CN1418895A - Solid catalyst composition and making method thereof for polymerizing propene - Google Patents

Abstract

The solid catalyst component for propylene polymerization contains magnesium compound, titanium compound, halogen compound and first electron-donating compound as necessary component. The component of said solid catalyst can be prepared by using the following stepsa: forming the solid catalyst component using magnesium compound, titanium compound, halide compound and first electron-donating component as necessary component for polymerization, the mole ratio of the carried first electron-donating compound (D) and titanium is (D/T); then the solid catalyst component of polymerization can be treated, and improved to make the above-mentioned mole ratio (D/T)i into (D/T)m, in which (D/T)m/(D/T)i is greater than I.

Description

Propylene polymerization solid catalyst component and method for making thereof

It is good and be applicable to acrylic polymer and method for making and composition and the polymerization catalyst component and the method for making thereof of automobile, household electrical appliances, wrapping material to the present invention relates to rerum naturas such as rigidity, surface hardness, thermotolerance, water vapor shielding.

Acrylic polymer is general relatively more cheap, and, utilization is as the transparency, the physical strength of its feature, character such as thermotolerance, surface gloss, resistance to chemical reagents, oil-proofness, rigidity, the bent fatigability of resistance can be widely used in the fields such as Industrial materials, packaging material for food, toiletry bag package material, drug material.

Acrylic polymer, as mentioned above, utilize its rigidity, anti-in characteristics such as hitting property, and be widely used in each industry such as automobile, household electrical appliances, groceries.Recently, in order to alleviate the weight of finished product, or reduce cost, or for the thin-walled property of finished product with prevent the surface tear of finished product, studying and how to improve its surface hardness.Just requiring acrylic polymer is high rigidity, high surface hardness, and have good anti-in hitting property.In addition, also more and more higher to the requirement of its rerum natura, processibility, particularly urgent hope can keep rigidity and intensity when high temperature, and can improve the formability of its weather resistance and big part finished product.

In the past, for the high rigidization of acrylic polymer and the improvement of the transparency, following known method has been used in the improvement of surface luster, promptly uses the salt (for example Sodium Benzoate) of monocarboxylic Ia and IIa family metal, di-carboxylic acid (hexanodioic acid), the salt of the III-IV family metal of aliphatic dicarboxylic acid (for example hexanodioic acid aluminium), the dibenzylidene sorbitol derivative, weighting agent classes such as talcum are as method (the special public clear 39-1809 communique of nucleating agent, the spy opens clear 60-139731 communique etc.) and (spy opens clear 56-2307 communique to widen the method for acrylic polymer molecular weight distribution, the spy opens clear 59-172507 communique, the spy opens clear 62-195007 communique etc.).

When using these nucleating agents,, can't say according to different purposes to have reached well-content effect though above-mentioned rerum natura improvement effect is arranged.

Therefore, wish to have physical strength such as a kind of shock-resistance, rigidity and surface hardness, excellent heat resistance, be suitable for the acrylic polymer of automobile, household electrical appliances, wrapping material, and by reducing weighting agent such as talcum etc., reach and reduce finished product density, and make the purpose of finished product thin-walled property.

In addition, stereoregularity (isotaxy regularity) by improving acrylic polymer, widen molecular weight distribution, improve the intensity that depends on high molecular weight components, weather resistance and also carrying out hardy in the research that improves aspect the formabilities such as extrusion moulding and slush molding.

Wherein, the exploitation that particularly demonstrates the catalyzer of high reactivity and high stereoregularity is being studied in recent years with might and main.The catalyzer that discloses, all be to contain magnesium, titanium, halogen and give the electronics compound be must composition solid catalyst with, by organoaluminum, the catalyzer of forming for the electronics compound is for example opened clear 57-63310 the spy, the spy opens clear 58-32604, the spy opens clear 58-83006, the spy opens clear 59-206408, the spy opens clear 59-219311, the spy opens clear 60-130607, the spy opens clear 61-209207, the spy opens clear 61-211309, the spy opens clear 62-72702, the spy opens clear 62-104811, the spy opens clear 62-11705, the spy opens clear 63-199703, the spy opens clear 63-264609, Te Kaiping 1-126306, Te Kaiping 1-311106, Te Kaiping 3-62805, Te Kaiping 3-70710, Te Kaiping 4-103604, Te Kaiping 4-114009, disclosed content on the Te Kaiping 4-202505 communique.

In addition, present inventors open flat 4-43407, spy the spy recently and open flat 4-149217, spy and open flat 4-178406, spy and open flat 4-180903, spy and open flat 4-185613, spy and open flat 4-198202, spy and open that flat 4-198204, spy open flat 5-9209, the spy opens on each number communiques such as flat 5-287019 and also discloses associated viscera.

Be disclosed in these known diplomatic acrylic polymers, the insoluble part of wherein using xylene extraction is used less than 99% ¹³The C nuclear magnetic resonance spectrum (is designated hereinafter simply as ¹³C-NMR) isotactic five modular constructions (Pentad) ratios (mmmm) of the polyacrylic methyl of Ce Dinging, the highest reaching only about 93-98%, so, be limited to the raising of all rerum naturas such as its rigidity, thermotolerance.

The objective of the invention is to, do not damage the original characteristic that has of acrylic polymer, provide rigidity, surface hardness, thermotolerance, the transparency, surface luster, water vapor shielding etc. good, be applicable to catalyst component and its method for making that its method for makings of acrylic polymer of automobile, household electrical appliances, wrapping material and composition and polymerization are used.

Present inventors study for various methodologies in order to solve above-mentioned problem, and the result finds that the acrylic polymer with following character can solve above-mentioned problem, thereby finished the present invention.Promptly the insoluble part of (1) xylene extraction (XI) is more than 99.0% (weight), and (2) are used ¹³The C nuclear-magnetism isotactic five modular construction ratios (IP) that spectrum measures that shake are more than 98.0%, (3) isotactic mean chain length (N) is more than 500, and the insoluble part of (4) p-Xylol is separated with the post partition method and the mean chain length (Nf) of each cut of obtaining accounts for more than 10% all (weight) in the total amount of the cut more than 800.

Below specify the feature of acrylic polymer of the present invention.

(1) be the weight percentage that is insoluble to the polymkeric substance of dimethylbenzene 25 ℃ the time with the insoluble part (XI) of xylene extraction.In detail, be 135 ℃ all be dissolved in o-Xylol after, in the weight percentage of 25 ℃ of polymkeric substance of being separated out down.The XI of acrylic polymer of the present invention is more than 99.0%, preferably more than 99.5%, more preferably more than 99.7%.XI does not reach at 99.0% o'clock, then can not satisfy desired rigidity, thermotolerance, surface hardness, surface luster, the transparency, water vapor shielding etc.

(2) use ¹³Isotactic five modular construction ratios (being designated hereinafter simply as IP) in the polypropylene molecular chain of C nuclear magnetic resonance spectroscopy are according to A.Zambelli, Macromolecules.6, and 925 (1973) method is carried out.That is to say the nuclear magnetic resonance spectrum that uses isotropic substance carbon ( ¹³C-NMR), in determined propylene system polymer molecular chain with the isotactic ratio of five modular construction unit representations.Moreover IP of the present invention is the mensuration position of the polypropylene that obtains by polymerization itself, rather than is carrying out above-mentioned xylene extraction, the polyacrylic measured value after the operation such as other extractions, separation.

The affirmation at peak is according at Macromole cules, and the correction of the above-mentioned documents of record is used in 8,687 (1975) ¹³In the C-NMR spectrum, the volume efficiency at the mmmm peak in the hypersorption peak in methyl carbon field is measured IP's.

IP in the acrylic polymer of Ce Dinging must when lower than this value, then not reach character such as desired rigidity, thermotolerance, surface hardness, surface luster, the transparency, water vapor shielding more than 98.0% like this.IP in the preferred acrylic polymer is more than 98.5%.Particularly preferably be IP and be the acrylic polymer more than 99.0%.

(3) isotactic mean chain length (N) is meant the isotactic mean chain length of the methyl in the polypropylene molecule, according to method of reporting (the PolymerSequence Distribution of J.C.Randall institute, Academic Press, New, York, 1977, Chapter2) come out for basic calculation.

Concrete is that polypropylene is amplified 1,2, in the mixed flux of 4-trichlorobenzene/biphenyl, is warmed to 130 ℃, makes it dissolving, 10% (weight) that reaches up to polymer concentration.

This solution is joined in the glass test tube that internal diameter is 10mm, under the condition determination identical, measure with above-mentioned isotactic five modular construction ratios (IP) ¹³C-NMR.

According to, Shan-Nong ZHU, Xiao-Zhen YANG, RiichiroCHUJO; Polymer Journal, vol.15, two position models of record definition among the NO.12, P859-868 (1983), the active site when promptly supposing polymerization has two kinds, and wherein a kind is called the catalyzer controlled polymerization, and a kind is called terminal controlled polymerization in addition.(about catalyzer controlled polymerization and terminal controlled polymerization, pure two high molecular essence and the outlines of being shown 2 in ancient river, " Polymer Synthesizing " P73, (strain) chemistry is with in people's distribution (1986) book detailed argumentation being arranged.)

Two position models can be put in order out,

α: D body and the probability of L body of catalyzer controlled polymerization (enantiomorphism change process) addition on the polymerization end, be the index of random degree in the isotactic composition,

σ: terminal controlled polymerization (bernoulli process) can addition and the probability of the terminal identical mesomeride of polymerization,

ω: the ratio of alpha position

Homo-polypropylene splits into 10 peaks according to the stereoregularity of methyl in five modular construction units, consistent with computed strength (area) in order to make the practical measurement value, obtains c with method of least squares, σ, and ω, and obtain each five modular construction with following formula

The amount A of unit ₁-A ₁₀

Mesomeride	??A 1?＝mmmm＝ω(1-5β+5β 2)+(1-ω)σ 4??A 2?＝mmmr＝ω(2β-6β 2)+2(1-ω)σ 3(1-σ) ??A 3?＝rmmr＝ωβ 2+(1-ω)σ 2(1-σ) 2
		The racemize structure	??A 4?＝mmrr＝ω(2β-6β 2)+2(1-ω)σ 2(1-σ) 2??A 5?＝mmrm＝2ωβ 2+2(1-ω)σ 3(1-σ) ??A 5?＝rmrr＝2ωβ 2+2(1-ω)σ(1-σ) 3??A 7?＝rmrm＝2ωβ 2+2(1-ω)σ 2(1-σ) 2
??A 3?＝rrrr＝ωβ 2+2(1-ω)(1-σ) 4??A 3?＝mrrr＝2ωβ 2+2(1-ω)σ(1-σ) 3??A 10＝mrrm＝ω(β-3β 2)+(1-ω)σ 2(1-σ) 2

*?β＝α(1-α)

Then, according to the definition of the mean chain length of putting down in writing on the above-mentioned J.C.Randall document (N)

The unit number of the chain number/mesomeride of N=mesomeride

With the above-mentioned A that obtains ₁-A ₇Each five modular construction unit substitution the time, use $N=\frac{A_1+A_2+A_3+0.5(A_4+A_5+A_6+A_7)}{0.5(A_4+A_5+A_6+A_7)}$ Can obtain the N value.

Moreover the N value among the present invention is the measured value of the polypropylene that obtains by polymerization itself, rather than carried out above-mentioned xylene extraction, other extractions, the polyacrylic measured value after separating.The N of the acrylic polymer of tool height stereoregularity of the present invention is more than 500, preferably more than 700, most preferably more than 800.The N value is last by 500 o'clock, then the rigidity that can not obtain wishing, thermotolerance.

As two, polyacrylic ¹³The C-NMR signal can be expressed 3 main peaks of methylene radical, methyne, methyl.

Wherein, when enlarging the peak in methyl field, can obtain data, be as can be seen as Fig. 1 ... mmmmrmmmm ... ... mmmmmmrrmmmmm ... form etc. irregular key.

Can think that relation reciprocal is arranged between the quantity of isotactic mean chain length of possible crystalline and irregular key.

The quantity of irregular key is many more, and the racemize structure that just cuts into the mmmm structure is many more, and then mean chain length (N) shortens.

The mean chain length of obtaining like this (N) is the above-mentioned length that can crystalline isotactic structure sequence of expression, thus can think this length long more (just irregular key is few more), then can improve the rerum naturas such as rigidity, thermotolerance, water vapor shielding of acrylic polymer more.

(4) mean chain length (Nf) of each cut that obtains with the post partition method of the insoluble part of so-called dimethylbenzene is meant that the polypropylene of the insoluble part of xylene extraction that will obtain in (1) is dissolved in right-dimethylbenzene under 130 ℃, add diatomite, drop to 30 ℃ with 10 ℃/hour rate of temperature fall, make it to be adsorbed on the diatomite, this diatomite is filled in the post, begin to heat up with each 2.5 ℃ speed from 70 ℃ of temperature to 130 ℃, separate each cut respectively, obtain the mean chain length (N) of each isolated each cut with above-mentioned method, with these mean chain lengths (Nf) as each cut.

In acrylic polymer of the present invention, so the mean chain length (Nf) of isolated each cut is that the total of the cut more than 800 accounts for 10% all (weight) when above, this polymkeric substance preferably accounts for more than 30% (weight) for well, particularly preferably is to account for more than 50% (weight).

The total of the cut of mean chain length (Nf) more than 800 accounts for 10% all (weight) when following, then rigidity, surface hardness, thermotolerance, water vapor shielding to improve effect bad.

Acrylic polymer manufacture method of the present invention below is described.

Propylene of the present invention is that polymerization is to make by using the polymerizing catalyst that is made of following component to carry out propylene polymerization, promptly (A) gives the electronics compound as the neccessary composition in the polymerization solid catalyst composition with magnesium compound, titanium compound, halogen contained compound and the 1st kind, and carries polymerization solid catalyst component, (B) organo-aluminium compound, (C) that the 1st kind of being held in the solid catalyst component should satisfy D/T 〉=1 for the mol ratio (D/T) of electronics compound/titanium atom content and give the electronics compound for the 2nd kind.

Here, can enumerate the magnesium halide of magnesium chloride, magnesium bromide, magnesium iodide class as magnesium compound; The alkoxyl magnesium of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, two phenoxy group magnesium classes; The carboxylate salt of Magnesium monolaurate, Magnesium Stearate, magnesium acetate class; The alkyl magnesium of dimethyl magnesium, magnesium ethide, butyl ethyl magnesium class etc.In addition, these various magnesium compounds can a kind use separately, also can use to mix more than 2 kinds and use.Preferably use magnesium halide, alkoxyl magnesium, perhaps when catalyzer forms, can form the material of magnesium halide.Particularly preferably being above-mentioned halogen is chlorine.

As titanium compound, can enumerate the halogenated titanium of titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tetra iodide class; The titan-alkoxide of tetramethoxy titanium, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxide, four phenoxide titanium classes; The titan-alkoxide halogenide of ethanolato-titanium muriate, titanium butoxide muriate, phenoxide titanium muriate, dibutoxy titanium dichloride, three titanium butoxide chloride-based etc.In addition, these titanium compounds can a kind use separately, also can more than 2 kinds and use.Preferably contain the quaternary titanium compound of halogen, particularly preferably be titanium tetrachloride.

Halogen in the halogen contained compound is fluorine, chlorine, bromine or iodine, chlorine preferably, and the particular compound that in fact exemplifies is the compound method that depends on catalyst component, but can list the halogenated titanium of titanium tetrachloride, titanium tetrabromide etc.; Silicon halide such as silicon tetrachloride, Silicon bromide; The Phosphorates phosphorus Halides of phosphorus trichloride, phosphorus pentachloride class etc., but, also can use halon, halogenic molecule, haloid acid according to the catalyst component preparation method.

Give the electronics compound as the 1st kind, generally can enumerate oxygenatedchemicals, nitrogenous compound, P contained compound, sulfocompound etc.Can enumerate as alcohols, ethers, ester class, acyl halide class, anhydrides etc. as oxygenatedchemicals.

Alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, 2-ethanol, oleyl alcohol, benzylalcohol, phenylethyl alcohol, phenol, cresols, ethylphenol, naphthols more particularly;

Ethers and two ethers such as methyl ether, ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran (THF), methyl-phenoxide, phenyl ether.

Vinyl acetic monomer, the monochloroacetic acid ethyl ester, ethyl propionate, ethyl butyrate, ethyl propenoate, butenoic acid ethyl, ethyl oleate, Stearic ethyl stearate, the phenyl vinyl acetic monomer, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, the toluic acid methyl esters, the toluic acid ethyl ester, the toluic acid propionic acid, the toluic acid butyl ester, the ethyl benzoate methyl esters, p-Methoxybenzoic acid methyl ester, ethyl anisate, ethoxy-benzoic acid methyl ester, the ethoxy benzonitrile acetoacetic ester, ethyl phenylacrylate, rutgers, diethyl phthalate, the phthalic acid dipropyl, the phthalic acid di-n-butyl, the phthalic acid diisobutyl ester, the phthalic acid dihexyl, dioctyl phthalate, gamma-butyrolactone, δ-Wu Neizhi, the ester class of NSC 11801 class;

The acyl chloride of Acetyl Chloride 98Min., Benzoyl chloride, toluyl chlorine, phthalyl chloride etc.;

Acid anhydrides such as maleic anhydride, phthalate anhydride.

In addition, can a kind use for the electronics compound individually, also can more than 2 kinds and use for these the 1st kind.Preferably the ester class particularly preferably is the phthalic acid ester class.

Certainly, magnesium compound, titanium compound, halogenide, the 1st kind give a compound in the electronics compound can be simultaneously in these 4 kinds of compounds more than 2 kinds.

The usage quantity of above-mentioned each composition, if in the present invention can efficiency confirmed fruit, its amount can be arbitrarily, but generally is preferably in the following scope.

The consumption of titanium compound, with respect to the usage quantity of magnesium compound, its mol ratio is preferably in the scope of 0.0001-1000, preferably in the 0.01-100 scope.In case of necessity, need to use halogen compounds, but when using halogen compounds, its usage quantity does not rely on and contains halogen or not halogen-containing in titanium compound, the magnesium compound, usage quantity with respect to magnesium, its mol ratio is preferably in the scope of 0.01-1000, preferably in the scope of 0.10-100.The 1st kind of usage quantity of giving the electronics compound, for the usage quantity of above-mentioned magnesium compound, its mol ratio is preferably in the scope of 0.001-10, preferably in the scope of 0.01-5.

The compound method of solid catalyst component used in the present invention, can use in the past known with magnesium compound, titanium compound and the 1st kind are given the electronics compound, in case of necessity, contact once or by stages, react with auxiliary agents such as halide-containings and obtain the compound method of solid catalyst component.

As the object lesson of known method, following compound method is arranged.

(1) makes magnesium halide, add the 1st kind in case of necessity and give electrical sub-compound, the method that contacts with titanium compound.

(2) make magnesium halide contact the method that the solids component that obtains contacts with the halogenide of halogenated titanium compound and/or silicon again with four titan-alkoxides and specific polymer silicon compound.

(3) give the electronics compound dissolution with magnesium compound with four titan-alkoxides and the 1st kind after, the method that the solids component of separating out after handling with halogenating agent or halogenated titanium compound contacts with titanium compound again.

(4) with Phosphorates phosphorus Halides compound treatment aluminum oxide or magnesium oxide, again with itself and magnesium halide, the 1st kind of method of contacting for electronics compound, halogenated titanium compound.

(5) will be effects such as the Grignard reagent of representative and reductive agent, halogenating agent with the organo-magnesium compound after, with the 1st kind of method of contacting for electronics compound titanium compound.

(6) the 1st kind exist for the electronics compound or not in the presence of, the method that the alkoxyl magnesium compound is contacted with halogenating agent and/or titanium compound.

(7) with four titan-alkoxide dissolved magnesium compounds, after the polymer silicon compound treatment, the method that the halogenide of recycle silicon and organometallic compound are handled.

(8) with the 1st kind of method of handling spherical magnesium compound/alcohol complex for electronics compound and halogenated titanium compound etc.

In order to make acrylic polymer of the present invention, can adopt the compound method of above-mentioned any solid catalyst component, carry the 1st kind of being held in the solid catalyst component and satisfy the polymerization solid catalyst composition of D/T 〉=1 for the mol ratio (D/T) of electronics compound/titanium atom content but will use at least.At this moment, be more preferably D/T 〉=1.5.

D/T＜1 o'clock is difficult to obtain the acrylic polymer of high stereoregularity of the present invention.

Like this, according to the present invention, can provide with magnesium compound, titanium compound, halogenide and the 1st kind is the solid catalyst of neccessary composition to the electronics compound, and is to carry the 1st kind of being held on the solid catalyst component to satisfy the solid catalyst component for alpha-olefin polymerization of D/T 〉=1 for the mol ratio (D/T) of electronics compound (D) and titanium (T).Moreover, though this solid catalyst component is in order to be used to make above-mentioned high stereoregularity polypropylene, be that the general polymerization of the alpha-olefin beyond the polymerization also is useful with solid catalyst component as general acrylic polymer or propylene.In particular for obtaining the stereoregularity height, during the acrylic polymer of rigidity, good heat resistance, best D/T 〉=1.5.

In addition, for compound method in the past,, also can be modified to the solid catalyst component that satisfies above-mentioned condition by following processing even can not satisfy the solid catalyst component of above-mentioned condition (D/T 〉=1).

At this moment, in the solid catalyst component before the improvement the 1st kind gives between electronics compound/Ti atom content mol ratio (D/T) m for the 1st kind in the catalyst component of mol ratio (D/T) i of electronics compound/Ti atom content and improvement, must satisfy the relation of (D/T) m/ (D/T) i＞1, be more preferably (D/T) m/ (D/T) i 〉=2.

For example, can with the preparation of above-mentioned myriad of well known method to give the electronics compound with magnesium, titanium, halogen and the 1st kind be the solid catalyst component of neccessary composition, by further handling for electronics compound and/or halogen contained compound with the 1st kind, make D/T and increase, with improved catalysts than before handling.There is not special restriction for order and the number of times giving the electronics compound treatment and handle with the 1st kind with halogenide, but treatment process as general solid catalyst component, be to give the electronics compound treatment with the 1st kind, carry hold after, handle with halogen contained compound, clean, and then wash with hydro carbons.

Be used for catalyst component when improvement used the 1st kind give the electronics compound can with use during the solid catalyst component preparation before the improvement identical or different.Can a kind use for electronics chemical combination separately, also can more than 2 kinds and use for the 1st kind.Preferably use the ester class, the particularly preferred phthalic acid ester class that is to use.

The 1st kind of usage quantity of giving the electronics compound is for the titanium atom in the solid catalyst component, preferably in 0.001-500 mole scope doubly, preferably in 0.01-10 mole scope doubly.

The 1st kind of usage quantity of giving the electronics compound extremely after a little while, then be difficult to obtain (D/T) m/ (D/T) i＞relation, otherwise if the 1st kind of usage quantity of giving the electronics compound extremely for a long time, then since polymerization activity descend, also bad.

The halogen-containing chemical combination that is used for catalyzer improvement, can use with improve before the preparation solid catalyst component identical, also inequality.Wherein preferably halogenated titanium, silicon halide, halon.Halogen contained compound can a kind uses separately, also can more than 2 kinds and use.

The usage quantity of halogen contained compound is in the scope of 0.1-10000 mol ratio with respect to the titanium atom in the solid catalyst component, preferably in the scope of 1-3000 mol ratio, most preferably in the scope of 5-500 mol ratio.In addition, when the halogen contained compound usage quantity is few, then be difficult to obtain the relation of (D/T) m/ (D/T) i＞1, otherwise the usage quantity utmost point of halogen contained compound for a long time, then because polymerization activity descends, the degree liquid measure increases, and is also bad.

In order to improve, be for the temperature of electronics compound treatment solid catalyst component-30-150 ℃ with the 1st kind, preferably 0-100 ℃ scope.In addition, the temperature of handling solid catalyst component with halogen contained compound is 0-200 ℃, preferably 50-150 ℃.During temperature condition beyond these,, and should not adopt because polymerization activity descends.

Give the electronics compound, when halogen contained compound carries out improved treatment to solid catalyst component, can in hydrocarbon solvent, carry out usually with the 1st kind.At this moment, employed hydrocarbon aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane preferably; Unreactive hydrocarbons such as aromatics such as benzene,toluene,xylene.In addition, these hydrocarbon also can be used as at solid catalyst component and use with the 1st kind of cleaning solvent of handling the after scouring solid catalyst component for electronics compound, halogen contained compound.

Solid catalyst component is given the electronics compound treatment with the 1st kind before improveing, and with the resulting improved catalyst for olefines polymerizing in halogen contained compound washing back, the temperature when washing with above-mentioned hydrocarbon is 0-100 ℃, preferably 60-140 ℃.When this moment, wash temperature was extremely low, then be difficult to obtain the relation of (D/T) m/ (D/T) i＞1, otherwise when wash temperature is extremely high, though can obtain the relation of (D/T) m/ (D/T) i＞1, because it is polymerization activity descends, also bad.

When giving electronics compound treatment solid catalyst component with the 1st kind, if handle (washing) without halogen contained compound, then polymerization activity extremely descends, and can not embody effect of the present invention.The number of times of handling (washing) with halogen contained compound does not have special restriction, but in order to give full play to effect of the present invention, preferably carries out 2 to 4 times.Wash and can not fully show effect of the present invention 1 time, but number of times too for a long time, polymerization activity descends, and is also bad.

In addition, give the electronics compound as the 1st kind among the present invention, (in the formula, X represents halogen atoms such as Cl, Br, I, and a is 3 or 4 can to use usefulness general formula TiXaYb, Y represents to supply with electronics compound (1), a 〉=≤b≤3) titanium compound of expression, with this processing and carry hold after, wash with halogen contained compound, and then, can be modified to a year special amount and be the solid catalyst component of D/T 〉=1 with the hydrocarbon washing.In this method, when giving electronics compound treatment solid catalyst component with the 1st kind, handle the number of times of (washing) in general with halogen contained compound of the present invention, as previously mentioned, at least need 2 times, but when using TiXa.Yb, handle (washing) with halogen contained compound and just can demonstrate fully effect of the present invention 1 to 2 time.And then, as described later, because the usage quantity of halogen contained compound also can reduce, so during with hydrocarbon washing improvement solid catalyst component, the waste liquid amount of discharge also can reduce significantly.

TiXa is (in the formula, X is halogen atoms such as Cl, Br, I, a is 3 or 4), be documented in as, R, S, P, Coutts, P.C.Wailes, Advan.Organometal.Chem., 9,135 (1970), the 4th editions new experimental chemistry lectures 17, inorganic complex chelate complexes, Japanization association ball kind (1991) are P.35, H.K.Kakkoen, J.Pursiainen, T.A.Pkkanen, M.Ahlgren, E.Iiskola, J.Organomet.Chem., 453, on the documents such as 175 (1993), generally know that they become thing with giving electronics compound formation network at an easy rate.

X among the TiXa.Yb is halogen atoms such as Cl, Br, I, wherein Cl preferably.A is 3 or 4, preferably 4.Y (the 1st kind give electronics compound) can select from above-mentioned compound, and employed same compound during solid catalyst component before can using and improve also can be different.When modulation TiXa, Yb, can use a kind of the 1st kind to give the electronics compound individually, also can more than 2 kinds and use.Organic acid ester preferably among the Y particularly preferably is the phthalic acid ester class.B among the Y is according to preparation during TiXa.Yb, and Y selects for the reinforced mol ratio of TiXa, the supply electronic number that Y has, the valence of Ti, and making it satisfy at a is 3 o'clock, 0＜b≤3, and a is 4 o'clock, 0≤b≤2.Most preferably a is 4, and b is 1.

The usage quantity of TiXa.Yb is preferably in the scope of 0.001-500 mol ratio with respect to the titanium atom in the preceding solid catalyst component of improvement, preferably in the scope of 0.01-50 mol ratio, particularly preferably is the scope in the 0.1-10 mol ratio.In addition, when the usage quantity of TiXa.Yb is few, be difficult to obtain the relation of (D/T) m/ (D/T) i＞1, otherwise the usage quantity utmost point of TiXa.Yb for a long time, and is owing to polymerization activity descends, also bad.

The usage quantity of halogen contained compound is in the scope of 0.1-100 mol ratio with respect to the titanium atom in the solid catalyst, preferably in the scope of 1-500 mol ratio, preferably in the scope of 5-100 mole.

The selection of halogen contained compound also can be same as described above.

Temperature when handling solid catalyst component with TiXa.Yb can give the treatment temp of electronics compound identical with above-mentioned the 1st kind, and in addition, the temperature during with halogen contained compound washing solid catalyst component also can be same as described above.

With TiXa.Yb to the processing of solid catalyst component and to utilize washing that halogen contained compound carries out to give processing that the electronics compound carries out and the washing that utilizes halogen contained compound with the 1st kind of above-mentioned usefulness be identical.

For the number of times of handling with TiXa.Yb and utilize the washing times of halogen contained compound to have no particular limits, as mentioned above, after TiXa.Yb handled, as long as wash 1 time to 2 times with halogen contained compound, effect of the present invention just can fully display.If, just can not obtain the high performance that adopts the present invention to reach without the halogen contained compound washing.

Prepolymerization

The improved solid catalyst component that is modulated into aforesaid method combines for the electronics compound with organo-aluminium compound described below, second kind, can be used for the polymerization of propylene, but can make a spot of monomer prepolymerization earlier before polymerization.Usually, per 1 improved solid catalyst component of being modulated into of gram, the pre-polymerization resultant is about 0.01 gram-1000 grams, and prepolymerized temperature is arbitrarily, is-30-80 ℃.Prepolymerization generally is that the organo-aluminium compound that uses when having following described polymerization at the same time and second kind are given under the situation of electronics compound and carried out, and can carry out in the inert hydrocarbon solvent, also can carry out in liquid monomer or gas phase monomer.

Employed monomer in the prepolymerization can also use for example ethene, 1-butylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene 4, alpha-olefines such as 4-dimethyl-1-amylene, vinyl pentamethylene, vinyl cyclohexane except that propylene; Styrene derivatives such as vinylbenzene, alpha-methyl styrene; Divinyl, 1, dienes such as 9-decadiene; Allyl group trialkyl silica alkanes.In addition, these monomers not only can use a kind, also can use or mix use more than 2 kinds stage by stage.Can also use hydrogen as molecular weight regulator during prepolymerization.

Propylene polymerization

Above-mentioned improved solid catalyst component has machine aluminium compound and second kind at the same time and gives under the situation of electronics compound, can the polypropylene base polymer.

The representational example of the organo-aluminium compound that uses among the present invention can be enumerated: trialkylaluminium, as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three hexyl aluminium, trioctylaluminum; Alkyl aluminum hydride is as dimethyl alanate, diethyl aluminum hydride, dibutyl alanate; Aluminum alkyl halide, as dimethyl aluminium muriate, diethyl aluminum muriate, diethyl aluminum bromide, ethyl aluminium sesqui chloride etc.; Aluminum alkyls alkoxide or phenates are as diethyl aluminum ethylate, diethyl aluminum phenates; Aluminium alkane is as aluminium trimethide alkane, aluminium triethyl alkane, propyl group aluminium alkane.These organo-aluminium compounds can use a kind separately, also can more than 2 kinds and use.The preferential use trialkylaluminium of selecting.

Give the electronics compound for second kind that uses among the present invention, can give the electronics compound identical with first kind, also can be with it different, representational this compounds can enumerate aromatic carboxylic acid's ester cpds, have silicon compound, the acetal compound of Si-O-C or Si-N-C key and have the heterogeneous ring compound etc. of the germanium compound of Ge-O-C key, the nitrogen with alkyl substituent or oxygen.

The object lesson of these compounds can be enumerated as follows: aromatic carboxylic acid ester, for example ethyl benzoate, to toluic acid ethyl ester, paraanisic acid ethyl ester; Silicon compound, phenyltrimethoxysila,e for example, diphenylmethyl TMOS, di dimethoxy silane, diisopropyl dimethoxy silane, di-t-butyl dimethoxy silane, dicyclohexyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclohexyl methyl dimethoxy silane, tert-butyl trimethoxy silane, cyclohexyl trimethoxy silane, decyl (テ キ シ Le) Trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane; Acetal compound, for example benzophenone dimethoxy acetal, benzophenone diethoxy acetal, phenacyl dimethoxy acetal, phenacyl diethoxy diethoxy acetal; Germanium compound, phenylbenzene dimethoxy germane for example, phenyl triethoxy germane; Heterogeneous ring compound, for example 2,2,6,6-tetramethyl piperidine, 2,2,6,6-tetramethyl-ratio is muttered.

These can use a kind separately for the electronics compound, also can more than 2 kinds and use.The preferred selection used silicon compound, acetal compound, particularly has the silicon compound of Si-O-C key.

Polymerization process in the manufacture method of the present invention has no particular limits, and can adopt known method, except the liquid polymerization method of slurry polymerization and mass polymerization and so on, can also use gas phase polymerization process.In addition, not only available batchwise polymerization but also can use the method for successive polymerization, batch polymerization.Under the situation of slurry polymerization, can use representative examples of saturated aliphatic such as hexane, heptane, hexanaphthene, toluene or aromatic hydrocarbons as polymer solvent, they can be used alone, but also also mix together.In addition, the polymerization process in the manufacture method of the present invention can also use the multi-stage polymeric of 2 above polymerization reactors.

Polymerization temperature is-50-200 ℃, preferentially select 20-150 ℃, and polymerization pressure is normal atmosphere-100kg/cm ²G, preferably 3-50kg/cm ²In addition, when polymerization, can add hydrogen in right amount to regulate molecular weight.

Adopt method of the present invention, except the homopolymerization of propylene, can also make propylene with by general formula R-CH=CH ₂The alhpa olefin copolymerization of (R is the hydrocarbon residue of hydrogen atom or carbonatoms 1-20, also can be branched group) expression.Concrete example can be enumerated ethene, 1-butylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-amylene, vinyl pentamethylene, vinyl cyclohexane etc., can also enumerate styrene derivatives, divinyl such as vinylbenzene, alpha-methyl styrene in addition, 1,5-hexadiene, 1,7-octadiene, 1, dienes such as 9-decadiene, allyl group trialkyl silica alkanes etc.These monomers can only use a kind, also can mix use more than 2 kinds.

In the acronal of the present invention, propylene-ethylene block copolymer can adopt the multi-stage polymeric process manufacturing of 2 above polymerization reactors, preferably makes homo-polypropylene in the 1st stage.

In this case, as long as the homo-polypropylene that the polymerization of the 1st stage finishes to take out the back satisfies prerequisite of the present invention, the multipolymer that so finally obtains just can obtain to be enough to solve the rerum natura of task of the present invention.

In addition, the acronal with the present invention obtains by adding known nucleating agent, can form crystallinity, the resin combination that high-speed molding further improves.

Nucleating agent can be exemplified below: weighting agent classes such as the salt (for example p-tert-butyl benzoic acid aluminium salt) of the salt (for example Sodium Benzoate) of monocarboxylic Ia and IIa family metal, di-carboxylic acid (hexanodioic acid), aliphatic dicarboxylic acid's III-IV family metal, two benzal base sorbitol derivatives, talcum.

What preferentially select is 1,3,2,4-two benzal base Sorbitol Powders, 1,3,2,4-two-(to methyl benzal base) Sorbitol Powder, 1,3,2,4-two-(to ethyl benzal base) Sorbitol Powder, 1,3,2,4-(to benzyl chloride fork base) Sorbitol Powder, 1,3-is to benzyl chloride fork base-2,4-is to methyl benzal base Sorbitol Powder, two-(4-tert-butyl-phenyl) sodium phosphate, 2,2-methylene radical-two-(4,4-two-tert-butyl-phenyl) sodium phosphate, 2,2 '-ethylidene-two (4,6-two-tert-butyl-phenyl) sodium phosphate, 2,2 '-ethylidene-two (4,6-two-tert-butyl-phenyl) sodium phosphate etc., and talcum, mineral fillers such as lime carbonate.

As for the add-on of these nucleating agents, if mix the nucleating agent of 0.05-15% (weight) at least in acronal, effect then of the present invention will be good significantly.

The addition of preferentially selecting for use is 0.08-0.8% (weight), particularly 0.1-0.5% (weight).But, as nucleating agent, the effect of mineral compound such as talcum is smaller than the effect of the nucleating agent of top example, and it is comparatively suitable therefore to add 1-15% (weight), preferably 2-13% (weight), particularly 5-10% (weight).

For acronal of the present invention or resin combination, in the scope of not damaging the object of the invention, habitual other additive in the suitably fusion thermoplasticity fat, for example antioxidant, weathering resistance stablizer, antistatic agent, lubricant, release agent, to turbid dose, dyestuff, pigment, oils, wax etc.

The example of these additives can be enumerated: antioxidant for example 2,5-di-tert-butyl hydroquinone, 2,6-di-t-butyl-p-Cresol, 4,4-thiobis-(6-tert.-butyl phenol), 2,2-methylene radical-two (4-methyl-6-tert butyl phenol), 3-(3 ', 5 '-di-t-butyl-1 '-hydroxyphenyl) propionic acid stearyl, 4,4 '-thiobis-(6-butylphenol); UV light absorber is for example: 2-cyano-3,3-diphenyl ethyl acrylate, 2-(2 '-hydroxy-5-methyl phenyl) benzotriazole, 2-hydroxyl-4-octyloxy benzophenone; Softening agent is rutgers, diethyl phthalate, wax, whiteruss, phosphoric acid ester for example; Antistatic agent for example monostearate, Sorbitol Powder monopalmitate, sulfation oleic acid, polyethylene oxide, carbon is cured; Lubricant is ethylenebisstearamide, stearic acid butyl ester for example; Tinting material is carbon black, phthalocyanine, quinoline a word used for translation ketone, dihydroindole, azo class pigment, titanium oxide, the red iron of oxidation for example; Weighting agent is glass fibre, asbestos, mica, artificial marble, Calucium Silicate powder, pure aluminium silicate etc. for example.In addition, can also fusion under the situation that does not harm effect of the present invention, effect many other macromolecular compounds.

There is no particular limitation for the melting index of acronal of the present invention (MFR-JIS-7210, table 1 condition 14), can be selected according to manufacturing process and purposes, and the scope of dividing at 0.1-500g/10 is comparatively suitable usually.

Acronal of the present invention can adopt known melt-shaping method or compression forming method, is processed into and is injection molded into body, film, plate, pipe, bottle etc., can use or use with other material laminate with monomer.

Method as for lamination, for example, can adopt dry laminate method or interlayer lay-up method, use dry laminate binding agents such as polyurethanes, polyester, stacked other thermoplastic resin on the individual layer thing of acronal of the present invention or resin combination can also adopt coextrusion lay-up method, coetrusion (feed compression molding, branch manifold mode) injection molded method, coextrusion pipe moulding method altogether in addition.

The laminated multi-layer body that obtains like this, subsequently can be with straight empty forming mill, pneumatic forming machine, drawing blow molding machine etc., heat once more and impose stretched operation, perhaps this laminated multi-layer body or monomer shaping thing are imposed the heating stretched operation with single shaft or biaxial stretch-formed machine.

Brief description of drawings.

Fig. 1 is the methyl zone of homo-polypropylene ¹³An example of C-NMR spectrum spectrogram.

With embodiment the present invention is described in further detail below.

Embodiment

The measuring method and the device thereof of each physics value among the present invention are described as follows:

(1) the insoluble part of dimethylbenzene (XI)

The 2.5g polymer dissolution in 135 ℃ o-Xylol (250ml), is decided to be the insoluble part of dimethylbenzene (XI) to the polymkeric substance of separating out at 25 ℃ (weight %).

(2) five one group ratio of isotactic (mmmm)

The mmmm ratio is that five modular constructions with the methyl in the polypropylene based polymers molecular chain are the isotactic ratio of unit, the JNM-GSX400 that makes with NEC (strain) ( ¹³C nuclear resonance frequency 100MHz) measures.Various information are recorded in the outstanding Macromolecules of people such as A.Zambelli, 13,267, (1980).Condition determination is as follows.

The mensuration mode: proton goes the lotus root method

Pulse width: 8.0 μ s

Pulse reciprocal time: 3.0 μ s

Cumulative frequency: 20000 times

Solvent: 1,2,4-trichlorobenzene/biphenyl mixed solvent (75/25 volume %)

Interior mark: hexamethyldisiloxane

Sample solution concentration: 300mg/3.0ml solvent

Measure temperature: 120 ℃

(3) isotactic mean chain length (N)

Isotactic mean chain length (N) is to calculate by J.C.Radall method of reporting (seeing " Polymer Sequence Distribution ", Academic press, New York, 1977, the 2 chapters).Specifically, polypropylene is placed 1,2, heat temperature raising to 130 ℃ in the mixed solvent of 4-trichlorobenzene/biphenyl makes it dissolving and polymer concentration and reaches 10% (weight).

This solution is put into the glass test tube of internal diameter 10mm, under the test condition identical, measure with above-mentioned isotactic five modular construction ratios (IP) ¹³C-NMR.Then, as previously mentioned,, can obtain mean chain length (N) by following definition by the chain number of mesomeride and the unit number of mesomeride.

The unit number of the chain number/mesomeride of N=mesomeride

(4) post partition method

Acronal with the insoluble part of dimethylbenzene under 130 ℃ is dissolved in the p-Xylol, adds diatomite, is cooled to 30 ℃ with 10 ℃/hour speed, and it is attached on the diatomite.This dirt settling is filled in the post, is warming up to 130 ℃, divide and get each fraction from 70 ℃ by each 2.5 ℃.

(5) injection moulding

IS-170FII (the theoretical shot capacity 250cm that uses Toshiba's (strain) to make ³), under the condition of 220 ℃ of mold temperatures, 50 ℃ of metal pattern cooling temperatures, make socle girder impact specimen, bending elastic modulus sample, temperature of deflection under load sample, surface luster usefulness sample (flat board of thickness 2mm * 15cm * 11cm).In the thermostatic chamber of 23 ℃ of humidity 50%, temperature, place two round the clock after, measure its rerum natura.

(6) cantilever beam impact strength (band otch)

Undertaken by JIS K710 standard.Testing apparatus adopts goes up the U-F shock-testing machine that the island makes institute's (strain) manufacturing.

(7) bending elastic modulus

Undertaken by JIS K7203 standard.

(8) ethylene content

Press the utilization of people's reports such as C.J.Carman ¹³The method of C-NMR (seeing Macromolecules, 10,537 (1977)) is calculated.

(9) MFR (melting index)

Standard by JIS K7210 table 1 condition 14 is carried out.The melt index determination device that testing apparatus adopts カ ラ (strain) to make.

(10) temperature of deflection under load

Press JIS K7207B standard, the HDT ε VSPT trier that adopts the smart mechanism of (strain) Japan to do manufacturing carries out.

(11) Rockwell surface hardness

Make the test sample with the compression molding forming machine of 230 ℃ of temperature, adopt the smart mechanism of Japan to make the AR-10 type Rockwell hardometer of institute's (strain) system, undertaken by JIS K7202 standard.

(12) film forming

The Φ 40mmT pattern head thin film forming machine that uses lucky well ironworker (strain) to make is under the condition that 230 ℃ of mould temperature, 30 ℃ of cooling temperatures, pulling speed 10m/ divide.Make the film of thick 60 μ m, measure water vapor amount, turbidity, surface smoothness thoroughly.

(B) turbidity (Hace)

Press JIS K7105 standard, use the turbidity time meter of the HGM-2D type of ス ガ trier (strain) manufacturing to carry out.

(14) surface gloss

Press JIS K7105 standard, use the VG-1D type glossiness meter of Japanese electric look industry (strain) system to carry out.

(15) steam permeable amount

Press the ASTM-E96 standard, the PERMATRAN W instrument that uses MODERN CONTROLSINC company to make is measured under the condition of 37.8 ℃ of temperature, relative humidity 90%.

(16) catalyst analysis

Decompose improvement preceding solid catalyst component, improved solid catalyst component for olefin polymerization with dilute sulphuric acid, extract organism with heptane again.Ti amount in the atomic absorption AA610S type Instrument measuring water layer that use Shimadzu Seisakusho Ltd. (strain) makes.The gas chromatograph 263-50 that makes with Hitachi (strain) measures and gives electronics compound amount in the heptane layer.

Embodiment 1

(1) modulation (usage) of the solid catalyst component before the improvement

Under nitrogen atmosphere and 120 ℃, Magnesium Chloride Anhydrous 56.8g (597mmol) is dissolved among the hydroxy silicon oil KF96 500ml that vaseline oil CP15N 500ml that dehydrated alcohol 100g (174mmol), the emerging product of bright dipping (strain) make and SHIN-ETSU HANTOTAI's silicon product (strain) make fully.TK intimate mixing device with special machine chemical industry (strain) is made stirred this mixture 3 minutes with 3000 rev/mins of rotating speeds under 120 ℃.One side stirs one side it is transplanted in 2 liters of anhydrous heptane, makes it be no more than 0 ℃.The gained white solid is with anhydrous heptane thorough washing, vacuum-drying at room temperature.

With the resulting MgCl of 30g ₂2.5C ₂H ₅The OH spherical solid is suspended in the anhydrous heptane of 200ml, and one side stirs one side down at 0 ℃ and dripped titanium tetrachloride 500ml (4.5mol) with 1 hour time.Begin heating then, add isobutyl terephthalate 4.96g (17.8mmol) when reaching 40 ℃, in about 1 hour time, be warming up to 100 ℃.After 2 hours, solid part is collected in hot filtration 100 ℃ of reactions.Then, titanium tetrachloride 500ml (4.5mol) is suspended in this reactant, 120 ℃ of reactions 1 hour.Solid part is collected in hot once more filtration after reaction finishes, and with 1.0 liters 60 ℃ hexane wash 7 times, uses 1.0 liters of hexane wash under the room temperature 3 times again.After measured, the titanium content in the gained solid catalyst component is 2.25% (weight), in addition, also contains 7.81% (weight) and gives electronics compound (1).

(2) modulation of improved solid catalyst component

Resulting solid catalyst component above the 20g is suspended in the 300ml toluene, reacted 1 hour down with isobutyl terephthalate 2.78g (10mmol) at 25 ℃.After reaction finishes, add titanium tetrachloride 100ml (900mmol), 90 ℃ of reactions 1 hour.Solid part is collected in hot filtration after question response finishes, and subsequently, toluene 300ml, titanium tetrachloride 100ml (900mmol) is suspended in this reactant, reacts 1 hour down at 90 ℃.After reaction finished, solid part was collected in hot once more filtration, with the toluene wash of 90 ℃ of 500ml 7 times, used the hexane wash 3 times under the 500ml room temperature again.After measured, the titanium containing ratio in the gained solid catalyst component is 1.01% (weight), gives the electronics compound for the 1st kind that also contains 12.0% (weight) in addition.Provided the comparison that improves forward and backward catalyst component analytical results in the table 1.

(3) prepolymerization

Under nitrogen atmosphere, with the improved olefin polymerization catalyst component 10g that obtains in normal heptane 500ml, triethyl aluminum 6.0g (53mmol), dicyclopentyl dimethoxyl silane 3.9g (17mmol) and above-mentioned (2) the inner body that holds of packing into is in 3 liters the autoclave, stirs 5 minutes in 0-5 ℃ temperature range.Then, infeed propylene according to the ratio of the improved olefin polymerization catalyst component polymerization of every 1g 10g propylene in autoclave, prepolymerization is 1 hour in 0-5 ℃ temperature range.Resulting prepolymerized solid catalyst composition is used for the manufacturing of following acronal with 500ml normal heptane washing 3 times.

(4) formal polymerization

Under nitrogen atmosphere, to be in 60 liters the autoclave of band stirrer with the synthetic prepolymerized solid catalyst composition of aforesaid method 2.0g, triethyl aluminum 11.4g (100mmol), dicyclopentyl dimethoxyl silane 6.84g (30mmol) internal capacity of packing into, and then the propylene 18kg and import hydrogen of packing into, the import volume of chlorine is 13000molppm with respect to propylene, is warming up to 70 ℃ of polymerizations 1 hour.Removing unreacted propylene after 1 hour finishes polymerization.The result obtains the 6.56kg polypropylene, and polymerization activity is the 32.8kg/g solid catalyst component, and the MFR of polymkeric substance is the 33.0g/10 branch.Provide the evaluation of physical property result of polymkeric substance in the table 2.

Embodiment 2

(1) modulation of the solid catalyst component before the improvement

Identical with embodiment 1.

(2) TiCl ₄(C ₆H ₄(COO ⁱC ₄H ₉) ₂) modulation

Remain on 0 ℃, meanwhile use about 30 minutes the time isobutyl terephthalate: C ₆H ₄(COO ⁱC ₄H ₉) ₂27.8g (100mmol) be added drop-wise in 1.0 liters of hexane solutions that contain titanium tetrachloride 19g (100mmol).Be warming up to 40 ℃ after dropwising, reacted 30 minutes.Reaction finishes the back and collects solid part, with hexane 500ml washing 3 times, obtains the purpose product.

(3) modulation of improved olefin polymerization catalyst component

The solid catalyst component 20g that obtains in above-mentioned (1) is suspended in the 300ml toluene, under 25 ℃, uses TiCl ₄(C ₆H ₄(COO ⁱC ₄H ₉) ₂) 5.2g (11mmol) handled 1 hour, and made it to carry and hold.Carry to hold and utilize hot solid collected by filtration part after finishing, again it is suspended among toluene 300ml and the titanium tetrachloride 10ml (90mmol), 90 ℃ of following agitator treatings 1 hour, hot solid collected by filtration part, then, this reactant with the toluene wash of 90 ℃ of 500ml 5 times, is used the hexane wash 3 times under the 500ml room temperature again.After measured, the titanium containing ratio in the gained solid catalyst component is 0.91% (weight), gives the electronics compound for the 1st kind that also contains 10.6% (weight) in addition.Improve forward and backward catalyst analysis result's comparison shown in the table 1.

(4) prepolymerization

Under nitrogen atmosphere, with the improved olefin polymerization catalyst component 10g that obtains in normal heptane 500ml, triethyl aluminum 6.0g (53mmol), dicyclopentyl dimethoxyl silane 3.9g (17mmol) and above-mentioned (3) internal capacity of packing into is in 3 liters the autoclave, stirs 5 minutes in 0-5 ℃ of temperature range.Then, infeed propylene in the ratio of the improved olefin polymerization catalysis polymerization of every 1g 10g propylene in autoclave, prepolymerization is 1 hour in 0-5 ℃ temperature range.Resulting prepolymerized solid catalyst composition is used for the manufacturing of following acronal with 500ml normal heptane washing 3 times.

(5) formal polymerization

Under nitrogen atmosphere, with the synthetic prepolymerized solid catalyst composition of aforesaid method 2.0g, triethyl aluminum 11.4g (1 00mmol), dicyclopentyl dimethoxyl silane 6.84g (30mmol) internal capacity of packing into is in 60 liters the autoclave that has stirrer, pack into then 18kg propylene and import hydrogen, the import volume of hydrogen is 13000molppm with respect to propylene.Be warming up to 70 ℃ of polymerizations 1 hour, remove unreacted propylene after 1 hour polyreaction is stopped, the result obtains the 6.64kg polypropylene, and polymerization activity is the 34kg/g solid catalyst component, and the MFR of polymkeric substance is the 34.2g/10 branch.The evaluation of physical property result of polymkeric substance shown in the table 2.

Comparative example 1

Under nitrogen atmosphere, AA type titanous chloride 6.0g, the diethyl aluminum muriate 23.5g (195mmol) that eastern Cao Ai Kesuo (strain) the is made internal capacity of packing into is in 60 liters the autoclave that has stirrer, and then the 18kg propylene and import hydrogen of packing into, the import volume of hydrogen is 8000molppm with respect to propylene.Be warming up to 70 ℃ of polymerizations 1 hour, the propylene of removing the end reaction after 1 hour stops polymerization.The result obtains the 6.23kg polypropylene, and the MFR of polymkeric substance is the 32.2g/10 branch.Provide the evaluation of physical property result of polymkeric substance in the table 2.

Comparative example 2

Use the solid catalyst component before the synthetic improvement in (1) of embodiment 1, the import volume of hydrogen is 9300molppm during propylene polymerization, in addition carries out prepolymerization and propylene polymerization according to method and the condition identical with embodiment 2.The result obtains the 6.88g polypropylene, and the MFR of this polymkeric substance is the 33.0g/10 branch.The evaluation of physical property result of polymkeric substance shown in the table 2.

Embodiment 3-5

Hydrogen import volume when regulate making acronal makes the polyacrylic MFR of generation be respectively the 10.5g/10 branch, 2.7g/10 divides and the 0.7g/10 branch, in addition, makes polypropylene according to method and the condition identical with embodiment 2.The rerum natura review of resulting polymers the results are shown in the table 2.

Comparative example 3

Hydrogen import volume when adjusting acronal and making makes the MFR of the acronal of generation become the 3.2g/10 branch, in addition, makes acronal according to method and the condition identical with comparative example 1.The evaluation of physical property of resulting polymers the results are shown in the table 2.

Embodiment 6

(1) modulation of the solid catalyst component before the improvement

Under nitrogen atmosphere, Magnesium Chloride Anhydrous 47.6g (500mmol), decane 250ml and 2-Ethylhexyl Alcohol 234ml (1.5mol) are heated 2 hours to react at 130 ℃, form uniform solution, in this solution, add dry-out benzene dioctyl phthalate 11.1g (75mmol) then, further mixed 1 hour at 130 ℃, phthalic acid is dissolved in this homogeneous solution.The gained uniform solution is cooled to room temperature, with 1 hour its full dose is splashed in the titanium tetrachloride 2.0 liters (18mol) that remains on-20 ℃ then.Dropwise the back and with 4 hours mixing solutions is warming up to 110 ℃, when temperature reached 110 ℃, interpolation phthalic acid diisobutyl ester 26.8ml (125mmol) was 110 ℃ of stirring reactions 2 hours.Reaction finishes the hot solid collected by filtration part in back, subsequently tetrahydro-titanium 2.0 liters (18mol) is suspended in this reactant, 110 ℃ of reactions 2 hours.Hot once more solid collected by filtration part after reaction finishes is washed 7 times with 2.0 liters 110 ℃ decane, uses the hexane wash 3 times of 2.0 liters of room temperatures again, obtains solid catalyst component.Catalyst analysis the results are shown in the table 1.

(2) TiCl ₄(C ₆H ₄(COO ⁱC ₄H ₉) ₂) modulation

Identical with embodiment 2 they (2).

(3) modulation of improved olefin polymerization catalyst component

Be suspended in the 600ml toluene obtaining solid catalyst component among the 40g above-mentioned (1), at 90 ℃ of TiCl that obtain in descending with above-mentioned (2) ₄(C ₆H ₄(COO ⁱC ₄H ₉) ₂) 10.3g (22mmol) handles and to be held this year in 1 hour.Carry hold finish after hot solid collected by filtration part, again it is suspended among toluene 600ml and the titanium tetrachloride 20ml (180mmol), 90 ℃ of agitator treatings 1 hour, hot solid collected by filtration part, subsequently the toluene of this reactant with 90 ℃ is washed 5 times for 1.0 liters, hexane with room temperature washs the olefin polymerization catalyst component that is improved 3 times for 1.0 liters.Catalyst analysis the results are shown in the table 1.

(4) prepolymerization

Under nitrogen atmosphere, be in 3 liters the autoclave with the improved olefin polymerization catalyst component 10g that obtains in normal heptane 500ml, triethyl aluminum 6.0g (0.053mmol), dimethoxydiphenylsilane 4.15g (0.017mmol) and the foregoing description 2 they (3) internal capacity of packing into.In 0-5 ℃ of temperature range, stirred 5 minutes.Ratio in the improved olefin polymerization catalyst component polymerization of every 1g 10g propylene infeeds propylene in autoclave then, and prepolymerization is 1 hour in 0-5 ℃ of temperature range.Resulting prepolymerized solid catalyst composition uses for the manufacturing of following acronal with 500ml normal heptane washing 3 times.

(5) polymerization of propylene

Under nitrogen atmosphere, to be in 60 liters the autoclave of band stirrer with the synthetic prepolymerized solid catalyst composition of aforesaid method 2.0g, triethyl aluminum 11.4g (100mmol), dimethoxydiphenylsilane 7.32g (30mmol) internal capacity of packing into, the 18kg propylene of packing into subsequently imports hydrogen, the import volume of hydrogen is 5300molppm with respect to propylene, is warming up to 70 ℃ of polymerizations 1 hour.The propylene of removing the end reaction after 1 hour stops polyreaction.Polymerization activity is the 22.0kg/g solid catalyst component.The polyacrylic MFR of gained is the 14.5g/10 branch.The evaluation of physical property of polymkeric substance the results are shown in the table 2.

Embodiment 7

(1) modulation of the solid catalyst component before the improvement

Under nitrogen atmosphere, diethoxy magnesium 50.0g (440mmol), terephthalic acid di-n-butyl ester 15.3g (55mmol) refluxed in the 250ml methylene dichloride stirred 1 hour, gained suspension is pressed and delivered in the titanium tetrachloride 2.0 liters (18mol), be warming up to 110 ℃ of reactions 2 hours, after reaction finishes, the solid and the titanium tetrachloride 2.0 liters (18mol) of separating out were reacted 2 hours at 110 ℃.Then with 2.0 liters 110 ℃ n-decane washing 3 times, at room temperature with 2.0 liters of hexane wash until checking less than chlorion.Obtain the solid catalyst component of purpose product at 40 ℃ of following drying under reduced pressure.Catalyst analysis the results are shown in the table 1.

(2) TiCl ₄(C ₆H ₄(COO ⁱC ₄H ₉) ₂) modulation

Identical with embodiment 2 they (2)

(3) modulation of improved olefin polymerization catalyst component

The solid catalyst that obtains among the 40g above-mentioned (1) is suspended in the 600ml toluene, at 90 ℃ of TiCl that obtain in descending with above-mentioned (2) ₄(C ₆H ₄(COO ⁱC ₄H ₉) ₂) 10.3g (22mmol) handles to make it in 1 hour to carry and hold, carry to hold to utilize hot solid collected by filtration part after finishing.It is suspended among toluene 600ml and the titanium tetrachloride 20ml (180mmol), in 90 ℃ of following agitator treatings 1 hour, hot solid collected by filtration part, then with this reactant with 1.0 liters 90 ℃ toluene wash 5 times, with the hexane wash under 1.0 liters of room temperatures 3 times.Catalyst analysis the results are shown in the table 1.

Prepolymerization and propylene polymerization all carry out according to method and the condition identical with embodiment 6.As a result, polymerization activity is the 21.1kg/g solid catalyst component, and in addition, the polyacrylic MFR of gained is the 16.3g/10 branch.The evaluating characteristics of polymkeric substance the results are shown in the table 2.

Table 1: catalyst analysis result

	Solid catalyst component before the improvement			The improvement olefin polymerization catalyst component
								????Di ????(wt％)	??Ti ??(wt％)	????(D/T) i	??D m??(wt％)	??Ti ??(wt％)	????(D/T) m	????(D/T) m????/(D/T) i
	Embodiment 1 embodiment 2 embodiment 6 embodiment 7	????7.81 ????7.81 ????10.1 ????9.80	??2.25 ??2.25 ??2.57 ??2.31	????0.60 ????0.60 ????0.75 ????0.73	??12.0 ??10.6 ??15.6 ??13.3	??1.01 ??0.91 ??1.01 ??1.22	????2.05 ????2.01 ????1.98 ????1.53								????3.42 ????3.35 ????2.64 ????2.10

Table 2-1

Embodiment and comparative example	The insoluble part of xylene extraction (weight %)	Isotactic five modular construction ratio IPmmmm (%)	Isotactic mean chain length N	The weight ratio Nf (weight %) of the cut of isotactic mean chain length N＞800	MFR (g/10 branch)
						Embodiment 1	????99.5	????99.5	????816	????80	????33.0
????″????????2	????99.5	????99.5	????836	????81	????34.2
						Comparative example 1	????98.6	????97.7	????225	????＜1	????32.2
????″????????2	????98.8	????98.9	????326	????7	????33.0
						Embodiment 3	????99.5	????99.5	????715	????76	????10.5
????″????????4	????99.5	????99.4	????651	????72	????2.7
						????″????????5	????99.4	????99.3	????588	????65	????0.7
????″????????6	????99.3	????99.3	????703	????68	????14.5
						????″????????7	????99.3	????99.4	????765	????70	????16.3
Comparative example 3	????98.1	????96.3	????105	????＜1	????3.2

Table 2-2

Embodiment and comparative example	Injection-molded article						Film
										Cantilever beam impact strength (kgcm/cm)		Bending elastic modulus (kg/cm 2)	The load deflexion temperature (℃)	Rockwell surface hardness R scalar	Surface gloss (%)	Surface gloss (%)	Steam permeable amount (g/cm 2·day)	Turbidity (%)
	????23℃	????-20℃
			Embodiment 1	????1.7	????-	????17900	????130	????104	????86.0	????120	????5.6								????2.4
Embodiment 2	????1.8	????-										????18100	????131	????104	????86.4	????122	????5.6	????2.4
			Comparative example 1	????2.0	????-	????14600	????119	????93	????83.2	????46	????7.9								????23.3
Comparative example 2	????1.8	????-										????16200	????127	????101	????84.2	????116	????6.1	????3.2
			Embodiment 3	????2.0	????-	????17900	????130	????103	????85.1	????117	????5.5								????2.8
Embodiment 4	????2.8	????-										????17200	????130	????102	????84.3	????113	????5.4	????3.0
			Embodiment 5	????4.4	????-	????14200	????110	????96	????83.9	????-	????-								????-
Embodiment 6	????2.0	????-										????17300	????128	????101	????85.2	????-	????-	????-
			Embodiment 7	????2.0	????-	????17500	????128	????101	????85.3	????-	????-								????-
Comparative example 3	????2.5	????-										????12300	????104	????88	????81.6	????42	????7.7	????20.9

Embodiment 8

Similarly to Example 2, be in 60 liters the autoclave of band stirrer behind the polypropylene (first section) at internal capacity, remove liquid propene, under 75 ℃ respectively with 2.2Nm ³/ hour and 20NL/ hour speed supply with the mixed gas and the hydrogen of ethylene/propene=40/60 (mol ratio), copolymerization 40 minutes (second section).The gas of removing the end reaction after 40 minutes stops polymerization, and the result obtains the 8.0kg propylene-ethylene block copolymer.Utilize ¹³It is 9.7% (weight) that C-NMR records ethylene content, and MFR is the 17.8g/10 branch.The rerum natura evaluation result of polymkeric substance is shown in Table 3.XI in the table 3, IP, N are the parameters of the homo-polypropylene that takes out after first section end.

Comparative example 4

Same with comparative example 1, be 60 liters and have in the autoclave of stirrer and carry out propylene polymerization at internal capacity, remove alkene in the liquid then, under 65 ℃ respectively with 2.2Nm ³/ hour and 20NL/ hour the speed mixed gas and the hydrogen that infeed ethylene/propene=40/60 (mol ratio) reach 40 minutes, the gas of removing the end reaction after 40 minutes stops polymerization, the result obtains the 7.7kg propylene-ethylene block copolymer.Utilize ¹³It is 9.6% (weight) that C-NMR measures ethylene content, and MFR is the 18.3g/10 branch.The evaluation of physical property of polymkeric substance the results are shown in the table 3.XI in the table 3, IP, N are the parameters that first section polymerization finishes the homo-polypropylene of back taking-up.

Table 3-1

Embodiment and comparative example	The insoluble part of xylene extraction (weight %)	Isotactic five modular construction ratio IP mmm (%)	Isotactic mean chain length N	The weight ratio Nf (weight %) of the cut of isotactic mean chain length N＞800	MFR (g/10 branch)
						Embodiment 8	99.5	99.5	????830	79	????17.8
Comparative example 4	98.5	97.7	????217	＜1	????18.3

Table 3-2

Embodiment and comparative example	Injection-molded article						Film
										Hit intensity in the socle girder (kgcm/cm)		Bending elastic modulus (kg/cm 2)	Load deflexion temperature (%)	Rockwell surface hardness R scalar	Surface gloss (%)	Surface gloss (%)	Steam permeable amount (g/cm 2·day)	Turbidity (%)
	????23℃	???-20℃
			Embodiment 8	????6.4	????3.9	????14100	????124	????92	68.1	-	??????-								???-
Comparative example 4	????5.5	????3.3										????12100	????112	????87	62.3	-	??????-	???-

Embodiment 9,10 and comparative example 5

Example as propylene polymer composition, in the resulting acronal of the present invention fusion di-t-butyl base-p-Cresol 0.05% (weight), four (3-(3,5-dibutyl-4-hydroxyphenyl)) propionic acid five red moss esters 0.10% (weight), calcium stearate 0.10% (weight), the 20 liters of mixing machines (SMV20 type) that use the field, river to make manufacturing carry out fusion, with the AS30 type Φ 30mm twin screw extruder granulation of field paddy machinery society manufacturing.In addition, use following nucleating agent, but the blended amount appropriate change.

The kind of nucleating agent

Nucleating agent A: right-p t butylbenzoic acid aluminium

Nucleating agent B:2,2-methylene-bis (4,6-two-tert-butyl-phenyl) sodium phosphate.

The above-mentioned nucleating agent of fusion in embodiment 2 resulting polypropylene and the composition (embodiment 9,10) that obtains and in comparative example 1 resulting polypropylene fusion nucleating agent and the rerum natura evaluation result of the composition (comparative example 5) that obtains be shown in Table 4.

Embodiment 11 and comparative example 6

In embodiment 8 and comparative example 4 in the resulting propylene-ethylene block copolymer, fusion nucleating agent similarly to Example 9, the rerum natura evaluation result of resulting composition is shown in Table 4.

Table 4-1

Embodiment and comparative example	The insoluble part of xylene extraction (weight %)	Isotactic five modular construction ratio IP mmm (%)	Isotactic mean chain length N	The weight ratio Nf (weight %) of the cut of isotactic mean chain length N＞800	MFR (g/10 branch)	The kind of nucleating agent and blended amount (weight %)
							Embodiment 9	????99.5	????99.5	????836	????81	????34.2	A?0.2
????″????????10	????99.5	????99.5	????836	????81	????34.2	B?0.4
							Comparative example 5	????98.8	????98.9	????326	????7	????32.2	B?0.4
Embodiment 11	????99.5	????99.5	????830	????79	????17.8	A?0.2
							Comparative example 6	????98.5	????97.7	????217	????＜1	????18.3	A?0.2

Table 4-2

Embodiment and comparative example	Injection-molded article						Film
										Cantilever beam impact strength (kgcm/cm)		Bending elastic modulus (kg/cm 2)	The load deflexion temperature (℃)	Rockwell surface hardness R scalar	Surface gloss (%)	Surface gloss (%)	Steam penetrating capacity (g/cm 2·day)	Turbidity (%)
	??23℃	??-20℃
			Embodiment 9	??1.7	??-	???22000	????141	????105	????91.7	????81	????5.3								????13.5
????″??????10	??1.9	??-										???24500	????148	????109	????93.8	????84	????5.1	????11.6
			Comparative example 5	??1.7	??-	???19200	????131	????102	????86.3	????32	????7.2								????28.9
Embodiment 11	??6.2	??3.8										???16800	????134	????99	????72.2	????-	?????-	????-
			Comparative example 6	??5.3	??3.0	???14600	????124	????91	????67.2	????-	?????-								????-

By implementing the present invention, can make rerum naturas such as rigidity, surface hardness, thermotolerance, water vapor barrier property than more superior in the past acronal that is applicable to automobile, household electrical appliance, wrapping material and composition thereof, have a very high using value industrial.

Claims (12)

1. a propylene polymerization is with the manufacture method of solid catalyst component, comprising following operation, promptly form with magnesium compound, titanium compound, it be the polymerization solid catalyst composition of necessary composition that halogenide and the 1st kind are given the electronics compound, and carrying the 1st kind of mol ratio of supplying with electronics compound (D) and titanium (T) of holding is (D/T) i, then, handle above-mentioned polymerization solid catalyst composition, make it to be modified to that to carry the 1st kind of mol ratio of supplying with electronics compound (D) and titanium (T) of holding be the polymerization solid catalyst composition of (D/T) m, wherein (D/T) m/ (D/T) i＞1.

2. the described method of claim 1, wherein (D/T) m/ (D/T) i 〉=2.

3. the described method of claim 1, comprising in the processing of above-mentioned solid catalyst component, with the 1st kind supply with the electronics compound treatment, carry hold after, again with halogen contained compound handle, washing, and then with the operation of hydrocarbon washing.

4. the described method of claim 1, comprising following operation, it is the processing of above-mentioned solid catalyst component, be with the titanium compound that general formula TiXaYb represents handle above-mentioned solid catalyst component make it to carry hold after, with the halogen contained compound washing, and then wash with hydrocarbon, wherein X represents the halogen atom of Cl, Br and/or I, a is 3 or 4, and Y is first kind and supplies with electronics compound, 0＜b≤3.

5. the propylene polymerization solid catalyst component contains magnesium compound, titanium compound, halogen compounds and the 1st kind of titanium compound as neccessary composition, and this solid catalyst component is prepared by following method:

It serve as the polymerization solid catalyst composition of necessary composition that formation is given the electronics compound with magnesium compound, titanium compound, halogenide and the 1st kind, and carrying the 1st kind of mol ratio of supplying with electronics compound (D) and titanium (T) of holding is (D/T) i, then, handle above-mentioned polymerization solid catalyst composition, make it to be modified to that to carry the 1st kind of mol ratio of supplying with electronics compound (D) and titanium (T) of holding be the polymerization solid catalyst composition of (D/T) m, wherein (D/T) m/ (D/T) i＞1.

6. the described solid catalyst component of claim 5, wherein (D/T) m/ (D/T) i 〉=2.

7. the described solid catalyst component of claim 5, comprising in the processing of above-mentioned solid catalyst component, with the 1st kind supply with the electronics compound treatment, carry hold after, again with halogen contained compound handle, washing, and then with the operation of hydrocarbon washing.

8. the described solid catalyst component of claim 5, comprising following operation, it is the processing of above-mentioned solid catalyst component, be with the titanium compound that general formula TiXaYb represents handle above-mentioned solid catalyst component make it to carry hold after, with the halogen contained compound washing, and then wash with hydrocarbon, wherein X represents the halogen atom of Cl, Br and/or I, a is 3 or 4, and Y is first kind and supplies with electronics compound, 0＜b≤3.

9. the manufacture method of acrylic polymer comprises and uses the polymerizing catalyst that contains following compositions to carry out the operation of propylene polymerization:

(i) solid catalyst component of making according to each method of claim 1-4 wherein carries the 1st kind of being held in the polymerization solid catalyst composition and gives mol ratio (D/T) m 〉=1 of electronics compound (D) with titanium compound (T);

(ii) organo-aluminium compound;

(iii) give the electronics compound for the 2nd kind.

10. the described manufacture method of claim 9, use therein is the above-mentioned solid catalyst component of D/T 〉=1.5.

11. the manufacture method of claim 9 or 10 is to make the acrylic polymer with following character: (1) more than 99.0 weight %, (2) are used for the insoluble part of 25 ℃ xylene extraction (XI) ¹³The isotactic five modular construction ratios (IP) of C nuclear magnetic resonance spectroscopy are that (3) isotactic mean chain length (N) is more than 500 more than 98.0%, and the post partition method of mean chain length (Nf) (4) separate each cut that obtains with to(for) the insoluble part of dimethylbenzene accounts for more than the 10 all weight % in the total of the cut more than 800.

12. the manufacture method of propylene polymer composition is included at least a nucleating agent of the acrylic polymer fusion 0.05-15 weight % that claim 9-11 makes in each.