the aromatic ethenyl compound such as vinylbenzene, allyl benzene can be used together with these alpha-olefins; The alicyclic vinyl compounds such as vinyl cyclohexane, vinyl suberane.Further, the cyclic olefins such as cyclopentenes, suberene, norbornylene, tetracyclododecane can also be used; Isoprene, divinyl equiconjugate diene; What non-conjugated diene was such has the compound of many unsaturated link(age)s as polymer raw.These compounds both can be used alone or two or more kinds may be used (following, to be called " other alkene " by the alkene used together with the alpha-olefin being 4 ~ 20 with above-mentioned ethene and carbonatoms).

In other alkene, optimization aromatic vinyl compound.Further, in the total amount 100 % by weight of alkene, can with on a small quantity, such as less than 10 % by weight, be preferably less than 5 % by weight amount and use other alkene.

In the present invention, prepolymerization and main polymerization can be implemented with any means of the liquid polymerizations such as mass polymerization, solvent polymerization, suspension polymerization or gaseous polymerization.When main polymerization adopts the reaction form of slurry polymerisation, as reaction solvent, both can use the nonactive hydrocarbon used during above-mentioned prepolymerization, be the alkene of liquid under also can being used in temperature of reaction, pressure.

In the main polymerization of the manufacture method of propylene-based block copolymer of the present invention, above-mentioned solid titanium catalyst component (I), be scaled the titanium atom of every 1 liter of polymerization volume, usually with about 0.0001 ~ 0.5 mmole, the amount use being preferably about 0.005 ~ 0.1 mmole.In addition, above-mentioned Organometal compound catalyst composition (II), relative to the titanium atom in the pre-polymerized catalyst composition in polymerization system 1 mole, uses with the amount that about 1 ~ 2000 mole, preferably 5 ~ 500 moles are so usually.When use electron donor (III), relative to above-mentioned Organometal compound catalyst composition (II) 1 mole, with 0.001 ~ 50 mole, be preferably 0.01 ~ 30 mole, be more preferably 0.05 ~ 20 mole amount use.

If carry out main polymerization in the presence of the hydrogen, then the molecular weight of the polymkeric substance that (reduction) can be regulated to obtain, can obtain the polymkeric substance that melt flow rate (MFR) is large.In main polymerization, the polymerization temperature of alkene is generally about 20 ~ 200 DEG C, is preferably 30 ~ 100 DEG C, is more preferably 50 ~ 90 DEG C.Pressure (gauge pressure) is set as normal pressure ~ 100kgf/cm usually ²(9.8MPa), 2 ~ 50kgf/cm is preferably set to ²(0.20 ~ 4.9MPa).In the manufacture method of propylene-based block copolymer of the present invention, can be polymerized with any means of intermittent type, semi continuous, continous way.In addition, reaction conditions can also be changed polymerization is divided into more than two sections and carries out.If carry out such multi-stage polymeric, the molecular weight distribution of olefin polymer just can be further expanded.

Manufacture method for the propylene based block copolymer that the present invention relates to is described in detail.According to the other discovery of the present inventor, the insoluble part of n-decane (Dinsol) forming propylene based block copolymer of the present invention and alfon, propylene random polymkeric substance (with the amount being no more than 1.5mol% containing being derived from the acrylic polymer being selected from ethene and the skeleton of the alkene of more than a kind in the alpha-olefin of carbonatoms more than 4) or their two or more mixtures are identical in fact.

On the other hand, n-decane soluble part (Dsol) identical in fact with propylene-ethylene copolymers, propylene-alpha-olefin copolymers, propylene-ethylene-alpha-olefin copolymer or their two or more mixtures (wherein, " multipolymer " also comprises unregulated polymer).Therefore, propylene based block copolymer of the present invention substantially can by following any manufacture method manufacture.

method A

By two polymerization process (polymerization process 1 and polymerization process 2) be implemented as follows continuously, the method of the propylene based block copolymer of [1] ~ condition that manufacture satisfies condition [3] and preferably satisfy condition [4] and/or [5] is (following, sometimes the method is called " direct polymerization method ", the propylene based block copolymer obtained by the method is called " propylene based block copolymer (A) ").

[polymerization process 1]:

By propylene, more than one the alkene be selected from the alpha-olefin of ethene and carbonatoms 4 ~ 20 as required, under the existence of solid titanium catalyst component, manufacture the operation (crystalline propylene is (being total to) polymers manufacturing operation) of (be total to) polymkeric substance.

[polymerization process 2]:

By propylene and more than one the alkene that is selected from the alpha-olefin of ethene and carbonatoms 4 ~ 20, under the existence of solid titanium catalyst component, manufacture the operation (copolymer rubber manufacturing process) of multipolymer.

method B

Distinguish the multipolymer generated in the polymerization process 2 of (being total to) polymkeric substance and the aforesaid method A generated in the polymerization process 1 of manufacture method A under the existence of solid titanium catalyst component after, they are (following by the method for the means fusion of physics, sometimes the method is called " fusion method ", the propylene based block copolymer obtained by the method is called " propylene series copolymer (B) ").

The propylene based block copolymer that the present invention relates to, under the existence of above-mentioned catalyst for olefines polymerizing, as as described in method A, in polymerization process 1, carry out in the medium of propylene propylene homopolymerization or with the amount being no more than 1.5mol% containing be derived from be selected from ethene and carbonatoms 4 ~ 20 alpha-olefin in the manufacture of propylene system copolymerization of skeleton of the alkene of more than a kind, in polymerization process 2, carry out propylene and be selected from the copolymerization that ethene and carbonatoms are the alkene of more than a kind in the alpha-olefin of 4 ~ 20.Its result, the feature of the propylene based block copolymer finally obtained is, is made up of the part (Dinsol) 20 ~ 95 % by weight being insoluble to n-decane under dissolving in the part (Dsol) 5 ~ 80 % by weight of n-decane and room temperature under room temperature.

When using catalyst for olefines polymerizing as above to carry out the homopolymerization of propylene, can obtain decane insoluble composition containing ratio be more than 70 % by weight, be preferably more than 85 % by weight, be more preferably the stereospecific of weight more than 90% high, propylene based block copolymer that namely crystallinity component content is many.

In addition, according to the manufacture method of such propylene based block copolymer of the present invention, by the effect of catalyst for olefines polymerizing of the present invention, even if do not carry out multi-stage polymeric, with the polymerization of few hop count, such as single stage polymerisation, the wide propene polymer of molecular weight distribution also can be obtained.

According to the manufacture method of propylene based block copolymer of the present invention, it is characterized in that, be particularly equal existing olefin polymer compared to melt flow rate (MFR) (MFR), the high and olefin polymer that ratio that the is composition that molecular weight is low is low of the ratio that can obtain the high composition of molecular weight under most cases.This feature can be measured by gel permeation chromatography described later (GPC) and confirm, can obtain Mw/Mn value and the both high polymkeric substance of Mz/Mw value.

The polypropylene that the solid titanium catalyst component that use in the past contains magnesium, titanium, halogen and electron donor obtains, such as, be in the region of 1 ~ 10g/10 minute at MFR, usually the index Mw/Mn value being measured the molecular weight distribution of trying to achieve by GPC is less than 6, Mz/Mw value is less than 4, but when using the manufacture method of propylene based block copolymer of the present invention, Mw/Mn value can be obtained with above-mentioned same polymerizing condition and being 7 ~ 30, being preferably the propylene based block copolymer of 8 ~ 20.

In addition we know, according to the manufacture method of the propylene based block copolymer that the present invention relates to, can obtain the polymkeric substance that Mz/Mw value is high, Mz/Mw value is 6.0 ~ 25, is preferably 6.5 ~ 23, is more preferably 7.0 ~ 20.In addition, the higher limit of Mz/Mn value is preferably 300, is more preferably 250, is particularly preferably 200.Lower value is preferably 70, is more preferably 100, is particularly preferably 120.Particularly in the manufacture method of propylene based block copolymer of the present invention, Mz/Mw value, polymkeric substance that Mz/Mn value is high can be obtained.

The formability of the propene polymer that Mw/Mn value is high and excellent rigidity.On the other hand, Mz/Mw value height represents the high containing ratio of the composition that molecular weight is high, and the possibility that melting tension force is high, formability is excellent of the propene polymer obtained is high.

If use the manufacture method of the propylene based block copolymer that the present invention relates to, even if do not carry out multi-stage polymeric can obtain wide, that namely Mw/Mn value the is high polymkeric substance of molecular weight distribution yet, therefore, there is polymers manufacturing device etc. is simple form, and can obtain the possibility of the propene polymer of formability and excellent rigidity.In addition, can expect to use catalyst for olefines polymerizing of the present invention, when being polymerized by existing multi-stage polymeric method, the polymkeric substance that molecular weight distribution is wider can be manufactured, become melting tension force and the more excellent polymkeric substance of formability.

In addition, if use the manufacture method of propylene based block copolymer, can obtain that high molecular weight components content is many, i.e. Mz/Mw value, polymkeric substance that Mz/Mn value is high, therefore, can be accomplished the polymkeric substance had both of high workability and high melting tension force, also can realize injection molding and the shortening in injection molding cycle of massive article, in addition, the outward appearance of injection-molded article becomes good, and blow moldability, foaming become good etc., can give molding processibility.

As the additive method obtaining the wide polymkeric substance of molecular weight distribution, also has the method by polymer dissolution different for molecular weight mixing or melting mixing, but by the polymkeric substance that these methods obtain, operate more numerous and diverse, and the raising of melting tension force and formability is insufficient sometimes.Can infer this is because the different polymkeric substance of molecular weight is difficult to mixing substantially.On the other hand, the polymkeric substance obtained by the manufacture method of propylene based block copolymer of the present invention, the polymkeric substance that the molecular weight of pole wide region is different mixes with catalyst grade, i.e. nano-scale, therefore, can expect that melting tension force is high, formability is excellent.

The acrylic polymer that the present invention relates to, owing to using high activated catalyst, so have from the few feature of the metallic residue of catalyzer.Be used as the acrylic polymer that the titanous chloride series catalysts known by the catalyzer that can realize wide molecular weight distribution obtains, because the metallic residue in SA cause polymkeric substance is many.Although the difference to some extent according to purposes, can say when metallic residue is many, outward appearance or resin characteristics mostly can be caused to reduce or resin with detrimentally affects such as colors.Therefore, usually use the heating such as alcohol or acid to carry out deliming process, the metal ingredient from catalyzer remaining in polymkeric substance is removed.When titanous chloride series catalysts, titanium metal contained in the polymkeric substance before deliming is 30 ~ 200ppm, but by deliming process, can be reduced to 2 ~ 50ppm.On the other hand, when of the present invention for obtain propylene system block polymer high activated catalyst, the titanium metal composition before deliming is 1 ~ 30ppm in the polymer, can be reduced to 0.1 ~ 2ppm by deliming process.

[nucleator]

Nucleator has anisotropic organic metal salt nucleator.Have anisotropy to refer to, when using this nucleator, compared with when not using, the shrinking percentage in TD direction (direction rectangular with the flow direction of resin during forming process) is large.

Infer this is because when using this nucleator, in propylene resin composition, nucleator is in MD direction (flow direction of resin during forming process) upper orientation, the crystallizing layer of acrylic resin grows in the perpendicular direction, therefore in MD direction (flow direction) and TD direction (right angle orientation) the upper cause producing contraction rate variance.

The feature of propylene polymer composition of the present invention is, containing the acrylic polymer and the nucleator that meet following condition [1] ~ [4] simultaneously, wherein, this nucleator is organic metal salt, in this propylene polymer composition, contain the above-mentioned nucleator of more than 150ppm below 3000ppm relative to aforesaid propylene based polymer.

[1] part (Dsol) dissolving in n-decane under room temperature is less than more than 0 % by weight 80 % by weight, the part (Dinsol) being insoluble to n-decane under room temperature is less than more than 20 % by weight 100 % by weight (wherein, the total amount of Dsol and Dinsol is 100 % by weight)

[2] molecular weight distribution (Mw/Mn) recorded by gel permeation chromatography of Dinsol is less than more than 7.0 30, and Mz/Mw is less than more than 6.0 25

[3] the five-tuple mark (mmmm) of Dinsol is more than 93%

[4] fusing point (Tm) recorded by differential scanning calorimeter of Dinsol is more than 140 DEG C

And the feature of above-mentioned nucleator is, it is organophosphate.Wherein, " Adekastab NA-11 " " Adekastab NA-21 " " Adekastab NA-25 " (being Asahi Denka Co., Ltd. to manufacture) is preferably.

Propylene polymer composition of the present invention containing nucleator being used for injection molded article is preferred mode of the present invention, and wherein, this nucleator is being that organophosphate is for feature.

Further, propylene polymer composition of the present invention also may be used for thin-walled molding body.

Specifically, as having anisotropic organic metal salt nucleator, can enumerate and organicly phosphate-basedly make core agent, the metal-salt of carboxylic acid makes core agent, rosin series makes core agent.Wherein, be preferably organic phosphoric acid, such as can enumerate two (4-tert-butyl-phenyl) sodium phosphate salt, two (4-tert-butyl-phenyl) phosphoric acid lithium salts, two (4-tert-butyl-phenyl) phosphalugel, 2, 2'-methylene radical-bis-(4, 6-di-tert-butyl-phenyl) sodium phosphate salt, 2, 2'-methylene radical-bis-(4, 6-di-tert-butyl-phenyl) phosphoric acid lithium salts, 2, 2'-methylene radical-bis-(4, 6-di-tert-butyl-phenyl) phosphalugel, 2, 2'-methyne-bis-(4, 6-di-tert-butyl-phenyl) calcium phosphate salt, 2, 2'-ethylidine-bis-(4, 6-di-tert-butyl-phenyl) sodium phosphate salt, 2, 2'-ethylidine-bis-(4, 6-di-tert-butyl-phenyl) phosphoric acid salt lithium, 2, 2'-ethylidine-bis-(4, 6-di-tert-butyl-phenyl) phosphalugel, two-(4-tert-butyl-phenyl) calcium phosphate salt etc.They also can use commercially available product.Such as can enumerate by " the Adekastab NA-11 ", " AdekastabNA-21 ", " Adekastab NA-25 " etc. of ADEKA sold.

In prolylene polymer composition of the present invention, as the acrylic polymer of its essential component, as described later owing to being wide molecular weight distribution, so the polymkeric substance containing a large amount of high molecular.Therefore can think in injection molding, the crystalline orientation of MD direction (flow direction time shaping) is residual comparatively strong, produces the anisotropy of molding shrinkage, causes the buckling deformation of formed body.But can think by adding above-mentioned specific nucleator, nucleator is in MD direction orientation, acrylic resin is gone up crystalline growth for core in TD direction (direction vertical with MD) with this nucleator and is promoted, its result, by eliminating the anisotropy of molding shrinkage, effectively buckling deformation can be suppressed.

[stablizer contained by propylene resin composition, other compositions]

The propylene resin composition that the present invention relates to containing various additives shown below, preferably can contain inorganic filler and/or elastomerics.

Stablizer used in the present invention unrestrictedly can use the known stablizer such as heat-resisting stabilizing agent, weathering stabilizers, resistance to photostabilizer, chlorination absorption agent, weighting agent, tenderizer.Such as, the higher fatty acid metal salt, inorganic oxide, glass fibre etc. of known phenol system stablizer, organophosphite system stablizer, thioether system stablizer, hindered amine system stablizer, calcium stearate etc. can be enumerated.

Can also containing other heat-resisting stabilizing agent, weathering stabilizers, antistatic agent, slipping agent, antiblocking agent, antifogging agent, lubricant, dyestuff, pigment, natural oil, synthetic oil, wax etc. in the polypropylene resin composite that the present invention relates to.

In addition, the propylene resin composition that the present invention relates to can add elastomer components to give for the purpose of shock-resistance.As elastomerics, the propylene-alpha olefin block multipolymer different from propylene based block copolymer of the present invention, ethene-alpha-olefin random copolymers, ethylene-alpha-olefin-nonconjugated polyene random copolymer, copolymer, hydrogenated acrylonitrile-'alpha '-olefin block copolymers and other elastomeric polymer and their mixture etc. can be enumerated.These elastomer components are not particularly limited, and preferably relative to propylene based block copolymer 100 weight part of the present invention, are 1 ~ 100 weight part, are more preferably 3 ~ 60 weight parts.

The propylene resin composition that the present invention relates to can add other propylene polymer component as required in the scope of effect not damaging invention.In addition, the propylene resin composition that the present invention relates to can contain silicon-dioxide in the scope not damaging object of the present invention, diatomite, aluminum oxide, titanium oxide, magnesium oxide, pumice sand, float stone hollow ball, aluminium hydroxide, magnesium hydroxide, alkaline magnesium carbonate, rhombspar, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talcum, clay, mica, asbestos, glass fibre, sheet glass, granulated glass sphere, Calucium Silicate powder, montmorillonite, wilkinite, graphite, aluminium powder, moly-sulfide, boron fibre, the inorganic fillers such as silicon carbide fiber, polyethylene fibre, polypropylene fibre, trevira, tynex, the organic filler of carbon fiber etc.These weighting agents are not particularly limited, and preferably relative to propylene based block copolymer 100 weight part of the present invention, are 1 ~ 100 weight part, are preferably 3 ~ 60 weight parts.In the present invention, the crystallinity nucleator used to improve buckling deformation can enumerate phosphate metal salt, carboxylic metallic salt.Particularly preferably phosphate metal salt.

(injection molded article)

The injection molded article that the present invention relates to uses the manufacture of aforesaid propylene polymer composition.Acrylic polymer contained by this prolylene polymer composition has following feature: owing to meeting above-mentioned condition [1] ~ [4] simultaneously, so rigidity-shock-resistance balances, and owing to being wide molecular weight distribution, so melt fluidity is high, polymkeric substance containing a large amount of high molecular, based on this, high-molecular weight polymer performance is as the effect of crystallization nucleating agent, and crystallization rate is accelerated thus.Due to such feature, the balancing good of rigidity-shock-resistance, shaping time high to the mobility of mould, and then due to crystallization rate fast so have the feature that can shorten shaping cycle.In addition, by containing specific nucleator as mentioned above, can suppress the buckling deformation of thin wall injection formed body, molded appearance is good.

Therefore, the purposes of the injection molded article that the present invention relates to does not limit, and can be adapted at automobile exterior parts, automobile inside components, other the middle use such as trolley part, appliances parts, food product containers, beverage container, medical container, freight container (container).

Particularly owing to suppressing the effective of buckling deformation in the injection molded article of thin-walled, so be particularly suitable for using in the thin-walled pressure vessel of food product containers, medical container etc.In the present invention, the injection molded article of thin-walled refers to that thickness is less than the formed body of 3mm.Preferably when more than 0.3mm below 2.0mm, buckling deformation inhibition is good.

Embodiment

The present invention will be described particularly further to utilize following embodiment.Wherein, as long as the present invention is no more than its main points, the record of following embodiment is not limited to.The physical property measurement of acrylic polymer or propylene polymer composition, mechanical properties evaluation, formability evaluation are undertaken by following method.

(1) solvable under room temperature (insoluble) is in the component amount ((wt%)) of n-decane

In the mensuration container of glass, load propylene based block copolymer be about 3g and (be measured to 10 ^-4the unit of g.In addition, this weight is expressed as b (g) in following formula), decane 500ml and dissolve in the heat-resisting stabilizing agent of decane on a small quantity, under nitrogen atmosphere, while stir while be warmed up to 150 DEG C with 2 hours with agitator, propylene based block copolymer is dissolved, after keeping 2 hours at 150 DEG C, slowly cooled to 23 DEG C with 8 hours.By the obtained glass filter filtration under diminished pressure comprising liquid Pan Tian glass Co., Ltd. 25G-4 specification of the precipitate of propylene based block copolymer.Gather filtrate 100ml, its drying under reduced pressure is obtained the part dissolving in decane composition, measures its weight to 10 ^-4the unit (this weight is expressed as a (g) in following formula) of g.After this operation, determine according to following formula the component amount dissolving in decane.

Composition (the D of n-decane is dissolved under room temperature _sol) containing ratio=100 × (500 × a)/(100 × b)

Composition (the D of n-decane is insoluble under room temperature _insol) containing ratio=100-100 × (500 × a)/(100 × b)

(2) molecular weight distribution

Liquid chromatography: the Alliance GPC2000 type (differential refractometer detector is one-piece type) using Waters.

Chromatographic column: GMH6-HT × 2 of TOSOH Co., Ltd piece are connected in series with GMH6-HTL × 2 piece.

Moving phase medium: orthodichlorobenzene

Flow velocity: 1.0ml/ minute

Measure temperature: 140 DEG C

The making method of typical curve: use standard polystyrene sample.

Sample concentration: 0.15% (w/v)

Sample solution amount: 500 μ l

Measure with above-mentioned condition, resolved the color atlas obtained by known method, calculate Mw/Mn value thus.Each sample tests time is 60 minutes.

(3) five-tuple mark (mmmm: (%))

Study its microtacticity of one of the index as the stereospecific of polymkeric substance.Five-tuple mark (mmmm, %) according in propene polymer based on Macromolecules 8,687 (1975) belong to ¹³the peak intensity ratio of C-NMR spectrum calculates. ¹³c-NMR spectrum uses the device of NEC EX-400, be benchmark with TMS, temperature 130 DEG C, use orthodichlorobenzene solvent measure.

(4) fusing point (Tm)

Use the DiamondDSC of Perkinelmer Inc..

Example weight: 5mmg

Use material for aluminium and the sample disc of bottom flat, sample uses the compressing tablet that 0.5mm is thick, makes sample not overlapping in sample disc.After being warmed up to 230 DEG C (heat-up rate 500 DEG C/min), keep this temperature 10 minutes, after being cooled to 30 DEG C with cooling rate 10 DEG C/min, keep 1 minute at 30 DEG C.Then, 230 DEG C are warmed up to, using the peak temperature at peak the highest for melting hump height as fusing point with heat-up rate 10 DEG C/min.

(5) content of the skeleton of ethene is derived from

In order to measure the skeleton concentrations being derived from ethene in Dsol, after sample 20 ~ 30mg being dissolved in 1,2,4-trichlorobenzene/deuterated benzene (2:1) solution 0.6ml, carry out nuclear magnetic resonance of carbon analysis ( ¹³c-NMR).The quantitative of propylene, ethene is tried to achieve by the distribution of diad chain.

When propylene-ethylene copolymers, use PP=S α α, EP=S α γ+S α β, EE=1/2 (S β δ+S δ δ)+1/4S γ δ, obtained by following calculating formula.

Propylene (mol%)=(PP+1/2EP) × 100/ [(PP+1/2EP)+(1/2EP+EE)

Ethene (mol%)=(1/2EP+EE) × 100/ [(PP+1/2EP)+(1/2EP+EE)

Wherein, the D in the present embodiment _solethene amount unit conversion be % by weight to mark.In addition, D _solin, CSD calculates according to following formula (i).

$\mathrm{CSD}=\frac{\left[\mathrm{EE}\right]\×\left[\mathrm{PP}\right]}{{\left(\right[\mathrm{PE}]/2)}^2}...\left(i\right)$

According to (in formula (i), [EE] is D _solin the mole fraction of ethylene chain, [PP] is D _solin the mole fraction of propylene chain, [PE] is the mole fraction of propylene-ethylene chain) measure.

(6) melt flow rate (MFR) (MFR: (g/10 minute))

According to ASTMD1238E, measure with 2.16kg load.Measuring temperature is 230 DEG C.

(7) modulus in tension

Use mold clamping pressure is the electric injection moulding machine (Toyo Jukikai Metal Corp. Si-80III) of 80 tons, under the condition of barrel temperature 200 DEG C, die temperature 40 DEG C, by modulus in tension test film ISO testpieces (test piece) type (type A type) injection molding, obtain the test film that modulus in tension measures.

Modulus in tension measures according to the modulus in tension test method(s) specified by ISO527-2.Wherein, stretching and measuring temperature is 23 DEG C, 0 DEG C, and trial speed is 1mm/min.

(8) Charpy impact test

(JIS small specimen)

Charpy impact test ((kJ/m ²)) measure with following test conditions according to JISK7111.

Temperature: 23 DEG C, 0 DEG C

Test film: 10mm (wide) × 4mm (thick) × 80mm (length)

Breach: mechanical workout

(9) eddy flow length

Use the resin flows length measurment mould with the stream on spiral of thickness 1mm, width 10mm.Measure with following eddy flow length measurment injection molding condition.

Injection moulding machine: FANUC Inc. Auto Shot T series model 100D

Barrel temperature: 230 DEG C

Die temperature: 40 DEG C

Inject time: 5 seconds (without pressurize setting)

(10) camber test

The method use mold clamping pressure measuring buckling deformation is the electric injection moulding machine (FANUC Inc. Auto Shot T series model 100D) of 100 tons, barrel temperature 210 DEG C, die temperature 20 DEG C, injection speed 20mm/sec, inject time 3.5sec, under cooling time 3sec condition, make the disc test sheet of the disk of trumpet assembly, diameter 250mm, thickness 2mm.

Use these test films, measure buckling deformation.Disc test sheet is placed in horizontal plane, under the state pressing with finger at 1, measures the levitation height of floating the highest part from horizontal plane.That is, numerical value is larger, and buckling deformation is larger.

(11) cooling time, fall sphere test

As injection moulding machine, use FANUC Inc. Auto Shot T series model 100D.Use the wide cup mould of wall thickness 3mm, base diameter 75mm, upper diameter 80mm, height 80mm, start shaping with mold temperature 230 DEG C, die temperature 50 DEG C, the condition of 20 seconds cooling times, shorten cooling time, when products formed is given prominence to from mould, measure the cooling time that products formed distortion occurs.

In addition, use wall thickness 0.5mm, base diameter 49mm, upper diameter 63mm, height 110mm, there is along the circumference on top the beverage cup mould of flange of width 4mm, wall thickness 0.5mm, carry out shaping with mold temperature 230 DEG C, die temperature 20 DEG C, the condition of 8 seconds cooling times, obtain formed body.Then, with test temperature 5 DEG C, make diameter 30mm, the iron ball of weight 130g drops to this formed body, measure height flange part occurring and breaks.

[Production Example 1]

(preparation of solid titanium catalyst component)

After abundant nitrogen displacement is carried out to the internal volume high-speed stirring apparatus (special machine chemical industry system (TK homomixerM type)) that is 2 liters, add refining decane 700ml, commercially available magnesium chloride 10g, ethanol 24.2g and trade(brand)name RHEODOL SP-S20 (Kao Corp's sorbitan SUNSOFT Q-182S) 3g in the apparatus, stir this suspension liquid while system heated up, suspension liquid is stirred 30 minutes at 120 DEG C with 800rpm.Then, this suspension liquid of high-speed stirring makes it not produce throw out on one side, while use teflon (registered trademark) tubulation of internal diameter 5mm, be transferred to the glass flask (belt stirrer) being incorporated with 2 liters of refining decane 1 liter being cooled to-10 DEG C in advance.By by moving the solid filtering that liquid generates, fully cleaning with refining normal heptane, thus, obtaining solid state adducts magnesium chloride 1 mole of coordination being had to ethanol 2.8 moles.With decane, this solid state adducts is made suspension, being that the above-mentioned solid state adducts of 23 mmoles under agitation imports and remains in the titanium tetrachloride 100ml of-20 DEG C by being scaled magnesium atom, obtaining mixed solution.With 5 hours, this mixed solution is warmed up to 80 DEG C, when reaching 80 DEG C, relative to the magnesium atom 1 mole of solid state adducts to be the amount interpolation 3 of the ratio of 0.0875 mole, 6-dimethyl cyclohexane-1,2-diisobutyl dicarboxylate (cis-isomeride, trans isomer mixture), was warmed up to 110 DEG C with 40 minutes.When reaching 110 DEG C, further with the amount interpolation hexanaphthene-1 relative to the magnesium atom 1 mole of solid state adducts being the ratio of 0.06 mole, 2-diisobutyl dicarboxylate (cis-isomeride, trans isomer mixture), while temperature is remained on 110 DEG C while stir 90 minutes, thus them are made to react.

After the reaction of 90 minutes terminates, gather solid part by heat filtering, this solid part is suspended in the titanium tetrachloride of 100ml again, afterwards, heat up, when reaching 110 DEG C, keeping stirring 45 minutes, thus making them react.After the reaction of 45 minutes terminates, again gather solid part by heat filtering, fully clean with the decane of 100 DEG C and heptane, until detect in washing lotion do not go on a tour from titanium compound.

Preserved with the form of decane suspension liquid by the solid titanium catalyst component (α 2) operating preparation above, but in order to Study of Catalyst composition is by part drying wherein.Solid titanium catalyst component (α 2) that such operation obtains consists of: titanium 3.2 quality %, magnesium 17 quality %, 3,6-dimethyl cyclohexane-1,2-diisobutyl dicarboxylate 10.9 quality %, hexanaphthene-1,2-diisobutyl dicarboxylate 8.5 quality % and ethanol residue 0.6 quality %.

(prepolymerization of solid titanium catalyst component)

Then, be in the there-necked flask of the belt stirrer of 200 milliliters with the internal volume after nitrogen displacement, add the hexane through dehydration, drop into triethyl aluminum 0.75 mmole and convert with titanium atom and count the suspension liquid of the above-mentioned solid titanium catalyst component (α 2) of 0.25 mmole, make total amount be 50 milliliters.Under the condition that it is stirred, maintain 20 DEG C, within 60 minutes, absorb the propylene of specified amount.Then, replace residual propylene with nitrogen, use hexane fully to clean, obtain pre-polymerized catalyst composition.

(polymerization)

Be in the autoclave of 17 liters, load propylene 3 kilograms, hydrogen 270 liters at internal volume, after being warmed up to 60 DEG C, loading triethyl aluminum 15 mmole, Cyclohexyl Methyl Dimethoxysilane 5 mmole and convert with titanium atom and count the above-mentioned pre-polymerized catalyst composition of 0.05 mmole.Then after being warmed up to 70 DEG C, being kept 30 minutes, carried out the homopolymerization of propylene, in order to remove the gases such as unreacted propylene after terminating, being opened breather valve, take off and be depressed into normal pressure.

After pressure reaches normal pressure, then, the copolymerization of ethene and propylene is carried out.Namely with 450 liters of supply ethene per hour, with 750 liters of supply propylene per hour, with 5.8 liters of supply hydrogen per hour, regulate the aperture of breather valve, pressure is kept 120 minutes at 1MPa.Now, temperature is 70 DEG C.

After specified time terminates, a small amount of ethanol being loaded autoclave and stops polymerization, removing unreacted gas by opening breather valve.Then, by the white particle in autoclave 80 DEG C, decompression under carry out drying, obtain the polymer beads of about 2.5kg.Repeat 3 these operations, obtain acrylic polymer (A-1).The evaluation result of acrylic polymer is represented in Table 1.

[embodiment 1]

Relative to the acrylic polymer obtained in Production Example 1 (A-1) 100 weight part, by heat-resisting stabilizing agent IRGANOX1010 (trade mark, Ciba Japan Co., Ltd.) 0.1 weight part, heat-resisting stabilizing agent IRGAFOS168 (trade mark, Ciba Japan Co., Ltd.) 0.1 weight part, heat-resisting stabilizing agent IRGANOX1076 (trade mark, Ciba Japan Co., Ltd.) 0.1 weight part, calcium stearate 0.1 weight part, crystallinity nucleator Adekastab NA-11 (trade mark, ADEKA) 0.1 weight part is with after rotary drum mixing, use twin screw extruder melting mixing, obtain the propylene polymer composition of partical.The evaluation result of the propylene polymer composition obtained is represented in table 2.

[embodiment 2]

Except making crystallinity nucleator be except 0.05 weight part, carry out similarly to Example 1 testing, evaluating.The results are shown in table 1.

[comparative example 1]

Except not using crystallinity nucleator, carry out similarly to Example 1 testing, evaluating.The results are shown in table 2.

[comparative example 2]

Except the J709QG (with reference to table 1) using Puriman Polymer Co., Ltd to manufacture as acrylic polymer, carry out similarly to Example 1 testing, evaluating.The results are shown in table 2.

[table 1]

[table 2]

Claims (5)

1. a propylene polymer composition, is characterized in that:

Containing the acrylic polymer and the nucleator that meet following condition [1] ~ [4] simultaneously, described nucleator has anisotropic organic metal salt, in this propylene polymer composition, contain the described nucleator of more than 150ppm below 3000ppm relative to described acrylic polymer

[1] part (Dsol) dissolving in n-decane under room temperature is less than more than 0 % by weight 80 % by weight, the part (Dinsol) being insoluble to n-decane under room temperature is less than more than 20 % by weight 100 % by weight, wherein, the total amount of Dsol and Dinsol is 100 % by weight

[2] molecular weight distribution (Mw/Mn) recorded by gel permeation chromatography of Dinsol is less than more than 7.0 30, and Mz/Mw is less than more than 6.0 25,

[3] the five-tuple mark (mmmm) of Dinsol is more than 93%,

[4] fusing point (Tm) recorded by differential scanning calorimeter of Dinsol is more than 140 DEG C.

2. propylene polymer composition as claimed in claim 1, is characterized in that:

The melt flow rate (MFR) (230 DEG C, 2.16kg load) of described acrylic polymer is more than 30g/10 minute.

3. propylene polymer composition as claimed in claim 1 or 2, is characterized in that:

Described nucleator is organophosphate.

4. an injection molded article, is characterized in that:

The propylene polymer composition comprised according to any one of claims 1 to 3 forms.

5. injection molded article as claimed in claim 4, is characterized in that:

It is thin-walled molding body.