JPS58138720A - Preparation of propylene random copolymer - Google Patents

Abstract

PURPOSE:To prepare the titled copolymer having excellent transparency and low surface tackiness and odor, by using a catalyst composed of an organo-Al compound, an organo-Si compound, and a highly active Ti catalyst component composed of Mg, Ti, halogen and an electron donor. CONSTITUTION:A propylene copolymer having a propylene content of 40- 90mol% and a crystallinity of <=40wt% is prepared by the random copolymerization of propylene with >=4C alpha-olefin in the presence of a catalyst composed of (A) a highly active Ti catalyst component containing Mg, Ti, halogen and an electron donor as essential components, wherein the electron donor is an ester of a polyfunctional compound such as polybasic carboxylic acid, polyvalent hydroxy compound, hydroxyl-substituted carboxylic acid, etc., a monocarboxylic acid ester of formula RCOOR' (R and R' are hydrocarbon group), or a carbonic acid ester, etc., (B) an organo-Al compound catalyst component and (C) an organo-Si compound catalyst component having Si-O-C bond or Si-N-C bond or a hindered amine catalyst component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a random conjugate of robylene (which has excellent transparency, low surface resistance, and low porosity).

The applicant has already identified magnesium, titanium and halo I”7.
JP-A No. 53-1987 describes a method for producing a propylene random coelectrolyte with low crystallinity having diluted properties using a titanium catalyst component as an essential component and a catalyst system as an essential component of an electron donor. No. 79984 and special raU defect 53-10468
Ume is proposed in issue 6. In the discussion after 7, @
In the catalytic system, the prior application specifically describes the use of a combination formulation of a specific electron donor without deformity, which provides various benefits such as increased catalytic activity and increased catalyst life. It was revealed that it is possible to produce a propylene random composite body with low JA properties, with -1- unclear transparency and -1ii# reduced tendency for surface layering. . Accordingly, the present invention relates to an improved method for producing propylene random copolymers. More specifically, the present invention comprises (A) a highly active titanium catalyst component containing magnesium, titanium, halodane, and an electron donor as essential components,
The electron donor is (α) an ester of a polyfunctional compound selected from the group consisting of polyvalent carmenic acid, a polyvalent hydroxy compound, and a hydroxy group-substituted calgon soap, (b) RCOO
The monocar represented by RI is a phosphoric acid ester, and the seven hydrocarbons -Ij! ! A titanium catalyst component in which at least one of R and R' is an ester selected from the group consisting of a monocarbic acid ester and (C) a carbon ester, in which at least one of R and R' is a branched carbide-like group. , (B) organoaluminated @*mSakibzmin and (C) formed from an organosilicon compound catalyst component having a 5i-0-C bond or a 5i-IV-C bond or a steric 4-an amine catalyst component In the presence of a catalyst, propylene and a random α-olefin having at least several carbon atoms are combined to form a random co-container t- (Relating to a method of manufacturing a random joint body.)

The titanium catalyst component used in the present invention is a highly active catalyst component whose essential components are magnesium, titanium, halogen, and an additional electron donor. This titanium catalyst component (4) contains magnesium 710rnide, which has lower crystallinity than commercially available magnesium 710rnide.
Usually, the specific surface area is about 3-/- or more, preferably about 40-/- or more.
or about 1000-/f1 9 preferably about 80 to about 800rI? /, its composition is not substantially changed by washing with hexane at room temperature. In the titanium catalytic component (A), the rhodan/titanium (atomic ratio) is about 5 to about 200, particularly about 5 to about 1.
00, f electron donor/titanium (molar ratio) from about αl to about 10, especially from about 0.2 to about 6, magnesium/
Titanium (atomic ratio) is preferably about 2 to about 100, particularly about 4 to about 50. The component (A)/″l
It may also contain other electron donors, gold-1 elements, functional groups, etc. It may also contain organic or inorganic diluents such as silicon compounds, aluminum compounds, polyolefins, etc.

Such a titanium catalyst component (A) can be obtained by mutual contact of magnesium compound I# (or magnesium gold@), an electron donor, and a titanated adduct, but in some cases, other reaction reagents, feed 1tS materials such as silicon, phosphorus alumnium, etc. can also be used.

As a method for forming such a titanium catalyst component (4), for example, JP-A-50-108385 and JP-A-5G-12
No. 6590, No. 51-2029745, No. 51-281
No. 89, No. 51-64586, No. 61-92885, No. 51-136625, No. 52-87489, No. 52-100596, No. 52-147688, No. 5
No. 2-104593, No. 53-2580, No. 53-4
No. 0093, No. 53-43094, No. 55-1351
No. 02, No. 55-135103, No. 56-811,
It can be produced according to the method disclosed in No. 45g-11908, No. 56-18606, etc.

Some examples of methods for producing these titanium catalyst components (A) will be briefly described below.

(11 Magnesium compound WS or complex compound vlJ of magnesium compound and electron donor is pulverized or not pulverized in the presence or absence of an electron donor, a grinding aid, etc.) Pre-treatment with a reaction aid such as an aluminum compound or a halodane-containing silicide,
Alternatively, the solid obtained without pretreatment is reacted with a titanium compound that forms a liquid phase under the reaction conditions. However, the above electron donor is used at least a few times. .

(2) A solid titanium complex is precipitated by reacting a liquid magnesium compound having no reducing ability with a liquid titanium adduct in the presence of an electron donor.

(3) Invert the titanized @ product to the one obtained in 12).

(41 (React the material obtained in (11) and (2) with an electron donor and a titanium compound.

(5) Magnesium compounds or magnesium compounds!
Complex compound of II and electron donor? , in the presence or absence of an electron donor, a grinding aid, etc., and in the presence of a titanium compound, and an electron donor and/or an unscrupulous aluminide or a halogen-containing silicide. The R1 form obtained with or without pretreatment is treated with a reaction aid such as a halodane or halodane compound or aromatic carbonization/l<$. However, the electron donor described above must be used at least once. 1° (6)
It is treated with the nine-compound halon or halodane compound obtained in (1) to (4) above, or an aromatic hydrocarbon.

Among these preparation methods, those using liquid titanium halide or those using a halogenated hydrocarbon after or during the use of a titanium compound are preferred in the preparation of the catalyst.

One of the electron donors that can be a component of the highly active titanium catalyst component (A) of the present invention is a polyhydric carmenic acid, a polyhydric alcohol, and a hydroxyl-substituted carboxylic acid. Esters of functional compounds ←).

Suitable esters of these polyfunctional compounds are R'-C-OCOE@R'-C-OCOR"
(where KR"Fl; is a substituted or unsubstituted hydrocarbon group,
R, R'' and R are hydrogen or a substituted or unsubstituted hydrocarbon group, Ra and R4 are hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of them is a substituted or unsubstituted hydrocarbon group. It is a hydrocarbon group. Also, Bs and R' may be connected to each other. The substituted hydrocarbon group in R1-R6 includes a heteroatom such as N, O, S, etc., for example, C-0 -C.

C00R (where R is a hydrocarbon group), C0OH.

It has groups such as OH%So, H, -C-N-C-1NH, and the like. ) can be exemplified.

Particularly preferred among these are nocarboxylic acid diesters in which at least one of R1 and R1 is an alkyl group having 2 or more carbon atoms.

Specific examples of preferable polyvalent carboxylic acid esters include diethyl succinate, sibutyl conophosphate, V-ethyl methylsuccinate, diimbutyl α-methylglutarate, dibutyl malon, soethyl methylmalonate, zoethyl ethylmalonate, and fat zoethyl lumalonate,
Butylmalo/diethyl acid, phenylmalonate diethyl,
Soethyl noethylmalonate, diethyl allylmalonate,
V-ethyl diisobutylmalonate, diethyl dinormylbutylmalonate, dimethyl maleate, monooctyl maleate, dioctyl maleate, zotutyl maleate,
Sibutyl butyl maleate, soethyl butyl maleate, V isopropyl β-methylglumerate, diallyl ethylsuccinate, y-g-ethylhexyl furoate,
Fat*/licalconic acid esters such as diethyl itaconate, diethyl itaconate, dioctyl citraconate, dimethyl citraconate; 1. i! -Alicyclic polycardimethyl such as cyclohexanecarboxylic acid zoethyl, 1,2-cyclohexanecarboxylate, diluted V-ethyl tetrahydrophthalate, V-ethyl nanosuccinate, methylethyl phthalate, monoin phthalate l-thyl, mono-normal butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl normal-butyl phthalate, di-glopyru phthalate, diisoglobyl phthalate, di-S- phthalate
Butyl, diisobutyl phthalate, di-hedecyl phthalate, 2-ethylhexyl phthalate, yS- phthalate
octyl, 7tal eR zoneopentyl, V decyl phthalate, penturuthyl phthalate, s)yenyl 7thalate,
Aromatic polycarbonate esters such as diethyl naphthalene dicarnate, v-butyl naphthalene dicarnate, triethyl trimellitate, and zotutyl trimellitate; 3
．． 4-7) Heterogeneous ring I radicals such as carboxylic acids
Nistil; etc. can be mentioned.

The specific examples of preferred polyvalent human tetraxyl compound esters are 1.1! -$7 Acetoxybenzene, l-methyl-2,3-/acetoxypenzea, 2-3
-Diacetoxynaphthalene, ethylene dalycolzobia a
4-rate, butane di-rubiflate, and the like.

Examples of esters of hydroxy-substituted carboxylic acids include esters, benzoylethyl salicylate, a7tyl isobutyl salicylate, and acetyl methyl salicylate.

Other examples of polycarboxylic acid esters that can be supported in the titanium catalyst component include diethyl adipate,
Diisozotyl asopate, zoisoglovir heptabatanate,
Mention may be made of esters of long-chain dicarmenic acids such as 1%-butyl sepacate, di-octyl cef-4 cenate, and di-2-ethylhexyl mono(di-2-ethylhexyl cenate).

Among these polyfunctional esters, preferred are those having the skeleton f of the nine general formulas described above, and more preferred are phthalic acid, maleic acid, substituted malonic acid, and substituted 1N
#1 is an ester of 1-2-cyclohexanecarboxylic acid or the like and an alcohol having 2 or more carbon atoms, and preferably an ester of phthalic acid and an alcohol having 3 or more carbon atoms.

Other electron donor components that can be supported on the titanium catalyst component include RCOORI (R%R' is a hydrocarbon group which may have a substituent, at least one of which has a branched bell-shaped valence product). The parent is a ring-containing chain group). For example, R and/or
or as R' (CM, ), CH-1C,H,CM(C
M,)-5((1'//,), CHCHt-1(CH
l) s'-1C1H, CH(CH,)CHl, ○-CH
, -1r]. If either R or R' is a group as described above, the other may be a group as described above,
Alternatively, other groups such as linear or cyclic groups may be used.

Specific examples of the above RCOORI include dimethyl acetic acid, trimethyl acetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid, various monoesters of carganic acid such as benzoyl acetic acid, imprononol, isobutyl alcohol,
Various monocardic acid esters of alcohols such as tart-butyl alcohol and the like can be exemplified. Among these, those in which R is branched are particularly preferred, and those in which R' is also branched are particularly preferred.

Carbonic acid esters (6) t- can also be selected as electron donors. Variantly, V ethyl car is nate,
Ethylene car is $-), N iso! Examples include bircarcanate, phenylethyl carnate, and diphenyl carnate. Among these, especially carbon number 6
The above carbonate esters are preferred.

When supporting these electron donors, it is not necessarily necessary to use them as starting materials, but Waj! These compounds may be converted at the stage of Il production.

The titanium catalyst component contains the above (α) 1. (6) and (
Electron donors other than 0) may be coexisting, but should be kept to a small amount since coexisting in too large a quantity will have an adverse effect.

In the present invention, the magnesium compound used in the preparation of the solid titanium catalyst component [A] is reduced
Magnesium compounds with or without i-functionality can be used. Examples of the former include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as V-methylmagnesium, diethylmagnesium, diprozylmagnesium, diptylmagnesium, sheagilmagnesium, zohexyl madanesicum, V-decylmagnesium, Examples include ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, arylmagnesium chloride, butyletho, shimadanesium, ethylbutylmagnesium, and butylmagnesium high Fride. These magnesium compounds can be used in the form of a complex compound with, for example, an organic alkali, and may be in a liquid state or a solid state. On the other hand, magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride 1.4 nogropoxymagnesium chloride, butoxy Alkoxymagnesium halides such as magnesium chloride, octoxymagnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, tortoise-octoxymagnesium, 2-ethylhexo Examples include alkoxymagnesiums such as medium magnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium calcarnates such as magnesium lauric eII and magnesium stearate. Furthermore, these magnesium compounds without reducing ability may be derived from the above-mentioned magnesium compounds having reducing ability, or may be derived at the time of preparing the beak of the catalyst component. For example, by contacting a magnesium compound with a reducing ability with a polysiloxane compound, a silane compound containing halodane, a halodane-containing ram compound, an ester, or an alcoholic compound, it is converted into a magnesium compound that does not have a reducing ability. There are several methods. Further, the magnesium compound may be a complex compound with other metal compounds, a composite compound, or a mixture with other metal compounds. Furthermore, these compounds
゛It may be a mixture of eight or more types. Among these, the preferred magnesium compound is a compound that does not have reducing ability, and preferably contains % of magnesium! Danesium compounds,
Specifically, magnesium chloride, alkoxymagnesium chloride, and pentaallyloxymadanesium chloride.

In the present invention, there are various titanium compounds used for preparing the solid titanium catalyst component [A], but usually Ti(
OR>, X4-, (R is a hydrocarbon group,
A tetravalent titanium compound represented by O≦σ≦4 is suitable. More specifically, TiC1, TiBr4, Til
, etc.: Ti (OC
Hl) C1,, T i (QC, H,) C11, T
i (Q 5-C4H,) C1,, T i (QC
lHl) Br, .

Trihanated fluco-initiated titanium such as T i (O4aoc, Il,) By, T((OCH,), C1
iTi(QC.

H@>@CliTi (Os-C4H,) , C1,,
Ti (QC.

R5) ■Dihalodanated alkoxytitanium such as By:
Ti (OCH,), C1%Ti (QC, Hl), C
1, Ti(0%-Ci'fe)sCj,T ((QC,
Monohalodanated trialkoxytitanium such as H,), Br: Ti(OCRl),,Ti(QC,H,))
4, T・-(θ%-〇4H6)4 etc.
Basket, a8.゛゛Among these, preferred are heron-containing titanium compounds,
In particular, titanium tetrahalide is preferable, and titanium tetrachloride is preferable.These titanium compounds may be used alone or in the form of a mixture. It may be used after being diluted with hydrogen or the like.

In the preparation of the titanium catalyst component (A), the titanium compound, the magnesium compound and the substances to be supported (b)), (6), (
#) A well-selected electron donor, as well as other reaction reagents that may be used as required, such as alcohol,
The amount of other electron donors such as phenol, monocarboxylic acid ester, silicon compound, aluminum compound, etc. to be used varies depending on the preparation method and cannot be unconditionally specified, but for example, the amount of electron donor to be supported per mol of magnesium compound. Approximately aos1 to approximately s basket, titanium compound approximately αo
z or about 600 moles 4! ! It can be a percentage of degrees.

In the present invention, a combination catalyst of one or more of the titanium catalyst components (A), an organoaluminum compound catalyst component (B), and an organosilicon compound catalyst component or sterically hindered adenoid catalyst component <C> described later is used to produce an olefin. polymerization or combination of
- Perform the matching.

The above CE) component is Ii, (1) an organoaluminum compound 1 having at least one At-p elementary bond in the molecule, for example, the general formula % (where R1 and R8 are carbon atoms, usually 1 to 15
The hydrocarbon groups preferably contain 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halo 3. q is o<q<
s, and 10% + f) + q = 3)
An organoaluminum compound represented by

(ii) Complex alkylated products of Group 1 metals and Al 1=um represented by the general formula M"AIB"4 (where Ml is Li, Nα, Ni, and Ri is the same as above), etc. be able to.

Examples of the organoaluminum compounds belonging to the above (1) include the following. General formula % Formula % (ζHere, R1 and R8 are the same as above. 禦 is preferably 1
The number jll is 3. ), general formula R",, Al-5 (and 81 is the same as above.
.

(Here, R'' is the same as above, and the sacrifice is preferably 2, 3
It is. ), general formula % formula %) (where R1 and R1 are the same as above, X is halo-perforated, +
Examples include those expressed as s+g''s).

Among the Al 1=ium compounds belonging to (1), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminium.

trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, diptylaluminum butoxide, alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide; -R number s
Partially alkoxylated alkylaluminum halides, such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminium pro-do, partially alkoxylated alkylaluminum halides having an average composition represented by A'(07?'')e s, etc. Ethylaluminum sesquicluride, butylaluminum sesquicluride,
Alkylaluminum sesquihalides such as ethylaluminum sesquipromide.

Partial 11C such as alkylaloonium V halides such as ethylaluminum dichloride, glopylaruminium cyclolide, butylaluminum dichloride, etc.
Partially hydrogenated alkylaluminum dihydrides such as dialkylaluminum dihydride, ethylaluminum dihydride, detetrabylaluminum dihydride, etc. Alkylaluminum, partially alkoxylated and halodanated nine-alkylaluminum, such as ethylaluminum ethoxy chloride, f-thylaluminum butoxychloride, ethylaluminum dimethoxyprod.

Compounds belonging to the above (11) include LtAl (
C,B,),.

Examples include LtAl (C, Bj, )4.

Further, as a compound similar to (1), an organic alkinium compound in which two or more Al 1=um are bonded via an oxygen atom or a nitrogen atom may be used. As such compounds,
For example, (C,H,), ALOAI (C,isu, , (C
,Ii,),Al0AI(C,Ii@),,('*”s
)t”NAj (C*Bs)tC,E.

Examples include:

Among these, it is particularly preferable to use trialkylaluminum and the above-mentioned alkyl aluminum in which two or more aluminums are combined.

5i-0-C or 5t-N- used in the present invention
The organosilicon compound catalyst component (C) having a C bond is 1, for example, an alkoxysilane, an aryloxysilane (a deci 11 ν8 (yellow → etc.). For example, 1 formula R% Nut (OR") ,-, (where O<s(3,R1
1i Hydrocarbon groups, such as alkyl groups.

Cycloalkyl group, aryl group, alkenyl group.

haloalkyl group, aminoalkyl group, etc.
, R1 is a hydrocarbon group 1 such as an alkyl group.

SchifzonoAlkyl group, aryl group, alkenyl group.

Al; xyalkyl group, etc., provided that % R1 (4-substance)
OE" groups may be the same or different.

Further, other examples include sitexanes having an OR1 group, silyl esters of carganic acid, and the like.

In addition, as another example, a compound that does not have a 5t-oc bond and a compound that has a 5 O-G bond are reacted in advance,
Alternatively, react at the polymerization site.

Examples of such compounds, which may be converted into compounds having Si-0-C bonds, include SiO-C silicon hydride, alkoxy group-containing aluminum compounds, alkoxy group-containing magnesium compounds, and other metal alcoholades. Examples include combination use with alcohol, formic acid ester, and ethylene oxide. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.).

Specifically, trimethylmethoxysilane, trimethylethoxysilane, somethyldumethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, ethyltrimethoxysilane, methoxytrimethoxysilane, etc.・'1 Nyltrimethoxysilane, phenyltrimethoxysilane% r-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane.

r-Aonoprobyltriethoxysilane, cooltriethoxysilane, ethyltriisode! 2-poxysilane, vinyltriptoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane.

Examples include methyltriaryloxy(allylosv)silane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and phenylshedoxydiethylaminosilane. Particularly preferred among these are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane.

Vinyltriethoxysilane, phenyltriethyl)-If'
Disilane, Zeltritoxysilane, Ethyl silicate,
The above formula R, S of diphenylzonotoxysilane, diphenyljethoxysilane, methylphenylmethoxysilane cape
t (OR1), .

Component <C> can also be used in the form of an adduct with other compounds.

In addition, as an example of the three-dimensional camp Akin catalyst component, [in the formula, R
R is a swollen hydrogen group, preferably a monovalent or unsubstituted alkylene group, and preferably the monoalkylene group is an alkylene group having 2 or 3 rotation primes. In the case of a substituted alkylene group, the substituent is, for example, a swollen hydrogen group, such as an alkyl group, an acyloxy group, an alkoxyl group, and the like. R”
, R4, R1.

RR is hydrogen or a hydrocarbon group which may have a substituent, at least one of Rh and 84 and at least one of RI and R is a hydrocarbon group, and R
8 and R4 or B RI and RI are connected to each other to form llI.

For example, all of FiR"*R'%"11" may form a carbocyclic ring or a heterocyclic ring, and preferably all of them are hydrocarbon groups. Ra and R4 and iJ RI and RI
When one of these is hydrogen, the other is preferably a secondary or tertiary hydrocarbon group. ", R"n, a hydrocarbon which may have an It substituent, R... and R... or R18 and R
14 may be connected to each other to form a column, and
Either R1 and R11 and either R''a and R14 may be connected to form a product. R11 is hydrogen or a hydrocarbon group, ] A substituted methylenecyamine compound having a skeleton represented by It is.

Specifically, N as the complex decay compound has the general formula [In the formula, E@, ``sR'', and k'' are the same as above.

R1 is hydrogen or expanded hydrocarbon & gold! 4, alkyl metal,
i substituent such as, R1@ is hydrogen, hydrocarbon group 1 such as alkyl group, acyloxy group, alkoxyl group E, O<%
<&.

O<2, and S and R10 are the same and 4
They may be different. Examples include compounds having the following skeleton.

At(C,)J-).

Examples include 2,6-substituted piperidines such as and 2,5-11i substituted pyrrolidines such as.

In addition, the above-mentioned I#-converted methylene diamine adducts include, specifically, N,N,Nl,Nl-tetramethylmethylenediamine, N,N,)Jl,Nl-tetraethylmethylenediamine, 1,3-dibenzyl imidazolidine, 1,3
-dibenzyl-2-phenylimidazolidine and the like can be exemplified.

Oa-: tyyne, such as l-butene, l-pentene, l-hexene, l-octene, l-decene.

1-dodecene, l-tetradecene, l-octadecene,
Random copolymerization with 4-methyl-1-pentene, a mixture thereof, etc. is carried out, and the propylene content is 40 to 90%.
In molar terms, tL< is 5 to 88 molar crystallinity (X
A random copolymer having a weight of less than 40 times 1 ILs (according to IJ), preferably Fio to 35 times 1 ILs, is produced. # Ethylene may be allowed to coexist in a small amount in the copolymer, but if the ethylene content in the copolymer is 6.
It should be kept below Moru.

In addition, a preferable random copolymer is 135[
, the limiting viscosity of 1 measured in decalin is 0.5 to 6.0 dllf, especially 1.0 to 5° dllf.
It is in the range of tuna. The melting point based on DSC (differential scanning calorimetry) is preferably 1j135r or less.

Especially below 130tll'. In addition, the amount of boiling soybean insoluble in butane &01 is less than 1, and the soluble portion of boiling methyl acetate is 2
01% or less is preferred.

Rounding to obtain random copolymers with such properties is as follows:
It is preferable to adopt a method of continuous copolymerization in which propylene and a di-olefin having a carbon number of 4 or more are fed into the polymerization system at regular intervals, but of course batch or semi-continuous copolymerization methods can also be adopted. . The propylene content ratio, crystallinity, etc.
The propylene supply ratio is adjusted depending on the uniformity of polymerization, etc. The above intrinsic viscosity is 1 molecular weight regulator.

For example, it can be arbitrarily adjusted by changing the amount of hydrogen used.

The polymerization can be carried out in the liquid phase or in the gas phase, but it is preferred to carry out the polymerization in the liquid phase. When carrying out liquid phase polymerization, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, or the olefin itself may be used as the reaction medium. The use of catalyst 11 requires a reaction volume of 1 t"i,
(A) component is approximately 1.0 mmol in terms of gold titanium atoms, and (B) component is approximately 1.0 mmol in terms of gold titanium atoms, and (B) component is approximately 1.0 mmol in terms of gold titanium atoms. About 1 to about 2,000 moles, preferably about 5 to about 500 moles, and the <C> component is equal to 1 mole of metal atom in component (B), Si atom or N in component (C). About α001 to about 10 moles of atoms.

Preferably about 0. It is preferred that the amount is from about 2 mol of Ol to about 2 mol, particularly preferably from about 0.05 to about 1 mol.

These catalyst components (A), (B), and (C) may be brought into contact with each other during the first reaction, or may be brought into contact with each other before polymerization. In this contact before polymerization, only Vi and any of the two components may be freely selected and brought into contact with each other, or some of the three components may be brought into contact with each other. Matashun 1%
The contact between the respective fractions of @4V may be carried out under an inert gas atmosphere or an olefin atmosphere.

The supply ratio of propylene and α-olefin having 4 or more carbon atoms depends on the composition of the desired random copolymer and the 1-coating conditions.
For example, the propylene/α-olefin (molar ratio) is generally 85/
It is in the range of about 15 to 10/90.

The olefin copolymerization temperature is preferably about 20 to about 200C, more preferably about 50 to about 180C, and the pressure is from normal pressure to about 100 kg/-1, preferably about 2
It is preferable to carry out under pressurized conditions of about 50 kg/cdl to about 50 kg/cdl. Furthermore, it is also possible to divide one batch into two or more stages with different reaction conditions.

According to the present invention, since the catalytic activity is high and the activity decreases little with the passage of polymerization time, the number of co-monomers per unit catalyst can be made very high. Moreover, the uniformity of the obtained copolymer is excellent.

In addition, since the content of low molecular weight by-products is very low, when formed into a film, etc., it has good transparency, hardly any stickiness is observed, and the film has little odor. Furthermore, high heat seal strength can be obtained even when the film is subjected to corona treatment or left under high temperature conditions.

The random copolymer obtained in the present invention can be used for film,
It is also particularly useful as a modifier for thermoplastic resins such as polypropylene.

Next, it will be explained in detail using examples.

Example 11 (Catalyst synthesis) After sufficiently exchanging N and rW in an autoclave with an internal volume of 3 tons, 1.5 tons of refined kerosene, commercially available MOCL, and 75 F were added.

Add 10 f of ethanol lo st oyohiemazole ago (manufactured by Kao Atlas Co., Ltd., sorbitan du stearate), raise the temperature of the system with stirring, and heat it at 125 tZ' for 600 dp? The mixture was stirred at FL for 20 minutes. The system internal pressure is N.

svs with an inner diameter of 3#III, which was directly connected to an autoclave and kept warm at 125tZ'.
The cock of the manufactured tube was opened, and the liquid was transferred to a 5 t glass flask (equipped with a stirrer) filled with 3 t of refined kerosene that had been cooled in advance to -15C. The amount of liquid transferred was 1 t, and the required time was about 20 seconds. The produced solid was collected by filtration and thoroughly washed with hexane. Microscopic observation revealed that the particles had a true spherical shape and the particle size was 5 to 30 microns.

Put TiC1 and L51 into a 3t glass flask.

The above solid suspended in 150ml of refined kerosene? After adding 5ff at 20C with stirring, diisobutyl phthalate 1'L9
- was added to raise the temperature of the braided yarn to 120C. After stirring for 1 hour,
& Stirring was stopped, the supernatant was removed by decantation, 7°icl of 151 was newly added, and the mixture was stirred at 130C for 2 hours. heat? The solid portion collected by filtration was sufficiently purified with hot kerosene and hexane to obtain a titanium composite. The complex contains 2.3 wt% Ti, 610 wt% Cl,
M (J20.0wt% and diisobutyl phthalate 9.9
Including wt%.

(Polymerization) An autoclave with a capacity of 17 tons was fully replaced with propylene. 50 moles of propylene, 33 moles of 1-butene, hydrogen? A7t was introduced into the system. Triethyl aluminum 3
millimoles, 0.3 mmoles of diphenyldimethoxysilane is converted to T (0.03 milligrams in terms of atoms - 7 atoms)
It was added at 0C and stirred for 1 hour. After 1 hour, a small amount of methanol was added to the system to obtain a depressurized offshore body.

One combined yield was 912f. According to the analysis, the content of delobyrene 1 is 87.2 mol%, and the melting point according to DECWC is 1.
2!6tll', 1!30C measured melting index is &8t/1
The odor level of the polymer was A according to the sensory test. In addition, a sheet with a thickness of 1+g+s+ made of this copolymer according to JIS K6758 is 80C1!4.
After aging for 1 hour, the surface appeared tacky, but there was no tackiness.

Odor direct A: No odor B: Almost no odor C: Slight odor D: Smell E: Strong odor Examples 2 to 5 In Example 1, the amount of propylene/1-butene added, the polymerization temperature, Table 4 shows the results obtained by changing the type and amount of organometallic compound, type of electron donor, and t during polymerization.

Example 6 (Catalyst synthesis) 210 mmol of commercially available magnesium chloride, 30 mmol of titanium tetrachloride, and 30 mmol of diethyl 2-allylmalonate were added to a stainless steel (S) with a diameter of 15 am in a nitrogen atmosphere.
Internal volume 8 that accommodates the UE-32) made by Lure 2.8Ti4
00-1 Stainless steel fi with inner diameter of 100cm! R to US
- Charged into a ball mill container made of 32mm, and the impact acceleration was 7G.
Leave in contact for 24 hours.

Obtained pulverized product 1Ott-, ethylene dichloride 1
oo- and stirred for 2 hours at 8(I').

The solid portion was collected by filtration. The solid material was analyzed to contain 1.8% by weight of titanium, 31% by weight of chlorine, magnesium goift*, and 227% by weight of ethyl 2-allylmalonate.
Add 100 d of one sample into a 200-ml flask.

Triethylaluminum 6 with sufficient element substitution in the system
0 mmol, phenyltriethoxysilane 30 mmol, and the above Ti catalyst component converted into Ti atoms, tsW
9 Add one atom. After stirring at 20C for 2 hours, the solid portion was washed with sufficiently purified bexane. The solid part is titanium 1
．． 6m-%, chlorine 5aO@lli, magnesium 1
8.0 mass, aluminum α81 dispersion and silicon 2
Includes 5″M quantity.

(Polymerization) In actual mflJ1, propylene and 1-hexene were substituted for propylene and l-butene, and their amounts were changed to 43 mol and 43 mol, respectively. I did it.

Examples 7 and 8.9 (Catalyst synthesis) In the catalyst synthesis of Example 6, 30 mmol of diethyl 2-allylmalonate was added to 30 mmol of zon-n-butyl maleate, respectively.
Millimoles, isobutyl piperate 41! Catalyst synthesis was carried out in the same manner except that 30 molar and 30 molar of zoethyl 1,2-cyclohexanecarboxylate were used.

(Polymerization) Under the conditions shown in Table 1, propylene/l-butene copolymerization was performed in the same manner as in Example 1.

Example 10 (Catalyst synthesis) Commercially available 9-ditylmagnesium chloride 0.1 mol (n
11 mol of tetraethoxysilane α was added dropwise to (butyl ether solvent) under a nitrogen atmosphere at room temperature.

The mixture was stirred at 60C for 1 hour. The produced solid was collected by filtration and thoroughly washed with hexane.

The solid was suspended in 30 g of kerosene and 0.0 g of diethyl phthalate.
015 mol was added dropwise and treated at 80C for 1 hour. Further T
After adding iC1,200- and treating at 120C for 2 hours, the supernatant was removed by decantation, and Ti
C1,200ydf was added and treated at 120t:' for 1 hour. The resulting solid was filtered hot and washed thoroughly with thermodecane and hexane. The Ti catalyst component is Ti in terms of atoms.
2.21 sanchi, C1610 heavy rice cake%, Mg21. Oi amount%
, contains 14.9 ditones of diethyl phthalate.

(N-polymerization) Polymerization was carried out using the Ti catalyst component described above in the polymerization of Example 1, by adding ethylene at a rate of 24) Jt/h for 1 hour. Polymer yield is 986t%MI! I
f/10', propylev content d8N8 mole, ethylene content L8 mole%, 1-butene content 114 mole. The melting point was 123C1 and the crystallinity was 2'lTo. There was no tackiness of the press sheet, and there was no odor of the polymer.

Example 11 (Catalyst synthesis) Commercially available magnesium chloride 9N3F, %-decane 4g8s
d and 2-ethylhexanol 464.5d to 130
A heating reaction was carried out at C for 2 hours to form a homogeneous solution, phthalic anhydride! Add 22t. This homogeneous solution was maintained at -20C and added dropwise to 4 tons of titanium 94 chloride with stirring over 20 minutes, and further stirred at -20C for 1 hour. After that, the temperature was gradually increased to 120t:', and then 975 octyl phthalate was added.
f was added and stirred at 120C for 2 hours. Collect the solid part by p-filtration, suspend it again in 4t of TiCl,
After stirring at 120 C for 2 hours, the solid material was collected by F yti' and thoroughly washed with purified hexane until no free titanium compounds were detected during the washing.

The titanium catalyst component contains Ti2. O heavy [t
s, C164.3% by weight, Mg22.011%, and dioctyl phthalate 11.05% by weight.

(1 cup) Add 100 d of fully purified bexane into a 200-ml flask. After the gold in the system was sufficiently replaced with nitrogen, 60 mmoles of diethyl aluminum chloride and 30 mmoles of 2,6.6-titramethylpiperidine and 15 wg of the above catalyst catalyst were added in terms of Ti atoms (15 wg). 2G
[After stirring for 2 hours, the solid portion was washed with sufficiently purified hexane. The solid part is made of titanium T8 heavy aS. Salt 157.0
Weight 1i196, Magnesilla A I '1.01kk%.
) p-yoctyl α8% by weight. 2.2.6.6-
Contains tetramethylbiperidine 1 & 5 wt.

(1i [combination] Triethylaluminum 1.5 μIJ under the conditions of Example 1)
Polymerization was carried out by adding only molar amount without adding any electron donor. The polymer resonance is 1100f, melt finger fi! 6, propylene-containing 1i87.6 mol%. The crystallinity was 31% and the melting point was 1s19C. The odor level of the M combination was A, and the press sheet had no stickiness.

Example 12
A copolymerization reaction of propylene and 1-butene was continuously carried out using a polymerization vessel (made of stainless steel) equipped with a stirrer.

Hexane Z5t7m is continuously supplied, and the polymerization liquid is continuously discharged so that the liquid volume in the combiner becomes Z5t. Ti catalyst component (from Example 1) α065 mmol/l.
) ethylaluminum & 25 mmol/l, diphenyldimethoxysilane 0. They were continuously fed into the polymerization vessel at a concentration of 325 mmol/l. Propyref 388Nt/Hr. 1-butene 31TN
It was added at a ratio of t/Hr, and polymerization was carried out at 70C. The discharged polymerization liquid was poured into a large volume of methanol to recover the polymer.

Propylene/l-butene copolymer was obtained at a rate of 172 f/hr. According to analysis, propylene/l-butene copolymer contains propylene @'I Z4molti, M I2
0. 6. The melting point was 110. Furthermore, the press sheet had no stickiness, and the odor level of the single unit was A. After applying a phenolic stabilizer to the polymer, it was formed into a 7°-cut cast film (50 μm thick). (Film forming machine: manufactured by Thermoglastic). Layer two films together.

85tl'. 90U. 100C%ll0C temperature, 2K
After heat sealing with a sealer width of 5 m for 1 second at a pressure of f/cd, it was allowed to cool. A test piece with a width of 15aI was cut from this sample, and the crosshead speed was 200μ/mis.
Table 2 shows the results of measuring the strength when the heat-sealed portion was peeled off. In addition, after the film was left at 40C for 2 weeks, it was heat-sealed using the method described above and the peel strength was measured.The results are shown in Table 2.

Table 2 (f/15gm) 85t:' 420
-90 1020 120100
1140 1020110 1
1! ! ! 0 1460 From the results in this table, it can be seen that even after the film has been left for a long time, sufficient strength can be obtained even if it is heat-sealed at a relatively low temperature.

Claims (1)

[Scope of Claims] (A) A positively active titanium catalyst component containing magnesium, titanium, halogen, and an atom donor as essential components,
The electron donor is (α) an ester of a multipotent compound selected from the group consisting of polyvalent carboxylic acids, polyvalent hydroxy compounds, and hydroxy-7-substituted carboxylic acids; (6) RC
A monocarboxylic ester represented by Q O7 <', in which at least one of the hydrocarbon groups R and R1 is a branched or monocarboxylic group, and (C) a carbonate ester. A titanium catalyst component consisting of an ester selected from the group consisting of (#) an aluminized annular catalyst component and (C) a 5i-0-C bond or a 5i-N-C bond.
In the presence of a catalyst formed from an M organic silicon compound solvent component or a sterically harmful amine catalyst component having Propylene nominally ¥40 to 90 molti, crystallized [
A method for producing a random coelectric compound of nolopyrene having a metal alloy of 40 mm and less than 1 sr.