CN1030771C - Process for producing olefin polymers and catalyst used therein - Google Patents

Abstract

A solid catalyst component for .alpha.-olefin polymerization containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 .mu.m and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 .ANG., a catalyst system comprising at least said solid catalyst component (A) and an organoaluminum compound (B), as well as a process for producing .alpha.olefin polymers using said catalyst system.

Description

Process for producing olefin polymers and catalyst used therein

The present invention relates to be used for a kind of ingredient of solid catalyst of alpha-olefin polymerization, the catalyst system that contains described ingredient of solid catalyst, the method for using described catalyst system production alpha-olefinic polymer and the polymkeric substance for preparing by described method.More particularly, the present invention relates to produce the method for alpha-olefinic polymer, particularly, utilize a kind of each transition metal atoms to have the ingredient of solid catalyst catalytic preparation of high catalytic activity by polymerizations such as slurry polymerization, bulk polymerization, gas phase polymerizations.Granular elastomer and the elastomeric method of particulate thermoplastic with high-bulk-density and low levels fine powder wherein can save operation of removing residual catalyst and amorphous polymer and the particle shape that can control ingredient of solid catalyst satisfactorily.

As everyone knows, in general, belong to the transistion metal compound of the IV to VI of family in the periodictable and the Ziegler-Natta catalyst of the organometallic compound composition that belongs to the metal of I to III in the periodictable, can be used for producing alpha-olefinic polymer, for example propylene, butene-1 etc.

Particularly in the industrial production of alpha-olefinic polymer class, be extensive use of titanium trichloride catalyst.

Yet, in aforesaid method,, also formed the by product amorphous polymer except the high upright structure alpha-olefine polymerizing beyond the region of objective existence of industrial value.

The industrial applicability of this amorphous polymer is very poor, and is processed to goods when alpha-olefinic polymer, for example when film, fiber etc., produces very adverse influence for the mechanical property of alpha-olefinic polymer.

Say that further from the viewpoint of industry, the formation of amorphous polymer also is disadvantageous, promptly it causes the starting monomer loss, and the specific installation that is used for removing amorphous polymer will be provided.

Therefore, if can eliminate the formation of amorphous polymer or be reduced to considerably less amount, this will produce very big benefit so.

In addition on the one hand, be contained in the catalyzer of certain residual quantity, see from stability, processing characteristics etc. to produce various problem by the alpha-olefinic polymer class of such polymerization technique preparation.Therefore, provide and be used for removing the residual catalyst special device and stabilization is very necessary.

If catalyzer has very high activity (representing with the alpha-olefinic polymer weight that the per unit weight catalyzer produces), this rough sledding can overcome.If use such catalyzer, can economize and get rid of the residual catalyst device, this can reduce the alpha-olefinic polymer productive expense.

In the past, [in Japanese Patent Application Publication (disclosing unsettled) № 61-287,904, (United States Patent (USP) 4,672,050)], the present inventor has found a kind of catalyst system, it consists of:

(1) ingredient of solid catalyst that contains trivalent titanium compound that obtains by processing-solid product, this cured product can be by in the presence of the silicoorganic compound that contain the Si-O key, use a kind of organo-magnesium compound, reduce a kind of titanium compound with the mixture of a kind of ester cpds and ester cpds and titanium tetrachloride and be prepared from, the general formula of this titanium compound is expressed as:

Ti(OR′)nX ₄－n

(R ' representative contains the alkyl of 1 to 20 carbon atom, and X represents halogen atom, and the number of 0＜n≤4 is satisfied in the n representative);

(2) a kind of organo-aluminium compound; And

(3) a kind of Si-OR of containing " key (R " representative contains the alkyl of 1 to 20 carbon atom) silicon compound, it demonstrates high activity and high specificity in alpha-olefin polymerization.

Yet, work as solid catalyst, when for example Ziegler-Natta catalyst carries out industrial practical application, the form of granules of catalyst plays important effect to the size and the mobility aspect thereof of controlling polymers tap density polymer beads, from the viewpoint of the particle form of solid catalyst, foregoing invention can't be satisfactory.

In the polyreaction of ethene, disclosing some attempts to use the curing catalysts of uploading titanium-magnesium compound preparation at silica gel to improve the patent of particle form [Japanese Patent Application Publication (disclosing unsettled) № 54-148,093 and 56-47,407 (United States Patent (USP)s 4,315,999)].

In addition, the present inventor has also proposed a kind of method, improves the method [Japanese Patent Application Publication № 62-256802] of particle characteristics by the solid catalyst with titanium-magnesium compound dipping preparation of silica gel.Although particle form can improve greatly by these methods, yet still remain in large quantities in the product as the silica gel of carrier, this can cause the quality that produces flake reduction product in the film.

On the other hand, by preparing polypropylene or other olefin resin and olefin copolymer rubber (for example ethylene-propylene rubber(EPR) etc.) at first respectively, oneself prepares olefinic thermoplastic elastomer so far with the method for their blend then.Yet well-known, from the viewpoint of cost, such technology should not adopt, because olefin copolymer rubber is normally by the solution polymerization process preparation, and olefin copolymer rubber and olefin resin blend needs very superpower and lot of energy.

On the other hand, at Japanese Patent Application Publication (disclosing unsettled) № s.55-80418 and 57-61, propose two step slurry polymerization processes in 012 (United States Patent (USP) 4,489,195), directly prepared thermoplastic elastomer under given conditions.Yet this technology also should not adopt, and promptly ethylene-propylene random copolymer is dissolved in the solvent in large quantities, has increased the viscosity of system, makes to be difficult to discharge heat of polymerization, and this impels the bonding of polymer particles intergranular greatly, and makes production technique be difficult to stable operation.With regard to addressing this problem, proposed under very low temperature (being lower than 30 ℃), to carry out ethene and propylene random copolymerization.Yet this method also has shortcoming, and promptly under such condition, activity of such catalysts is very low, and large-scale chilling unit is used to remove heat of polymerization, also is uneconomic therefore.

In addition, at Japanese Patent Application Publication (disclosing unsettled) №, 59-105 has proposed the preparation technology by the legal thermoplastic elastomer of gas phase two steps in 008 (Canadian Patent 1,219,996).Though in this technology, a kind of inorganic oxide, for example silica gel reduces the cohesive force of polymer beads as the carrier of ingredient of solid catalyst, and improvement effect still can not be satisfactory.

Olefin elastomer normally prepares by solution polymerization process.Solution polymerization process needs many steps, for example reclaim unreacted monomer, remove ash, washing or the like and resulting polymkeric substance exist with solution state, therefore system has very high viscosity, is difficult to stir, and temperature is not easy control, therefore from the viewpoint of production cost, this technology is backward.

With regard to ways of addressing this issue,, in 306, the slurry polymerization process of ethene and propylene has been proposed, i.e. random copolymerization in propylene liquid at Japanese patent application public affairs (disclosing unsettled) № 59-71.Though this process modification production efficiency, but this technology must be carried out under very low temperature (being lower than 40 ℃), therefore this technology relates to various problems, such as having reduced activity of such catalysts, need large-scale refrigeration unit to remove heat of polymerization, or the like, these all are backward from industrial theory.

In addition, at Japanese Patent Application Publication (disclosing unsettled) № 59-230, in 011 (Canadian Patent 1,219,400), vapour phase polymerization direct production olefin elastomer has been proposed.Yet, in this technology, must adopt low polymerization temperature, and in order to prevent the bonding of polymer beads and stably to carry out gas phase polymerization, treat that the polymeric monomer must be with a large amount of rare gas elementes, for example nitrogen or congener dilute.Therefore, this explained hereafter efficient is low, and industrial saying is backward.

From above-mentioned situation as can be seen, the problem to be solved in the present invention, purpose promptly of the present invention provides a kind of polymerizing catalyst, and this catalyzer has very high catalytic activity, so that needn't remove catalyst residue and amorphous polymer; A kind of technology is provided, this technology is used described Catalyst Production alpha-olefinic polymer, it is high and fine powder content is low and do not contain the alpha-olefinic polymer of inorganic oxide (described inorganic oxide is silica gel for example to obtain tap density with described catalyzer, when polymkeric substance is used as film, can produce flake); A kind of polymkeric substance by described prepared is provided.

In addition, another object of the present invention is the problems referred to above that solve prior art, thereby a kind of technology is provided, and this process using gas phase polymerization process is prepared very good particle olefinic thermoplastic elastomer of performance and particle olefin elastomer.In addition, another object of the present invention is that the particle olefin thermoplastic body and the particle elastomerics that adopt described polymerization technique preparation are provided.

Ethylene-propylene rubber(EPR) and analogue thereof contain the polymkeric substance that has low-crystallinity in a large number, and their polymer beads has very strong adhesion usually.Therefore, under the situation of such polymkeric substance, stably carry out the gas-phase (co-) polymerisation reaction and be difficult to.

With regard to the gas-phase polymerization reactor of alpha-olefines, stirring-mixing tank type reactor has been proposed up to now, fluid bed-type of reactor has the fluid bed-type of reactor of agitator, or the like.Because the sticking power of polymer beads increases,, like this, bring sizable difficulty to Design of device so need very high power to reach desired stirring velocity in the stirring-type reactor.In addition, under such state, uniform mixing is difficult to reach, some part still is in the high-temperature zone, this is because a part of polymkeric substance has been formed bulk, has damaged agitator and the thermometer in the reactor, makes polymer beads extract out very difficult by pipeline from reactor.

On the other hand, in reactor, there is a kind of slagging trend in unreacted monomer with the fluidized state polymerization in this reactor, and this trend has increased polymer beads significantly and flown into the amount of gas circulation pipeline, and deposits in pipeline, makes it to stop up.

In addition, in this state, have a problem, the difficulty of Jiao Baning causes the local polymer blocks that generates exactly.

In addition, when polymer beads has very strong adhesive force, in carrying the particulate pipeline, be easy to stop up.In addition, bottom or the hopper at cyclonic separator produces obstruction, this feasible being difficult to particle stabilized extraction.

Like this, adopt the gas-phase polymerization process preparation to contain the macromolecular material of a large amount of low crystallinity polymers, be actually very difficult, although vapour phase polymerization is advanced, it does not need the polymkeric substance of dissolution with solvents low-crystallinity.

In addition, the removing step that in improved gas-phase polymerization process, has saved residual catalyst basically.Like this, wherein the polymerization activity of employed catalyst system must improve greatly.

The present inventor adopts specific catalyst system, has solved above-mentioned some problems, and finds an effective technology, by gas phase polymerization production performance very good alkene particle thermoplastic elastomer and particle elastomerics.

Therefore, the invention provides:

A kind of alpha-olefine polymerization solid catalyst component (A) is as catalyst component, this catalyst component contains titanium, magnesium and chlorine at least, they are submerged on a kind of organic porous polymer carrier, the median size of this carrier is 5～1000 μ m, pore volume is equal to or greater than 0.1m1/g, pore radius is 100～5,000 ;

A kind of catalyst system that contains described ingredient of solid catalyst (A) and a kind of organo-aluminium compound (B) at least; And

A kind of preparation particle thermoplastic elastomer and the elastomeric technology of particle, this technology comprises according to following 1) to 3) adopting described catalyst system in any one technology, polymerization of Alpha-olefin or copolymerization alpha-olefin are to obtain olefin polymer; 1) to 3) technology as follows:

1) technology, this technology comprises: first step,

At propylene liquid and/or in gas phase, prepare isotatic polypropylene by polyreaction, carry out second step then, a kind of ethene-alpha-olefin random copolymers of preparation in gas phase, so that the ethylene content in the multipolymer for preparing in second step reaches 5～95% (weight), and its limiting viscosity in 135 ℃ tetraline is 0.3～10, the multipolymer weight for preparing in second step, by total polymer weight, account for 60～97% (weight);

2) technology, this technology comprises: first step, in propane solvent or butane solvent, slurry polymerization ethene or gas-phase polymerization ethylene, carry out second step then, adopt gas phase polymerization to prepare the ethene-alpha-olefin random copolymers, so that the ethylene content in the multipolymer for preparing in second step reaches 5～95% (weight), its limiting viscosity in 135 ℃ tetraline reaches 0.3～10, and the weight of the multipolymer for preparing in second step accounts for 60～97% (weight) of total polymer weight;

3) technology, this technology comprises: carry out the random copolymerization of ethene and alpha-olefin in gas phase, so that the ethylene content in the multipolymer of such preparation reaches 5～95% (weight), its limiting viscosity in 135 ℃ tetraline reaches 0.3～10; Obtain alkene particle thermoplastic elastomer or particle elastomerics by described technology then.

Fig. 1 is the grain size distribution curve of polypropylene powder, wherein (A), (B) and (C) represent at embodiment 21 grain size distribution curve of the polypropylene powder that obtains in embodiment 22 and the Comparative Examples 12 respectively.

Fig. 2 be one for being more readily understood the schema that the present invention draws.This schema is representative instance in the embodiment of the present invention, and the present invention never is limited to this schema.

Details of the present invention will be described below.

(I) ingredient of solid catalyst (A)

Employed curing catalysts component among the present invention, by flooding a kind of Porous-Organic polymer support by the catalytic component of titaniferous, magnesium and chlorine at least and be prepared from a kind of, the average grain diameter of this polymer support is 5～1000 μ m, and pore volume is equal to or greater than 0.1ml/g (when pore radius is 100～5000 ).

The desired performance of catalyst of the present invention comprises: it can have sufficiently high activity in ethylene ' alpha '-olefin random copolymerization, and prepares the copolymer of function admirable; It can form the polymer beads with good particle characteristics; Etc.. In addition, when carrying out the multi-step polymerisation in this technology, prepare the polymer that mainly is made up of polypropylene, requiring catalyst to have higher solid has then property.

According to present inventor's research, when catalytic component has very high catalyst activity, so that the formed total polymer of per 1 gram titanium atom in the curing catalysts component is 5 * 10⁴The gram or more than, best 7.5 * 10⁴Gram or more than, best 10 * 10⁴Gram or more than, when using this catalytic component, can prepare thermoplastic elastomer (TPE) and without any need for the step that is used for removing residual catalyst, so this suits.

When carrying out the propylene homogeneous polymerization, preferably use such catalyst system and catalyzing, so that in the polypropylene that obtains, viewpoint from performance of copolymer, like this preparation polypropylene have 10% (weight) or following steroselectivity, best 7% (weight) or below, the best be 5% (weight) or below, [representing with xylene soluble fraction (20 ℃) content, i.e. the weight of random polypropylene in the polypropylene of gained].

In order to prepare the copolymer with good particle characteristics, the average grain diameter of ingredient of solid catalyst is a key factor. Just, because the average grain diameter of body catalyst component should be 5～1000 μ m, 10～600 μ m preferably, the best is 15～500 μ m.

If average grain diameter is less than 5 μ m, in the fluidized bed type Gas-phase reactor, the adhesion strength of polymer beads increases, and produces the problem that catalyst and polymer beads disperse. If average grain diameter can not realize stable fluidized state greater than 1000 μ m in the fluidized bed type Gas-phase reactor, the minimum speed of fluidisation obviously increases, and polymer beads often lumps as a result.

Then, below the curing catalysts component will be described in further detail.

(a) titanium compound

Urge the general formula of the titanium compound of body agent composition to be expressed as Ti (OR ') aXb for the synthesis of curing used in the present invention, R ' represents the alkyl of 1 to 20 carbon atom in the formula, and X represents halogen atom, and 0≤a≤4 are satisfied in a and b representative, 0≤b≤4, a+b=3 or 4 number.

To describe the particular example that adopts below, wherein the general formula of titanium compound is expressed as Ti (OR ') nX₄-n, R ' represents the alkyl of 1 to 20 carbon atom in the formula, and X represents halogen atom, and the number of 0≤n≤4 is satisfied in the n representative. The instantiation of R ' comprises: alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, n-dodecane etc.; Aryl, for example phenyl, tolyl, xylyl, naphthyl, etc.; Cycloalkyl, for example cyclohexyl, cyclopenta, etc.; Allylic, acrylic for example, etc.; The aralkyl base class, benzyl for example, etc.

Among them, alkyl and aryl with 2～18 carbon atoms are preferred, and the straight chained alkyl class with 2～18 carbon atoms is particularly preferred.

Also can use the titanium compound with two or more different OR ' bases.

The example of the described halogen atom that X represents comprises: chlorine, bromine and iodine, the effect of chlorine is especially good in them.

Just synthetic general formula is Ti (OR ') nX_4－The method of n (0＜n≤4) titanium compound can adopt any known method. For example, Ti (OR ')₄And TiX₄Method and TiX with the certain proportion reaction₄All can adopt with the method for corresponding alcohol with the certain proportion reaction.

The instantiation that is preferred for compound of the present invention, that represented by aforementioned formula Ti (OR ') aXb comprises: titanium trichloride, ethyoxyl titanium chloride, butoxy titanium chloride, titanium tetrachloride, ethyoxyl titanium trichloride, butoxy titanium trichloride, phenoxy group titanium trichloride, dibutoxy titanium chloride, two phenoxy group titanium chloride, three butoxy titanium chlorides, purity titanium tetraethoxide, four titanium butoxide, four phenoxide titaniums, etc.

(b) contain the organo-silicon compound of Si-O key

With regard to optional containing with regard to the SiO organosilicone compounds in component of the present invention (A) synthetic, they are represented by following general formula:

Si(OR ³)mR ₄ ⁴－m

R ⁵(R ₂ ⁶SiO) _pSiR ₃ ⁷

(R ₂ ⁸SiO) R in the q formula ³Represent the alkyl of 1～20 carbon atom; R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Representative has 1～20 carbon atom alkyl or hydrogen atom respectively; The number of 0＜m≤4 is satisfied in the m representative; P is 1～1,000 integer; Q is 2～1,000 integer.

The specific examples of described organosilicone compounds comprises as follows:

Tetramethoxy-silicane, dimethyldimethoxysil,ne, tetraethoxysilane, triethoxy ethyl silane, the diethoxy diethylsilane, ethoxy triethyl silane, tetraisopropoxysilan, diisopropoxy di-isopropyl silane, tetrapropoxysilane dipropoxy dipropyl silane, four n-butoxy silane, two n-butoxy di-n-butyl silane, two cyclopentyloxy diethylsilanes, the diethoxy diphenyl silane, triethoxyphenylsilan, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, the octaethyl trisiloxanes, dimethyl polysiloxane, the phenylbenzene polysiloxane, the hydrogenated methyl polysiloxane, phenyl hydrogenation polysiloxane, or the like.

In these silicoorganic compound, by general formula Si (OR ³) mR ₄ ⁴The alkoxysilane compound containing trialkylsilyl group in molecular structure of-m representative is preferred, and m preferably satisfies the number of 1≤m≤4 in the formula.In them, quaalkane oxosilane compound (m=4) is particularly preferred.

(C) organo-magnesium compound

With regard to magnesium compound, use following compound.

With regard to the reductibility compound that contains magnesium-carbon bond, preferably use Grignard compound, its expression general formula is that (R ' is the alkyl of 1～20 carbon atom to R ' Mg X in the formula, X is a halogen atom), with dialkyl group or diaryl magnesium compound, it expresses general formula is R " R ' " Mg (R in the formula " and R ' " is respectively the alkyl of 1～20 carbon atom).R ', R " and R ' " can be identical or different, and be respectively alkyl, aryl, aralkyl or alkenyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, n-octyl, 2-ethylhexyl, phenyl, benzyl, or the like.

With regard to containing magnesium-hydrogen bond reductibility compound, preferably use the hydrogenation alkyl magnesium.The specific examples of above-claimed cpd comprises as follows: magnesium ethide, dibutylmagnesium, dihexyl magnesium, ethyl-magnesium-chloride, butyl magnesium chloride, chlorination hexyl magnesium, butyl magnesium ethylate, hydrogenation dibutyl magnesium, or the like be preferred the employing.These magnesium compounds can form the form use of title complex with organo-aluminium compound.On the other hand, the preferred embodiment of irreducibility magnesium compound comprises: two fontanel magnesium classes, and for example magnesium dichloride, dibrominated magnesium, or the like; The alkoxyl magnesium compounds, for example methoxyl group chlorination magnesium, oxyethyl group magnesium chloride, butoxy magnesium chloride, phenoxy group magnesium chloride, diethoxy magnesium, dibutoxy magnesium, two phenoxy group magnesium, or the like; The magnesium carboxylates class, for example Magnesium monolaurate, Magnesium Stearate, or the like.

Described irreducibility magnesium compound can be a kind of like this compound, and this compound is before the preparation curing catalysts, also can know technology with oneself during the course, derives out from the reductibility magnesium compound.

(d) organic porous polymer carrier

The example of employed organic porous polymer carrier comprises in the curing catalysts component of the present invention (A): polystyrene type, polyacrylate, polymethacrylate type, polyacrylonitrile type, polyvinyl chloride-type, polyolefin-type porous polymer particles, or the like.The specific examples of carrier component comprises: polystyrene, styrene diethylene benzene copoly mer, vinylbenzene-N, N '-alkylidene group diisobutylene base amide copolymer, vinylbenzene-methyl di glycol ester multipolymer, polymethacrylate, poly-ethyl propylene acid esters, methacrylic ester-divinyl benzene copolymer, ethyl propylene acid esters-divinyl benzene copolymer, polymethylmethacrylate, methyl methacrylate-divinyl benzene copolymer, poly-methyl di glycol ester, polyacrylonitrile, vinyl cyanide-divinyl benzene copolymer, polyvinyl chloride, polyvinylpyrrolidone/, polyvinylpyridine, vinyl xylene, ethyl vinyl benzene-divinyl benzene copolymer, polyethylene, the ethylene-methyl acrylate multipolymer, polypropylene, or the like.

In the material of these porous polymer spherolites, polystyrene type, polyvinyl chloride, polyolefins and polypropylene nitrile are preferred, and polystyrene type, styrene diethylene benzene copoly mer and polyvinyl chloride are particularly preferred.

The median size of porous polymer spherolite is 5～1,000 μ m, and 10～600 μ m preferably, the best is 15～500 μ m.In addition, be 100～5,000 in the actual measurement scope of pore radius, the pore volume of measuring it is equal to or greater than 0.21ml/g, preferably is equal to or greater than 0.2ml/g, and the best is equal to or greater than 0.25ml/g.

Porous polymer re-uses after being preferably in the water of removing absorption.Specifically, porous polymer under about 80 ℃ or above temperature, drying under reduced pressure, and then use.In addition, it can use organometallic compound then 60 ℃ or above drying, for example processing such as organic-magnesium, and then use.

(e) ester cpds

With regard to the ester cpds that can select arbitrarily to use in component of the present invention (A) synthetic, can use monocarboxylic ester class and multi-carboxylate's class, they comprise: alphatic carboxylic acid ester class, ethylenic carboxylate's class, alicyclic carboxylic ether's class and aromatic carboxylic acid ester class.The specific examples of described ester cpds comprises: methyl acetate, ethyl acetate, phenylacetate, methyl propionate, ethyl propionate, ethyl butyrate, Valeric acid ethylester, methyl acrylate, ethyl propenoate, methyl methacrylate, ethyl benzoate, butyl benzoate, the toluic acid methyl esters, ethyl toluate, ethyl anisate, ethyl succinate, dibutyl succinate, diethyl malonate, butyl ethyl malonate, dimethyl maleate, dibutyl maleinate, diethyl itaconate, dibutyl itaconate, phthalic acid-ethyl ester, dimethyl phthalate, the phthalic acid methyl ethyl ester, diethyl phthalate, phthalic acid diethyl propyl ester, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, heptyl phthalate ester, dinoctyl phthalate, diphenyl phthalate, or the like.

In these ester cpds, ethylenic carboxylate's class, for example methacrylic ester, maleic acid ester or the like are preferred with phthalate, phthalate esters is particularly preferred.

(f) ether compound

In synthetic component A of the present invention, can selectively use ether compound arbitrarily.The ether compound preferred embodiment comprises: dialkyl ether, for example diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, two n-amylethers, isoamyl ether, di neo-pentyl ether, two n-hexyl ethers, two octyl ethers, methyl n-butyl ether, methyl isoamyl ether, ethyl isobutyl ether, or the like.

In them, di-n-butyl ether and diisoamyl ether are particularly preferred.

(G) ingredient of solid catalyst A's is synthetic, will specify below to be used to flood organic porous polymer carrier, at least the catalyst component formed of titaniferous, magnesium and chlorine.

In catalyst component of the present invention, titanium/magnesium atom ratio is 0.01 to 0.8, best 0.02 to 0.2.Chlorine/magnesium atom ratio is 1.8～10, best 2.0～5.0.

With regard to the method for preparing this catalyst component, can be referring to such certain methods, for example, at Japanese patent laid-open publication gazette №, 35-495, Japanese Patent Application Publication (disclosing unsettled) №, 46-4393, Japanese patent laid-open publication gazette № 46-31330, Japanese Patent Application Publication (disclosing unsettled) № 47-42283, Japanese Patent Application Publication (disclosing unsettled) №, 49-86483, Japanese patent laid-open publication gazette №, 57-24361, Japanese Patent Application Publication (disclosing unsettled) №, 61-296,007, Japanese patent laid-open publication gazette №, 39-12105,43-13050, day 46-34092,46-34098,47-41676,55-23561, or the like in introduction is arranged.

With regard to the method for flooding organic porous polymer carrier with catalyst component, can adopt mechanical means, for example pulverize etc. and the chemical process of pulpous state attitude.In these methods, from the viewpoint of particle characteristics, chemical process is recommendable.

Specific examples about aforesaid method, can adopt the method for flooding porous support (for example silica gel etc.) with catalyst component, this method is disclosed in Japanese Patent Application Publication (separately unsettled) № 52-42585,54-148093,56-47407,59-230006 and 61-37803.

About the example of described method, can be with reference to following method:

(1) a kind of organo-magnesium compound of using, for example Grignard reagent etc. is handled porous support, and then the method for handling with TiCl or its analogue.

(2) a kind of organo-magnesium compound of using, for example Grignard reagent etc. is handled porous support, then and a kind of halide reagent and/or a kind of alcohol reaction, and then with the method for a kind of titanium compound (for example TiCl) processing.

(3) a kind of a kind of halogenated magnesium compound and/or a kind of alkoxy aluminum compound are dissolved in a kind of electron donor (for example alcohol, ether etc.), then make itself and TiCl ₄Form a kind of title complex, and then it is immersed in method in the porous support.

(4) a kind of with a kind of halogenated magnesium compound and/or a kind of alkoxyl magnesium compound dissolution in a kind of electron donor (for example alcohol, ether etc.), then it is immersed in during porous carries, and then uses a kind of titanium compound, for example TiCl ₄The method of handling.

(5) a kind ofly in the presence of porous support, use organo-magnesium compound, Grignard reagent etc. for example, the reduction alkoxy titanium compound, and then with a kind of method of mixture process of ether compound one titanium tetrachloride.

In these methods, method (5) is preferred.Following method is promptly in the presence of a kind of silicoorganic compound and a kind of organic porous polymer carrier that contain the Si-O key, reduce a kind of alkoxy titanium compound with a kind of organo-magnesium compound (for example Grignard reagent etc.), obtain a kind of solid product, use the mixture process of a kind of ether compound and titanium tetrachloride then, or be particularly preferred with the method for the mixture process of a kind of ester cpds and a kind of ether compound and titanium tetrachloride.

The amount that is immersed in the catalyst component in organic porous polymer carrier is 1～70% (weight), 3～60% (weight) preferably, and the best is 5～55% (weight) (representing with the content in the product ingredient of solid catalyst).If it is too high to be immersed in the content of the catalyst component in organic porous polymer carrier, then the particle characteristics of polymkeric substance reduces.If its content is too little, the activity of the solid catalyst of per unit weight can reduce.

To narrate aforesaid method in more detail below.

Concrete preparation example about preparation ingredient of solid catalyst of the present invention, a kind of method is below described, it is included in, and a kind of organic porous polymer carrier of a kind of Si-O of containing key silicoorganic compound is common to be existed down, reduce a kind of alkoxy titanium compound with a kind of organo-magnesium compound, then, handle the reductive titanium compound with a kind of ester cpds, and then handle the compound that ester was handled with a kind of ether compound and titanium tetrachloride.Yet ingredient of solid catalyst of the present invention is not limited to description below.

All building-up reactionss are at inert atmosphere, and for example nitrogen, argon etc. carry out down.

Therefore, by containing in the presence of Si-O key silicoorganic compound and a kind of organic porous polymer carrier, reduce a kind of organo-magnesium compound with a kind of titaniferous compound and come the synthesis of solid product a kind of.Desiredly in the reaction be, the deposition of solids that forms by reduction is on the particle of porous polymer carrier, and like this, solid product keeps poromeric form, and does not form any fine powder.Method about with organo-magnesium compound reduction titanium compound for example can be about to a kind of organo-magnesium compound and be added to a kind of by the method in the mixture of a kind of titanium compound, a kind of silicoorganic compound and porous polymer spherolite with reference to a kind of like this method.

Preferably titanium compound, silicoorganic compound and porous polymer spherolite are dissolved in a kind of appropriate solvent, promptly use a kind of solvent cut they, re-use them afterwards.

About described solvent, can reference be aliphatic hydrocarbon, for example hexane, heptane, octane, decane etc.; Arene, for example toluene, dimethylbenzene etc.; Alicyclic hydrocarbon type, for example hexanaphthene, methylcyclohexane, naphthalane etc.; With the ether compound class, for example diethyl ether, dibutyl ether, isoamyl ether, tetrahydrofuran (THF) etc.

The temperature of reduction reaction is-50 ℃～70 ℃, best-30 ℃～50 ℃, and best-25 ℃～35 ℃.

Though the dropping time is not crucial, normally about 10 minutes to 6 hours.If necessary, after reduction reaction is finished, under 20 ℃～120 ℃ temperature, carry out postreaction.

The amount ranges of silicoorganic compound is Si/Ti=1～50, and is best 3～30, best 5～25 (press in the titanium compound Siliciumatom represent than (Si/Ti) with titanium atom).

The organo-magnesium compound amount ranges is (Ti+Si)/Mg=0.1～10, and is best 0.2～5.0, best 0.5～2.0 (total amount and magnesium atom by titanium atom and Siliciumatom are represented than (Ti+Si)/Mg).

The consumption of porous polymer spherolite is a kind of like this consumption, and promptly its weight in solid product reaches 20～95% (weight), best 30～85% (weight).

The solid product of reduction reaction preparation is isolated from liquid phase, used unreactive hydrocarbons solvent then, for example hexane, heptane etc., flushing several times.

Then, the solid product that makes is as stated above handled with a kind of ester cpds.

For titanium atom in each mole solid product, the consumption of ester cpds is 0.1～50 mole, and best 0.3～20 mole, the best is 0.5～10 mole.

For magnesium atom in each mole solid product, the consumption of ester cpds is 0.01～10 mole, best 0.03～0.5 mole.

Handle solid product with ester cpds, can be undertaken, for example starch method, ball mill mechanical crushing method etc. by any known method that they are in contact with one another.But in these methods, from the viewpoint of industry, the method for mechanical disintegration is not a preferable methods, because it has produced a large amount of fine powders in ingredient of solid catalyst, thereby has widened size distribution.Preferably in the presence of thinner, two kinds of materials are in contact with one another.

The thinner that can be used for this kind purpose comprises aliphatic hydrocarbon, for example pentane, hexane, heptane, octane etc.; Aromatic hydrocarbons, for example benzene,toluene,xylene etc.; Alicyclic hydro carbons, for example hexanaphthene, pentamethylene etc.; Halogenated hydrocarbons, for example 1,2-ethylene dichloride, mono chloro benzene etc.In these thinners, halogenated hydrocarbons and aromatic hydrocarbons are particularly preferred.

The thinner consumption of per 1 gram solid product is 0.1ml～1.000ml, preferably 1ml～100ml.Treatment temp is-50 ℃～150 ℃, is preferably 0 ℃～120 ℃.The processing cycle is 10 minutes or longer, preferably 3 minutes～3 hours.After finishing dealing with, standing mixt is isolated solid from liquid phase, wash several times with unreactive hydrocarbons solvent then.Obtain the solid product that a kind of ester is handled like this.

When handling, also can in the presence of ether compound and titanium tetrachloride mixture, utilize ether compound, carry out aftertreatment with ether compound and titanium tetrachloride mixture with ester cpds.

Then, the solid product with ether compound and titanium tetrachloride mixture process ester were handled preferably carries out under slurry form.About the solvent of preparation slurry, this refers to aliphatic hydrocarbon, for example pentane, hexane, heptane, octane, decane etc.; Arene, for example toluene, dimethylbenzene etc.; Clicyclic hydrocarbon, for example hexanaphthene, methylcyclohexane, naphthalane etc.; Halogenated hydrocarbons, for example ethylene dichloride, trichloroethane, trieline, mono chloro benzene, dichlorobenzene, trichlorobenzene etc.

Slurry concentration is 0.05～0.5 gram solid/milliliter solvent, is preferably 0.1～0.4 gram solid/milliliter solvent.

Temperature of reaction is 30 ℃～150 ℃, best 45 ℃～120 ℃, and best 60 ℃～100 ℃.

Though the reaction times is not crucial, the usually preferred reaction times is 30 minutes～6 hours.

The charging process of the solid product that ester was handled, ether compound and titanium tetrachloride can be any in the following method, and promptly ether compound and titanium tetrachloride are added to the method in the solid product that ester handled and the solid product also can the reversed sequence ester handled is added to method in a kind of ether compound and the titanium tetrachloride solution.

In ether compound and titanium tetrachloride are added to method in the solid product that ester handled, the method that the method for adding titanium tetrachloride or etherate and titanium tetrachloride added simultaneously after ether compound added is preferred, and the method that adds the mixture of previously prepared ether compound and titanium tetrachloride is particularly preferred.

Reaction between solid product that ester was handled and ether compound and the titanium tetrachloride can repeat twice or repeatedly.From the viewpoint of catalyst activity and stereospecificity, recommend to repeat two secondary responses at least with the mixture of ether compound and tetracol phenixin.

The consumption of ether compound is 0.1～100 mole of a titanium atom in every mole of solid product, is preferably 0.5～50 mole, particularly 1～20 mole.

The amount of titanium tetrachloride to be added is 2～2000 moles of titanium atoms in every mole of solid product, is preferably 10～1000 moles, particularly 30～800 moles.

For every mole of ether compound, the amount of titanium tetrachloride to be added is 1～100 mole, is preferably 1.5～74 moles, particularly 2～50 moles.

The ingredient of solid catalyst that contains trivalent titanium compound that obtains is as stated above gone out from liquid phase separation, and wash several times such as unreactive hydrocarbons solvents such as hexane, heptane, then prepare to be used for polymerization with a kind of.

Viewpoint from catalyst activity and stereospecificity, solid product is isolated in recommendation from liquid phase, and a kind of excessive aromatic hydrocarbon (as toluene etc.) or halogenated hydrocarbon solvent (as mono chloro benzene etc.) at 50 ℃～120 ℃ with its washing at least twice, use a kind of aliphatic solvents (as hexane etc.) with its repeated washing (several times) then, and prepare to be used for polyreaction.

(II) organo-aluminium compound (B)

Be used from organo-aluminium compound of the present invention (B) with above-mentioned ingredient of solid catalyst (A), in a molecule, have an aluminium-carbon bond at least.Its typical example is represented by following general formula:

R ⁹rAlY _3-r

R ¹⁰R ¹¹AL-O-ALR ¹²R ¹³R wherein ⁹, R ¹⁰, R ¹¹, R ¹²With ¹³Each representative has the alkyl of 1-8 carbon atom; Y represents the plain atom of fontanel, hydrogen atom or alkoxyl group; R represents a number that satisfies 2≤r≤3.

The specific examples of organo-aluminium compound comprises the trialkylaluminium class, for example triethyl aluminum, triisobutyl aluminium, three hexyl aluminium etc.; Hydrogenation aluminum dialkyl class, for example diethyl aluminium hydride, diisobutylaluminium hydride etc.; The mixture of trialkylaluminium and halo aluminum dialkyl; Alkylaluminoxane class, for example tetraethyl-two aikyiaiurnirsoxan beta, the tetrabutyl two aikyiaiurnirsoxan beta etc.

In these organo-aluminium compounds, trialkylaluminium class, trialkylaluminium and fontanel are recommended for the mixture and the alkylaluminoxane of aluminum dialkyl, and triethyl aluminum, triisobutyl aluminium, triethyl aluminum and fontanel are particularly preferred for the mixture and tetraethyl-two aikyiaiurnirsoxan beta of diethyl aluminum.

The consumption of described organo-aluminium compound is very wide, and the titanium atom in every mole of solid catalyst is 1～1,000 mole.The most preferred scope of its consumption is 5～600 moles of every mole of titanium atoms.

(III) electron donor (C)

For the molecular weight of telomerized polymer,, when polyreaction, a kind of known electron donor can be added in the system perhaps in some cases in order to improve the stereospecificity of polymkeric substance.About described electron donor (C), use a kind of being selected to have Si-OR ²Key (R ²Represent a alkyl with 1-20 carbon atom) or the compound of silicoorganic compound, aromatic carboxylic acid's ester cpds and the steric hindrance amine of Si-N-C key.

Described silicoorganic compound preferably use by general formula R ¹⁴TSi (OR ²) 4-t (R ¹⁴And R ¹²Each represents an alkyl with 1-20 carbon atom, and t represents a number that satisfies 0≤t≤3) alkoxysilane compound containing trialkylsilyl group in molecular structure of representative.

The example of aromatic carboxylic acid ester comprises methyl benzoate, ethyl benzoate, Propyl benzoate, isopropyl benzoate, the positive butyl ester of phenylformic acid, phenol benzoate, the toluic acid methyl esters, ethyl toluate, p-Methoxybenzoic acid methyl ester, ethyl anisate, phthalic acid-ethyl ester, dimethyl phthalate, the phthalic acid methyl ethyl ester, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, heptyl phthalate ester, dinoctyl phthalate, diphenyl phthalate etc.

The example of described bulky amine comprises 2, the piperidines that 6-replaces, 2, the pyridine that 5-replaces, and the methylene diamine compounds that replaces, routine N, N, N ' N '-tetramethyl-methylene diamine etc.

In these electron donors, general formula (R ¹⁴TSi (OR ²) the alkoxysilane compound containing trialkylsilyl group in molecular structure class of 4-t representative provides good especially result.

This alkoxysilane compound containing trialkylsilyl group in molecular structure specific examples comprises: tetramethyl oxosilane, methyltrimethoxy silane, dimethyldimethoxysil,ne, ethyl trimethoxy silane, phenyltrimethoxysila,e, phenyl methyl dimethoxy silane, tetraethoxysilane, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, phenyl triethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, butyl triethoxyl silane, four butoxy silanes, vinyl three butoxy silanes, diethyl diethoxy silane, or the like.

For the aluminium atom in every mole of organo-aluminium compound (B), giving the consumption of electric body is 0.01～5 mole, is preferably 0.03～3 mole, particularly 0.05～1.0 mole.

(IV) polymerization process

(1) with regard to catalyst component adds with anhydrous state under inert atmosphere (as nitrogen, argon gas etc.), it is not crucial that their add the method for polymerization reactor.

Ingredient of solid catalyst (A), organo-aluminium compound (B) and the electron donor of selecting for use arbitrarily (C) both can add individually, also can add after two kinds of contacts in advance in them.

When producing crystalline polymer, adopt in the following method.

Polyreaction can be carried out in-30 ℃～200 ℃ very wide temperature ranges.But if temperature is lower than 0 ℃, then polymerization velocity reduces; And temperature is higher than 100 ℃, can not obtain having the polymkeric substance of very high stereospecificity.So, in general be recommended under 0～100 ℃ of temperature and carry out polyreaction.Though the pressure of polyreaction is not strict, from industry and economic viewpoint, it is more satisfactory to be about 3～100 atmospheric pressure ratios.Polyreaction can be undertaken by continuous processing and batchwise polymerization thing method.Can also adopt the slurry polymerization process of using a kind of inert solvent (as propane, butane, pentane, hexane, heptane, octane etc.), not adopt the liquid polymer method and the gas phase polymer method of solvent.

The applicable alpha-olefin of the present invention is those alkene with 3 or a plurality of carbon atoms, and their specific examples comprises: propylene, heptene-1, amylene-1, and hexene-1,3-methylpentene-1,4-methylpentene-1, or the like.But the present invention never is subjected to the restriction of above-claimed cpd.Polymerization of the present invention can be any homopolymerization and copolymerization, is included with the copolymerization of ethene.

In carrying out copolyreaction, the mutual blended of two or more alkene contacts, thereby can obtain their multipolymer.In addition, the block copolymerization of also can easily mixing, in this copolymerization, polymerization is the two or more steps of branch.

For the molecular weight of controlling polymers, also can add chain-transfer agent, for example hydrogen etc.

(2) in addition, the invention provides a kind of method of producing granular elastomer, this method comprises the gas phase random copolymerization that carries out ethene and alpha-olefin with above-mentioned catalyst system, and the present invention also provides a kind of method of producing the particle thermoplastic elastomer, and this method consists essentially of two steps.

To narrate the concrete scheme of polymeric below,

Producing in the granular elastomer process by ethene and alpha-olefin gas-phase copolymerization, the alpha-olefin that carries out copolymerization with ethene comprises propylene, butene-1, propylene-1, hexene-1,4-methylpentene-1,3-methylpentene-1 etc., among them, what recommended most is propylene and butene-1.

In copolymerization of the present invention, in order to obtain the sulfuration of polymkeric substance fast, a kind of polyenoid can be in addition and ethene and alpha-olefin carry out copolymerization.Described polyenoid specific examples comprises: divinyl, Dicyclopentadiene (DCPD), 1,3,7-sarohornene, vinyl cyclohexane, 5-second diene-the 2-norborneol is rare, 5-isopropenyl-2-nirbornene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, or the like, among them, the non-conjugated diene class is preferred, and is good with the straight chain conjugated diene especially.

In ethene-alpha-olefin copolymer, ethylene content is 5～95% (weight), is preferably 15～90% (weight).If ethylene content surpasses above-mentioned scope in the multipolymer that forms, then the rubber property of product is damaged.If its content is lower than above-mentioned scope, then cold property and rubber property will be damaged.

When copolyreaction is carried out in the presence of propylene, control reaction, so that the iodine number of its multipolymer reaches 2～50, be preferably 3～40.

In the present invention, with the variation of ethylene concentration, polyreaction can be in two steps or multistep carry out.In this case, can in the first step, make the equal polymerization of ethene or alpha-olefin proceed to very low degree (for example,, arriving about 3% (weight) or lower degree) according to the total amount meter of polymkeric substance.

Best, polymerization is to dissolve temperature not being higher than polymkeric substance, preferably at 20～85 ℃, particularly carries out at 40～75 ℃, and the pressure of polyreaction is normal pressure to 3.9 * 10 ⁶Pa, polymerizing condition do not make monomer liquefaction in polymerization reactor.In order to control the molten properties of flow of final product, preferably hydrogen is added polymerization with in the gaseous mixture as molecular weight regulator.But, use too a large amount of rare gas element (surpassing 25% (mole)) unsatisfactory, because of it has obviously reduced production efficiency as its amount.

With in 135 ℃, the limiting viscosity of in 1,2,3,4-tetralin, measuring [η] expression, the molecular weight of the ethene-alpha-olefin random copolymers that polyreaction forms between 0.3～10, preferably 0.5～8, particularly 1～5.If [η] is too low, can not get enough tensile strength.In the present invention, can also produce the particle thermoplastic elastomers by the methods that mainly comprised for two steps, described two-step approach is the equal polymerization of carrying out propylene or ethene before the gas phase random copolymerization of above-mentioned ethene and α-alkene (below be called " step 1 ").

Carrying out the equal polymerization reaction of propylene in the step 1 carries out in liquefied propylene and/or gas phase.Effect of the present invention can reach by following any method, and these methods comprise: carry out polymerization in liquefied propylene; Polymerization in liquefied propylene, polymerization in gas phase then; And in gas phase, carry out polymerization.

Secondly, under the situation of equal polymerization propylene, the aggregation scheme of step 1 is as described below in step 1.

For example, polyreaction is undertaken by independent polypropylene itself, also can make propylene and a kind of comonomer (ethene or have the alpha-olefin of 4～6 carbon atoms) carry out copolymerization.In this case, should regulate the amount of comonomer, so that make the content of comonomer in the multipolymer that obtains preferably reach 6% (mole) or lower, the best is 4% (mole) or lower.

When in liquefied propylene, carrying out polymerization, be preferably in 40 ℃～90 ℃, 1.7 * 10 ⁶-4.9 * 10 ⁶Carry out polymerization under the Pa.On the other hand, when carrying out polymerization in gas phase, the melt temperature that is not higher than polymkeric substance, preferably 40 ℃～100 ℃, pressure is from normal pressure～3.9 * 10 ⁶Pa, and in polymerization reactor, do not carry out polymerization under the condition of liquefied monomer.In addition, in this method,, be preferably under the existence of a kind of molecular weight regulator (as hydrogen etc.) and carry out polymerization in order to improve the molten properties of flow of final product.

Ethylene homo is fashionable when carrying out in step 1, and step 1 is with slurry polymerization form in propane solvent or the butane solvent, or carry out with the vapour phase polymerization form of ethene.

To narrate in this case step 1 aggregation scheme more specifically below.

The polymerization of step 1 not only relates to the equal polymerization of ethene, and relates to ethene and a spot of copolymerization with alpha-olefin of 3～6 carbon atoms as comonomer.In this case, should control the consumption of comonomer, so that make its content in resulting multipolymer preferably reach 6% (mole) or lower, the best is 4% (mole) or lower.

When polymerization is when carrying out, be recommended in 40 ℃～95 ℃ and 1.7 * 10 in propane solvent or butane solvent ⁶-4.9 * 10 ⁶Carry out polymerization between the Pa.

On the other hand, when polymerization is when carrying out in gas phase, polymerization should be carried out below with under the condition: temperature is not higher than polymer melting temperature, preferably at 40 ℃～110 ℃; Pressure is from normal pressure to 4.9 * 10 ⁶Pa; In polymerization reactor, do not make monomer liquefaction.In addition, in this method,, be recommended under the situation of molecular weight regulator (as hydrogen etc.) and carry out polymerization for improving the molten properties of flow of final product.

In any case, the polymerization of step 2 is followed step 1 and is carried out.That is to say that the random copolymerization of ethene and alpha-olefin is to carry out in gas phase, its details is narrated in the above.

60～97% (weight) of the copolymer comprised polymkeric substance total amount that forms in the step 2 of the present invention are preferably 70～95% (weight), particularly 75～90% (weight).The polymkeric substance that forms in step 2 is many more, and the product that provides just is rich in rubbery more; And the polymkeric substance that forms in step 2 is few more, and the product that provides just shows higher plastic behavior.

By implementing polymerization process of the present invention, obtained particle thermoplastic elastomer and particle elastomerics with particle characteristics, their bounding force generally is 6.0g/cm ²Or it is lower.

It is not crucial to implement the gas-phase polymerization reactor that the present invention uses, and can use any known fluid bed-type of reactor that mixes box reactor, fluid bed-type of reactor, is furnished with agitator, or the like.

It is any by continuous processing (adopting the two or more reactors of polyphone bonded), batchwise polymerization thing method (adopting one or more reactors) and the bonded of above-mentioned two kinds of methods to carry out polyreaction of the present invention.

Below, with reference to following limiting examples, method of the present invention is done more detailed description.

The physical data that relates among these embodiment is measured as follows.

Limiting viscosity (hereinafter to be referred as [η]):

Measure down and in the 1,2,3,4-tetralin at 135 ℃.

[η] E, [η] p---the limiting viscosity of the polymkeric substance of formation in the step 1,

[η] T---the limiting viscosity of total polymer,

[η] EP---form the limiting viscosity of polymkeric substance in the step 2.

[η] Ep is calculated as follows: $\[\mathrm{\η}\]\mathrm{Ep}=\frac{\[\mathrm{\η}\]T-\[\mathrm{\η}\]E\left(E\right)}{\left(\mathrm{Ep}\right)}$ Or $\frac{\[\mathrm{\η}\]T-\[\mathrm{\η}\]p\left(P\right)}{\left(\mathrm{Ep}\right)}$

In the formula (E) and (P) respectively represent the ratio (weight part) of amount of polymers in the step 1, (Ep) represent the ratio of amount of polymers in the step 2.

Ethene and 1, the content of 9-decadiene:

By infrared measurement, from 722,733 and 736cm ^-1Absorption band determines ethene, from 1640cm ^-Absorption band determines 1, the 9-decadiene.Therefore the ethylene content of measuring roughly with determine that from surplus materials numerical value conforms to.

The bounding force of polymer beads:

Two platens (cell) that will be used for shearing test closely are stacked together up and down, put into polymer beads to be tested therebetween.Described is to be made by aluminium sheet, wide 30mm, long 53mm, thick 12mm.In preliminary compacting under the 1000g load after 30 seconds, at normal temperatures and at 50g, 100g, 200g, the draw speed with 100mm/ minute under the vertical load of 300g or 400g carries out the one side shearing test.To measure the shearing stress under each vertical load.According to minimum 2 multiplication, subtract the curve approximation linearity of shearing stress and vertical load, being extrapolated to vertical load is that zero shear-stress is got as bounding force.The component of 20 ℃ of following xylene soluble (hereinafter to be referred as making XCS):

1 gram polymkeric substance is dissolved in the boiling xylene of 200ml, and slowly is cooled to 50 ℃, then it is immersed in the frozen water, under 20 ℃, it was left standstill 3 hours, and after-filtration is to remove sedimentary polymkeric substance.From filtrate, evaporate dimethylbenzene, and residuum is carried out vacuum-drying under 60 ℃, reclaim the polymkeric substance that dissolves in dimethylbenzene down at 20 ℃.

Pore volume:

Use apertometer 9310 (manufacturing of Micromertic company) and adopt mercury injection (40～75,000 ) in radius to measure pore volume.

The median size of solid catalyst:

Measure by the optical microphotograph measurement.

Embodiment 1

(A) organo-magnesium compound is synthetic

At a volume is 11, and is furnished with in the flask of agitator, reflux exchanger, dropping funnel and thermometer, after argon replaces, with the small pieces MAGNESIUM METAL input flask of 32.0 grams.

Add 120 gram n-butyl chloride and 500 milliliters of di-n-butyl ethers by dropping funnel, and mixture that will about 30ml is added drop-wise in the magnesium in the flask, begins to react.After the reaction beginning, under 50 ℃, the mixture in the dropping funnel is dripped continuously, last 4 hours, then, proceed 1 hour again in 60 ℃ of following reactions.Then, filter out with the reaction mixture cool to room temperature and with solid matter.

With 1N sulfuric acid the chloro normal-butyl magnesium in the n-butyl ether is hydrolyzed, and adopts phenolphthalein, with 1N aqueous sodium hydroxide solution back titration as indicator.Find that thus the concentration of chloro normal-butyl magnesium is 2.0M/l.

(B) solid product is synthetic

A volume be in 200ml and the flask of being furnished with agitator, dropping funnel after argon replaces, the porous polymer spherolite (chromosorb101, Johns-Manville company produces) that 20ml n-butyl ether and 5.0 grams are made of the multipolymer of vinylbenzene-Vinylstyrene drops in the flask.Carry out measurement result with apertometer in the pore radius scope of 100～5000 and show, the polymkeric substance spherolite has the pore volume (below be called " dvp ") of 0.92ml/g.Spherolite is prepared to use in advance 80 ℃ of vacuum-dryings 0.5 hour then.In stirred flask, in the article, synthetic organo-magnesium compound in 14 grams (A) was dripped 10 minutes from dropping funnel, make the temperature in the flask keep 80 ℃ simultaneously.Then, under this temperature, the article in the flask were reacted 1 hour again.After the normal heptane washed product with the n-butyl ether of each 20ml and 20ml, drying under reduced pressure obtains the product that 5.0 gram organic-magnesiums are handled.

A volume be 100ml and be furnished with agitator and the flask of dropping funnel in after the argon replaces, the products that the above-mentioned synthetic organic-magnesium of 5.0 grams is handled restrain (21.6 mmole) tetraethoxysilanes and drop in the flask with 25ml normal heptane, 0.44 gram (1.3 mmole) four titanium butoxide and 4.5, and article in 30 ℃ of stirred flask 30 minutes.

Then, synthetic organo-magnesium compound among the 4.6ml (A) was dripped 1 hour from dropping funnel, make the temperature in the flask remain on 5 ℃ simultaneously.After the dropping, under 5 ℃, the article in the flask were stirred 1 hour, then restir 1 hour at room temperature.After the stirring, with its normal heptane washed twice with each 25ml part, and drying under reduced pressure, obtain 6.2 gram brown solid products.

The solid product that obtains thus contains the magnesium atom of the titanium atom and 3.9% (weight) of 0.4% (weight).

(C) ingredient of solid catalyst is synthetic

In the flask that a volume is 100ml, after argon replaces, reacted 1 hour with synthetic solid product, 300 gram-chlorobenzenes and 0.41 gram (1.5 mmole) diisobutyl phthalate introducing flask in the 6.0 gram reduction reactions (B) and in 80 ℃.

Under 80 ℃, solid product isolated from liquid phase and with each 30ml part normal heptane washed twice.

After the washing, join 30.0ml-chlorobenzene, 0.53ml (3.1 mmole) n-butyl ether and 9.6ml (87.3 mmole) titanium tetrachloride in the flask and in 80 ℃ of reactions 3 hours.After the reaction, solid product isolated from liquid phase and under this temperature with the monochloro-benzene washed twice of each 30ml part.Mixture with n-butyl ether and titanium tetrachloride repeats above-mentioned processing, lasts 1 hour, and the product of processing is with the normal heptane washed twice of each 30ml part, and drying under reduced pressure obtains 5.4 gram brown solid catalyst components then.

The curing catalysts component contains the titanium atom of 0.5% (weight), the phthalic ester of the magnesium atom of 4.3% (weight) and 0.7% (weight).

The median size of the ingredient of solid catalyst that obtains here is 200 μ m, and dvp (pore volume) is 0.75ml/l.

(D) polymerization

With long-pending is 5 liters of autoclaves of being furnished with agitator, 1 carries out equal polymerization set by step, then 2 random copolymerizations that carry out ethene and propylene set by step.

80 ℃ of dry autoclaves 1 hour and and the vacuum pump evaporation after, add the ingredient of solid catalyst of preparation among 0.5 gram triethyl aluminum, 0.13 gram phenyltrimethoxysila,e and the 564.0mg (C), and introducing hydrogen reaches 5.2 * 10 up to its dividing potential drop ⁴Pa.

Then, under atmospheric pressure the 1.3kg liquefied propylene is introduced autoclave, and temperature is elevated to 75 ℃., after 15 minutes unreacted monomer is removed at 75 ℃ of following propylene polymerizations, from the small amount of polymer sampling, so that measure [η] p and CXS.Then, charge into 7.4 * 10 ³The hydrogen of Pa makes pressure bring up to 7.8 * 10 with propylene again ⁵PaG then further makes pressure bring up to 9.8 * 10 with ethene ⁵PaG.Then, with temperature regulation to 70 ℃, begin to carry out the polymerization of step 2.

Is 9.8 * 10 adding ethylene/propene gaseous mixture [50%/50% (volume)] to keep total pressure ⁵In the time of Pa, carry out ethene and propylene gas phase copolymerization, the time is 420 minutes.

After the polymerization fully, remove unreacted monomer, obtain the particulate thermoplastic elastomerics that 643 grams have good particle characteristics.This elastomerics neither contains fine powder and does not also contain coarse particles.

After opening autoclave, check its inside, found that does not have polymer deposition on inwall or agitator.

For titanium atom in every gram solid catalyst, total polymkeric substance of formation (to be called pp/Ti) is 228,000 (g/g).In alfon that step 1 forms (below be called P), CXS is 3.8% (weight).

In total polymkeric substance, the content of the ethylene/propene copolymer that step 2 forms (below be called EP) is 85% (weight).In EP, the content of ethene is 48% (weight).The molecule of polymkeric substance is as follows:

[η]p=1.7、[η]Ep＝3.8、[η]T＝3.5

The bounding force of the polymer beads that obtains here is 2.8g/cm ²

Polymerizing condition and result are summarized in table 1 and the table 2 respectively.

Comparative Examples 1

(A) solid product is synthetic

A volume be 200ml and be furnished with agitator and the flask of dropping funnel in will be after argon replaces in 2 hours 15 gram ultra-fine grain silica gel (ID types of 100 ℃ of vacuum-dryings, Fuji DevisionKagaku K.K produces, and dvp=0.84ml/g) drops into flask with the 46ml n-butyl ether.When stirring, synthetic organo-magnesium compound among the 42.0ml embodiment (A) was dripped 10 minutes from dropping funnel, make the internal temperature of flask remain on 30 ℃ simultaneously.Then, under this temperature, the article in the flask were reacted 2 hours again.Product is used the normal heptane washed twice of each 40ml part again with the n-butyl ether washed twice of each 20ml part, and drying under reduced pressure obtains the silica gel that 14.8 gram organic-magnesiums are handled then.

A volume be 300ml and be furnished with agitator and the flask of dropping funnel in after argon replaces, 13.8 silica gel, 69ml normal heptane, 0.77 gram (2.3 mmole) four titanium butoxide and 8.04 gram (38.6 mmole) tetrem oxosilanes that restrain the organic-magnesium processing that obtains are above added in the flasks, and in 30 ℃ of stirrings 30 minutes.

Then, 22.6ml embodiment 1 (A) synthetic organo-magnesium compound was dripped from dropping funnel 1 hour, make the temperature in the flask remain on 5 ℃ simultaneously.After the dropping, the article in the flask were stirred 1 hour in 5 ℃, restir 1 hour at room temperature then with normal heptane washed twice and the drying under reduced pressure of product with each 60ml part, obtains 21.1 and restrains the brown solid products then.

The solid product that obtains thus contains the magnesium atom of the titanium atom and 5.9% (weight) of 0.5% (weight).

(B) ingredient of solid catalyst is synthetic

In the flask that a volume is 100ml, after argon replaces, add 5.6 grams synthetic solid product, 18.8ml toluene and 0.74ml (2.8 mmole) diisobutyl phthalate in reduction reaction (A), and reacted 1 hour down at 95 ℃.

After the reaction, solid product isolated from liquid phase and with twice of the toluene wash of each 20ml part.

After the washing, add 18.8ml toluene, 0.65ml (3.8 mmole) n-butyl ether and 11.4ml (104 mmole) titanium tetrachloride, and reacted 3 hours down at 95 ℃.After the reaction, under 25 ℃, solid product is isolated from liquid phase, and under this temperature with twice of the toluene wash of each 20ml part.Then, repeat once above-mentioned processing again with the mixture of n-butyl ether and titanium tetrachloride, the time is 1 hour, and product is with the normal heptane washed twice of each 20ml part, then, drying under reduced pressure, thus 4.8 gram brown solid catalyst components obtained.

This ingredient of solid catalyst contains the titanium atom of 1.1% (weight), the phthalic ester of the magnesium atom of 7.8% (weight) and 1.5% (weight).

The median size of this ingredient of solid catalyst is 40 μ m, and dvp (pore volume) is 0.35ml/g.

(C) polymerization

Use the 297.0mg ingredient of solid catalyst that obtains in (B), in embodiment 1 (D), carry out the block copolymerization of P-EP under the similarity condition.Polymerizing condition and result are shown in table 1 and table 2 respectively.

Owing in this test, replace organic porous polymer as support of the catalyst, so the polymer lumps that obtains with silica gel.Its particle characteristics extreme difference, its bounding force are 7.7g/cm ²

Polymerizing condition and result are shown in table 1 and table 2 respectively with Comparative Examples 2～4.

Comparative Examples 2

(A) solid product is synthetic

A volume be 200ml and be furnished with agitator and the flask of dropping funnel in after argon replaces, with 8.25 gram silica gel (trades mark 952 of under 800 ℃ and nitrogen atmosphere, having calcined, Fuji DevisionKagaku K.K. produces) (dvp=0.88) ml/g) restrain (56.7 mmole) tetraethoxysilanes and join in the flask with 41.3ml normal heptane, 1.12 gram (3.3 mmole) four titanium butoxide and 11.8, at room temperature, the article in the flask were stirred 30 minutes.

Then, synthetic organo-magnesium compound among the 30.0ml embodiment 1 (A) was dripped from dropping funnel 1 hour, make the temperature in the flask remain on 5 ℃ simultaneously.After the dropping, resulting mixture was stirred 30 minutes in 5 ℃, then in 30 ℃ of restir 1 hour, then, product is with the normal heptane washed twice of each 40ml part, and drying under reduced pressure, obtains 17.5 and restrains the brown solid products.

(B) ingredient of solid catalyst is synthetic

After argon replaces, adding 4.5 restrains solid products, 15.1ml toluene and 1.67ml (6.2 mmole) diisobutyl phthalate and reacted 1 hour in 95 ℃ in the flask that a volume is 100ml.

After the reaction, solid product isolated from liquid phase and with twice of the toluene wash of each 15ml part.

After the washing, with 15.1ml toluene, in 1.0ml (5.7 mmole) n-butyl ether and 17.7ml (161 mmole) the titanium tetrachloride adding flask and in 95 ℃ of reactions 3 hours.After the reaction, under 95 ℃, solid is isolated from liquid phase, and under this temperature with twice of the toluene wash of each 15ml part.Then, repeat once above-mentioned processing again with the mixture of n-butyl ether and titanium tetrachloride, the time is 1 hour; With the normal heptane washed twice of product with each 15ml part, then drying under reduced pressure obtains 3.6 gram brown solid catalyst components.

The ingredient of solid catalyst that obtains thus contains the titanium atom of 1.9% (weight), the phthalic ester of the magnesium atom of 9.0% (weight) and 2.3% (weight).Its pore volume dvp is 0.25ml/g.

(C) polymerization

Use synthetic ingredient of solid catalyst among the 103.2mg (B), in embodiment 1 (D), carry out the block copolymerization of P-Ep under the similarity condition.

Be used for replacing the carrier of organic porous polymer with silica gel, so the polymer lumps that obtains as catalyzer in this experiment.Its particle characteristics extreme difference, its bounding force are 8.4g/cm ²

Comparative Examples 3

(A) solid product is synthetic

A volume be 500ml and be furnished with agitator and the flask of dropping funnel in after argon replaces, add 150ml normal heptane, 7.6 gram (22.4 mmole) four titanium butoxide and 78 gram (378 mmole) tetrem oxosilanes, form a kind of homogeneous solution.Then,, in 3 hours, slowly drip, make the temperature in the flask remain on 5 ℃ simultaneously from dropping funnel with synthetic organo-magnesium compound in the 182ml example 1 (A).After the dropping, at room temperature mixture was stirred 1 hour again, and from liquid phase solid is isolated, with the normal heptane washed twice of each 300ml part, drying under reduced pressure obtains 62.0 gram brown solid products then.

(B) ingredient of solid catalyst is synthetic

In the flask that a volume is 200ml, after argon replaces, add synthetic solid product, 75ml toluene and 8.1ml diisobutyl phthalate in 15 grams (A), and in 95 ℃ of reactions 1 hour.

After the reaction, solid is gone out and with the normal heptane washed twice of each 75ml part from liquid phase separation.

Then, add 38ml toluene, 5.0ml (88.5 mmole n-butyl ethers and 88.5ml (807 mmole) titanium tetrachloride and in 95 ℃ of reactions 3 hours.

After the reaction, under 95 ℃, solid isolated from liquid phase and under this temperature with twice of the toluene wash of each 15ml part.

Then, in 1 hour, repeat once above-mentioned processing again, and with the normal heptane washed twice of product with each 75ml part, drying under reduced pressure obtains the khaki ingredient of solid catalyst of 13 grams then with the mixture of n-butyl ether and titanium tetrachloride.

This ingredient of solid catalyst contains the titanium atom of 1.9% (weight), the phthalic ester of the magnesium atom of 19.4% (weight) and 5.0% (weight).Its median size is 30 μ m, and its pore volume dvp is 0.27ml/g.

(C) polymerization

Use synthetic ingredient of solid catalyst among the 31.8mg (B), in embodiment 1 (D), carry out the block polymerization of P-Ep under the similarity condition.Polymerizing condition and result are shown in table 1 and table 2 respectively.

Because ingredient of solid catalyst does not inject porous support in this experiment, so although sizable pore volume is arranged, the particle characteristics extreme difference, inspection to unlimited autoclave shows, polymer beads deposits on the inwall of autoclave, form layers, and almost solidify.

Comparative Examples 4

(A) ingredient of solid catalyst is synthetic

According to the same operation synthesis of solid catalyst component of pointing out among Japanese patent application (disclosing unsettled) 61～287,917 (USP4,412, the 049) embodiment.

Thereby, a volume be 300ml and be furnished with agitator and the flask of dropping funnel in after argon replaces, add synthetic organo-aluminium compound among 5.72ml embodiment 1 (A).Temperature in making flask remains in 20 ℃, in 1 hour, the 12.8ml silicon tetrachloride is added drop-wise to lentamente in the solution of chloro normal-butyl magnesium (in n-butyl ether).After the dropping, under 20 ℃, again mixture was stirred one hour, and reaction mixture is filtered, then with solid product with the hexane wash of each 100ml part four times, obtain a kind of carrier.

Then, add the 70ml hexane, and interior temperature is remained on 60 ℃ with the preparation slip.

Then, add the solution of 4.2 gram phenol (in the 100ml hexane) and 6.4ml ethyl benzoate and in 60 ℃ of reactions 30 minutes.Filter reaction mixture, solid product with the hexane of each 150ml part 60 ℃ of following washed twice.

Then, add the 80ml mono chloro benzene, afterwards, add by 122.4 gram Ti with the preparation slip

The solution of forming with the 48ml mono chloro benzene and in 100 ℃ of following filter reaction mixtures, and with 150ml toluene wash solid is used twice of the hexane wash of each 100ml part and dry then, obtains 15.1 and restrains the curing catalysts components.

This ingredient of solid catalyst contains the magnesium atom of the titanium atom, 20.9% (weight) of 2.5% (weight), the ethyl benzoate of the phenol of 1.7% (weight) and 9.1% (weight).The median size of this ingredient of solid catalyst is 30 μ m, and its aperture dvp is 0.29ml/g.

(polymerization)

Carry out the block copolymerization of P-Ep by the same manner among the embodiment 1 (D), different is to use (A) middle synthetic 32.4mg ingredient of solid catalyst and restrain the phenyltrimethoxysila,e that methyl p toluate replaces being used as among the embodiment 1 electron donor with 0.2.

Polymerizing condition and result are shown in table 1 and table 2 respectively.In this experiment, catalyst activity changes in time greatly, the ethene of step 2 during with propylene random copolymerization activity completely lose, like this, obtain having the thermoplastic elastomer of the present invention's composition.

Embodiment 2

Carry out the block copolymerization of P-EP with synthetic ingredient of solid catalyst among the embodiment 1.

Under 80 ℃ with dry 1 hour of autoclave, and with vacuum pump with its evaporation after, add the ingredient of solid catalyst of preparation among 0.5 gram triethyl aluminum, 0.13 gram phenyltrimethoxysila,e and the 282.9mg embodiment 1, charge into argon then and reach 5.2 * 10 until its dividing potential drop ⁴Pa.

Then, under atmospheric pressure the 1.3kg liquefied propylene is introduced autoclave and heated 75 ℃.After 10 minutes, remove unreacted monomer at 75 ℃ of following vinyl polymerizations, and from a spot of polymkeric substance sampling, to measure [η] p and CXS.

Then, charge into 2.9 * 10 ⁴Pa ²Hydrogen, and pressure is elevated to 3.9 * 10 with propylene ⁵PaG is elevated to 9.8 * 10 with ethene with pressure again ⁵PaG afterwards, with temperature regulation to 70 ℃, begins to carry out the polymerization of step 2.

When adding the ethylene/propene gaseous mixture so that make stagnation pressure remain on 9.8 * 10 ⁵During PaG, in gas phase, carry out ethylene/propylene copolymer and close, polymerization time is 540 minutes.

After the polymerization fully, remove unreacted monomer, obtain the particle thermoplastic elastomer that 368 grams have the good powder characteristic.It neither contains fine powder, does not also contain coarse particles.

Open autoclave and check its inner discovery, on the inwall of autoclave and agitator, do not have deposited polymer at all.

Polymerizing condition and result are shown in table 1 and table 2 respectively.

Embodiment 3

Carry out the block copolymerization of P-EP under the same condition of embodiment 1 (D), different is to use synthetic 377.0mg ingredient of solid catalyst among the embodiment 1, and charge into 2.0 * 10 in the polymerization of step 2 ⁴Pa hydrogen.Polymerizing condition and result are respectively at table 1 and table 2.

Embodiment 4

Use synthetic ingredient of solid catalyst among the embodiment 1, in step 1, carry out the equal polymerization of propylene, in step 2, carry out the random copolymerization of ethene and butene-1.

Under 80 ℃ dry 1 hour, and, add synthetic ingredient of solid catalyst among 0.5 gram triethyl aluminum, 0.13 gram phenyltrimethoxysila,e and the 372.4mg embodiment 1, charge into hydrogen and very reach 5.2 * 10 to its dividing potential drop with after the vacuum pump evaporation to autoclave ⁴Pa.

Afterwards, under high pressure 1.3kg liquid being stopped propylene joins in the autoclave and is heated to 75 ℃.Under 75 ℃, the equal polymerization of propylene was removed unreacted monomer after 10 minutes, from a spot of polymkeric substance sampling, to measure [η] p and CXS.Then, charge into 7.4 * 10 ³Pa hydrogen, and charge into ethylene/butylene-1 gaseous mixture [80%/20% (volume)], so that make stagnation pressure remain on 3.9 * 10 ⁵Pa.Under 75 ℃, carry out the copolymerization of ethene and butene-1, polymerization time is 420 minutes.After the polymerization fully, remove unreacted monomer, obtain the thermoplastic elastomer that 260 grams have good particle characteristics.

Open autoclave and check its inner back discovery, all do not have deposited polymer on the inwall of autoclave or the agitator.

The total polymer (PP/Ti) that per 1 gram titanium atom forms is 14000.Total polymer contains ethylene/butylene-1 multipolymer (to call EB in the following text) that forms in 73% (weight) step 2.In EB, the content of ethene is 77% (weight).

Molecular weight is as follows: [η] p=2.2, [η] EB=4.1[η]=3.6.The bounding force of the polymkeric substance that obtains thus is 2.4g/cm ²

Embodiment 5

(A) solid product is synthetic

At a volume is 200ml, and be furnished with stir and the flask of dropping funnel in after argon replaces, 7.0 of following 80 ℃ of vacuum-dryings 1 hour are restrained chromosrob101 and the 28ml n-butyl ether joins in the flask.Article in the stirred flask dripped synthetic organo-magnesium compound among the 20ml embodiment 1 (A) 30 minutes simultaneously from dropping funnel, during this period, the temperature in the flask is remained on 80 ℃.Under this temperature, make article in the flask react 1 hour again after, with the n-butyl ether washed twice of product, use the normal heptane washed twice and the drying under reduced pressure of each 20ml part again with each 20ml part, obtain 7.0 gram organic-magnesiums processing products.Afterwards, at an internal volume is after 100ml and the flask of being furnished with the dropping funnel of agitator charge into argon gas, the product that synthetic organoaluminum above 7.0 grams is handled joins in the flask with 30ml normal heptane, 0.62 gram (1.8 mmole) four titanium butoxide and 6.31 gram (30.2 mmole) tetrem oxosilanes, and under 30 ℃ the article in the flask is stirred 30 minutes.

Then, synthetic organo-magnesium compound among the 16.0ml embodiment 1 is dripped from dropping funnel, make the temperature in the flask remain on 5 ℃ simultaneously.After the dropping, under 5 ℃, the article in the flask were stirred 1 hour, restir 1 hour at room temperature then, and with normal heptane washed twice and the drying under reduced pressure of product with each 30ml part, obtain 11.6 and restrain the brown solid products.

(B) ingredient of solid catalyst is synthetic

After argon replaces, adding 4.1 gram solid products, 13.8ml toluene, 0.91ml (5.4 mmole) n-butyl ether and 16.1ml (146 mmole) titanium tetrachloride also reacted 3 hours under 90 ℃ in the flask that a volume is 100ml.After the reaction, under 95 ℃, solid isolated from liquid phase and under this temperature with twice of the toluene wash of each 20ml part.Mixture with n-butyl ether and titanium tetrachloride repeats once above-mentioned processing again, and the time is 1 hour.Then, with the normal heptane washed twice of product with each 20ml part, afterwards, drying under reduced pressure obtains 3.5 gram brown solid catalyst components.

This ingredient of solid catalyst contains the magnesium atom of the titanium atom and 6.3% (weight) of 1.6% (weight).

Its median size is 200 μ m, and pore volume dvp is 0.53ml/g.

(C) polymerization

Be 5 liters and the autoclave of agitator be housed that 1 carries out the equal polymerization of ethene set by step with a volume, set by step 2 random copolymerizations that carry out ethene and propylene.

Autoclave charged into the 800g butane and was heated to 60 ℃ after under 80 ℃ dry 1 hour.Feed argon gas then and reach 2.9 * 10 until its dividing potential drop ⁵PaG afterwards, feeds ethene up to pressure 2.0 * 10 ⁶PaG, then the 0.5g triethyl aluminum, 0.13g phenyltrimethoxysila,e and 313.2mg introduce autoclave by the ingredient of solid catalyst of (B) preparation and a small amount of normal heptane together under pressure.When keeping total pressure is 2.0 * 10 ⁶PaG, when temperature is 60 ℃, the equal polymerization of ethene has been carried out 50 minutes, removes unreacted monomer and butane thereafter, and takes out a spot of polymer sample so that measure [η] E.Afterwards, feeding pressure is 7.4 * 10 ³PaG hydrogen, and the feeding propylene makes increased pressure to 7.8 * 10 ⁵PaG then feeds ethene, pressure and then increase to 9.8 * 10 ⁵PaG, after this temperature transfers to 70 ℃ and begun the second step polymerization.

Feeding ethylene/propene gaseous mixture (volume ratio is 50%/50%) so that keep total pressure is 9.8 * 10 ⁵In the time of PaG, ethylene/propylene copolymer closes to react and carried out 90 minutes in gas phase.After polymerization is finished, remove unreacted monomer, can obtain the particle thermoplastic elastomer that 338g has the good powder characteristic, wherein do not contain fine powder and coarse particle.After opening autoclave, check that still is interior as seen, do not have polymer attached on the inwall of still and the agitator fully.

The total polymer that every 1g solid catalyst is generated (hereinafter being called P/Cat (g/g)) is 1.080.

The limiting viscosity of the homopolymer that step 1 generated (being referred to as E in this article) is 1.7.Total polymer contains 2 ethylene/propene copolymers that generated (being referred to herein as EP) set by step of 85% (weight).The content of ethene is 48% (weight) in EP, and the limiting viscosity of total polymer and EP is as follows: [η] T=2.9, [η] Ep=3.1.Here the bounding force of resulting polymer particle is 4.2g/cm.

Comparative Examples 5

(A) synthesis of solid product

A volume is 500ml and is equipped with agitator and the flask of dropping funnel, after the argon replaces of footpath, adds the 150ml normal heptane, 7.6g (22.4mmol) four titanium butoxide and 78g (378mmol) tetraethoxysilane, forms uniform solution.Then, slowly dripped synthetic organo-magnesium compound among 182ml (400mmol) embodiment 1 (A) with dropping funnel in three hours, during this period, the temperature in the flask remains on 5 ℃.After dropwising, after this material in stirred flask under the room temperature 1 hour, is at room temperature separated solid product from liquid phase, and with each 300ml normal heptane washing secondary, can obtain the brown solid product of 62.0g after the drying down in decompression.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, after argon replaces, adds the solid product that 10.7g obtains in (A), 35.6ml toluene, and 2.36g (13.9mmol) n-butyl ether and 41.6ml (378mmol) titanium tetrachloride reacted three hours down at 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 35ml toluene wash.

Then, in one hour, repeat above-mentioned n-butyl ether and the titanium tetrachloride used again and handle once, use twice of each 35ml normal heptane washed product and drying under reduced pressure afterwards, obtain 9.8g loess look ingredient of solid catalyst.

So the curing catalysts component that obtains contains the magnesium atom of the titanium atom and 18.5% (weight) of 7.6% (weight).Its median size is 35 μ m, and its pore volume dvp is 0.17ml/g.

(C) polymerization

With the ingredient of solid catalyst that 127.0mg obtains, under the condition identical, carry out the block copolymerization of E-Ep with embodiment 5 (c) in (B).Polymerizing condition and result are shown in table 3 and table 4 respectively.

Because in this test, ingredient of solid catalyst does not flood porous support, so the non-constant of particle properties.That is to say, open autoclave and check in it, find to have polymer beads to be deposited on autoclave inwall stratification and similar fixed.

Comparative Examples 6

(A) synthesis of solid product

A volume is 200ml and agitator is housed and the flask of dropping funnel, through after the argon replaces, adding 10.2g4B type ultra micro pearl silica gel (is made by Fuji Devison Kagaku K.K., dvp=0.15ml/g, the roasting eight hours in nitrogen atmosphere in advance of this silica gel) and the 51.0ml normal heptane, 0.47g the material in (1.4mmol) four titanium butoxide and 5.20g (23.2mmol) tetraethoxysilane, and flask stirred 45 minutes down at 30 ℃.

Then, dripped 12.4ml with dropping funnel and press synthetic organo-magnesium compound among the embodiment 1 (A) in 45 minutes, during this period, the temperature in the flask remains on 5 ℃.After dripping off, the material under this temperature in the flask is stirred 45 minutes, and then, product can obtain the brown solid product of 13.8g after with each 51.0ml part normal heptane washed twice and drying under reduced pressure.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, adds synthetic solid product among the 6.22g (A) after the process argon replaces, 20.7ml toluene, and 1.37ml (8.1mmol) n-butyl ether and 24.2ml (220mmol) titanium tetrachloride reacted three hours down in 95 ℃.After the reaction, under 95 ℃, isolate the solid product in the liquid phase and respectively use 20.7ml part toluene washed twice under this temperature.After this, the mixture with n-butyl ether and titanium tetrachloride in a hour repeats above-mentioned processing once, and each obtains 5.8g brown solid catalyst component with twice of 20.7ml normal heptane washed product and drying under reduced pressure afterwards.

So the ingredient of solid catalyst that obtains contains the titanium atom of 2.1% (weight), the magnesium atom of 3.5% (weight).If this ingredient of solid catalyst contains considerable fine powder, its median size 40 μ m then.Its pore volume dvp is very little, and 0.07ml/g is only arranged.

(C) polymerization

Adopt synthetic ingredient of solid catalyst among the 359.0mg (B), under the condition identical, carry out the block copolymerization of E-EP with embodiment 5 (c).

Polymerizing condition and result thereof are respectively shown in table 3 and table 4.Because in this test, the pore volume of ingredient of solid catalyst is very little, so, the particle poor performance of resulting polymkeric substance.Therefore, check the autoclave after opening, can see that polymer beads deposits stratification on the autoclave inwall, and almost fixed.

Embodiment 6

(A) synthesis of solid catalyst component

The flask that volume is 100ml adds the solid product for preparing in the reduction process among 4.96g embodiment 5 (A) after argon replaces, 16.5ml toluene and 1.26ml (4.7mmol) diisobutyl phthalate is in 95 ℃ of reactions one hour down.

Isolate in the liquid phase solid product and with twice of each 16.5ml toluene wash.After the washing, add 16.5ml toluene in flask, 1.1ml (6.4mmol) n-butyl ether and 19.3ml (176mmol) titanium tetrachloride reacted 3 hours down in 95 ℃.Reaction finishes, under 95 ℃, isolate in the liquid phase solid and under this temperature with twice of each 16.5ml toluene wash.

Adopt the mixture of n-butyl ether and titanium tetrachloride to repeat above-mentioned processing once, last one hour.After this, with each twice of 16.5ml part normal heptane washing reaction product and dry down, thereby obtain 3.90g brown solid catalyst component in decompression.

The ingredient of solid catalyst of Huo Deing contains the titanium atom of 0.5% (weight) like this, the phthalic ester of the magnesium atom of 4.3% (weight) and 0.7% (weight).

Its median size is 200 μ m, and wherein volume dvp is 0.75ml/g.

(B) polymerization

Adopt synthetic 421.3mg ingredient of solid catalyst in (A), carry out the E-EP block copolymerization according to the condition identical with embodiment 5 (c).Polymerizing condition and result are respectively shown in table 3 and table 4.

Embodiment 7

(A) polymerization

To adopt a volume be 5 liters and the autoclave of agitator is housed, and 1 carries out the equal polymerization of ethene and 2 random copolymerizations that carry out ethene and propylene set by step set by step.

Dry autoclave added the 800g butane and temperature is increased to 60 ℃ after 1 hour under 80 ℃.Feed argon gas then and reach 2.9 * 10 up to its dividing potential drop ⁵PaG is because the feeding of ethene makes increased pressure to 2.0 * 10 ⁶PaG thereafter, injects autoclave at following 0.5g triethyl aluminum of the high pressure of argon gas and 378.5mg by ingredient of solid catalyst and a spot of normal heptane of the method preparation of embodiment 5 (B) together.Total pressure remains on 2.0 * 10 in still ⁶PaG, when temperature remained on 60 ℃, the equal polymerization reaction of ethene had been carried out 40 minutes.Afterwards, remove unreacted monomer and butane, take out that a spot of polymkeric substance is made sample so that measure [η] E.Then, feed 4.9 * 10 ³The hydrogen of PaG feeds propylene and makes pressure rise to 7.8 * 10PaG, feeds ethene then and makes pressure rise to 9.8 * 10 ⁵PaG, after this, temperature regulation to 40 ℃, 2 polymerizations of carrying out have just begun set by step.

Then, feed ethylene/propene gaseous mixture (volumeter 50%/50%) so that make pressure remain on 9.8 * 10 ⁵PaG, the copolyreaction of ethene was carried out 80 minutes in gas phase.After the polyreaction, remove unreacted monomer, obtain the particulate state thermoplastic elastomer that 450g has the good powder characteristic.It neither contains fine powder and does not also contain coarse particle.Can see not having fully on the inwall and agitator of polymkeric substance attached to autoclave during autoclave that inspection is opened.

The total polymer (P/Cat) that every 1g catalyzer is generated is 1,190.Limiting viscosity is: [η] E=2.4, [η]=2.0 and [η] Ep=1.9.Ethylene content is 49% (weight) in Ep.The bounding force of thus obtained polymkeric substance is 3.2g/cm ²

Embodiment 8

The ingredient of solid catalyst that adopts 413.7mg to prepare in embodiment 6 (A) carries out the block copolymerization of E-EP under the condition identical with embodiment 7 (A).Polymerizing condition and result are shown in table 3 and table 4 respectively.

Comparative Examples 7

The condition of block copolymerization of carrying out E-Ep is identical with embodiment 7 (A), and institute's difference is the ingredient of solid catalyst (by the method preparation of Comparative Examples 4 (B)) with 144.0mg, also has, and the polymerization temperature of EP is reduced to 30 ℃.The condition of polyreaction and result are shown in table 3 and table 4 respectively.Because in this experiment, because of the pore volume of body catalyst component is very little, although polyreaction is carried out at low temperatures, the particle characteristics of the polymkeric substance that is obtained is very poor.

Embodiment 9

The preparation method of ingredient of solid catalyst is identical with condition among the embodiment 5, and different is, presses the random copolymerization reactions steps of ethene and propylene in the example 5 (C), feeds ethylene/propene gaseous mixture (by volume 85%/15%).Adopt this ingredient of solid catalyst to carry out polyreaction.The condition of polyreaction and result are shown in table 3 and table 4 respectively.

Embodiment 10

(A) synthesis of solid product

A volume is 200ml and agitator is housed and the flask of dropping funnel, through after the argon replaces, add 13.2g through 80 ℃ of vinyl cyanide-divinyl benzene copolymers of 60 minutes of following drying under reduced pressure (dvp=0.68ml/g), 65.5ml normal heptane, 0.60g (1.8mmol) four titanium butoxide and 6.23g (29.9mmol) tetraethoxysilane stirred 45 minutes at 30 ℃.

Then, dripped synthetic organo-magnesium compound among 16.0ml embodiment 1 (A) with dropping funnel in 45 minutes, during this period, the temperature in the flask remains on 5 ℃.After the titration, the material in the flask stirred 45 minutes down at 5 ℃, stirred 45 minutes down at 30 ℃ then, and thereafter, each can obtain 16.7 brown solid products with 65.5ml part normal heptane washed product twice behind the drying under reduced pressure.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, through after the argon replaces, adds synthetic solid product among the 5.38g (A), and 18.0ml toluene and 0.82ml (3.1mmol) diisobutyl phthalate reacted 1 hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 18.0ml part toluene wash product.After the washing, add 18.0ml toluene in flask, 1.2ml (7.1mmol) n-butyl ether and 21.0ml (191mmol) titanium tetrachloride make it react 3 hours down in 95 ℃.Reaction finishes, and isolates the solid product in the liquid phase under 95 ℃, and uses twice of each 18.0ml part toluene wash under this temperature respectively.Then, adopt the mixture of the titanium tetrachloride of n-butyl ether to repeat above-mentioned processing once, last one hour, product is with each 18.0ml part normal heptane washed twice, and this is after drying under reduced pressure can obtain 7.61g brown solid catalyst component.

So the ingredient of solid catalyst that obtains contains the titanium atom of 6.2% (weight), the phthalic ester of the magnesium atom 1.4% (weight) of 40% (weight).

The median size of this ingredient of solid catalyst is 80 μ m.(C) polymerization

The ingredient of solid catalyst that adopts 513.4mg to obtain in (B) carries out the block copolymerization reaction of E-EP under the condition identical with embodiment 5 (C).Polymeric condition and result are respectively shown in table 3 and table 4.

Embodiment 11

Adopt the ingredient of solid catalyst of preparation among the embodiment 5, set by step 1 carry out the homopolymerization of ethene and set by step 2 random copolymerizations of carrying out ethene and butene-1 react.

Volume is 5 liters and the autoclave of agitator is housed, and at 80 ℃ down after dry one hour, adds the 800g butane and temperature is increased to 60 ℃.Then, feed hydrogen, make the dividing potential drop of hydrogen reach 2.9 * 10 ⁵PaG feeds ethene and makes pressure rise to 2.0 * 10 ⁶PaG under argon pressure, injects 0.5g triethyl aluminum, the ingredient of solid catalyst and a spot of normal heptane that obtain among 0.13g phenyltrimethoxysila,e and the 370.5mg embodiment 5 (B) thereafter in autoclave.The homopolymerization of ethene has carried out 45 minutes.During this period, the total pressure in the autoclave remains on 2.0 * 10 ⁶PaG, temperature remains on 60 ℃, behind the homopolymerization, removes unreacted monomer and butane, takes out that a spot of polymkeric substance is made sample so that measure [η] E.Then, feed 7.4 * 10 ³Pa hydrogen, and feed ethylene/butylene-1 gaseous mixture (by volume 80%/20%) so that total pressure remains on 3.9 * 10 ⁵PaG under 75 ℃, carries out the copolyreaction of ethene and butene-1 in gas phase, lasts 420 minutes.

After polyreaction is finished, remove unreacted monomer, obtain the thermoplastic elastomer that 456g has good particle characteristics.

The autoclave that inspection is opened can see there is not polymer attached fully on autoclave inwall and agitator.

The total polymer (P/cat) that every 1g catalyzer is generated is 1,230.

This total polymer contains 2 ethylene/butylene-1 multipolymers that generate set by step of 85% (weight).In EB, the content of ethene is 80% (weight).The molecular wt of polymkeric substance is as follows: [η] E=1.8, [η] EB=3.0, [η] T=2.8.The bounding force of the polymkeric substance that obtains like this is 4.3 * 10 ⁵Pa.

Embodiment 12

(A) synthesis of solid product

A volume is 1000ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, add 74.0g through 80 ℃ of styrene diethylene benzene copoly mers of 30 minutes of following drying under reduced pressure (dvp=1.05ml/g), the 370ml normal heptane, 6.69g (19.7mmol) four titanium butoxide and 70.9g (340mmol) tetraethoxysilane stirred 45 minutes down in 30 ℃.

Then, in 45 minutes, synthetic organo-magnesium compound 180ml among the embodiment 1 (A) is dropped in the flask, during this period the temperature in the flask is remained on 5 ℃ with dropping funnel.Dropwise, the material in 5 ℃ of following stirred flask 45 minutes is subsequently in 30 ℃ of following restir 45 minutes.After this, with each twice of 300ml normal hexane washed product and dry down, obtain 126.3g brown solid product in decompression.

(B) synthesis of solid catalyst component

A volume is the flask of 1000ml, through after the argon replaces, adds 114.6g reduction reaction institute synthetic solid product in (A), and 382ml toluene and 32.1ml (120mmol) diisobutyl phthalate reacted 1 hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 300ml part toluene wash.

Washing finishes, and adds 382ml toluene in flask, and 25.3ml (149mmol) n-butyl ether and 447ml (4,070mmol) titanium tetrachloride and in 95 ℃ of reactions 3 hours down.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 300ml part toluene wash.Adopt n-butyl ether and the formed mixture of titanium tetrachloride to repeat above-mentioned processing once, last one hour, wash this product twice with each 300ml part normal hexane afterwards and, obtain 93.9g brown solid catalyst component in the drying down that reduces pressure.

The titanium atom that contains 0.51% (weight) in this ingredient of solid catalyst, the phthalic ester of the magnesium atom of 7.2% (weight) and 2.5% (weight).

The median size of this ingredient of solid catalyst is 50 μ m.(C) polymerization

Be 5 liters and be equipped with the random copolymerization reaction of carrying out ethene and propylene in the autoclave of agitator at a volume.

Find time as the polypropylene powder of dispersion agent is last adding in autoclave, temperature in the kettle is increased to 60 ℃.Feed 6.0 * 10 then ⁴The hydrogen of PaG also adds ethylene/propene gaseous mixture (by volume 50%/50%) and reaches 9.8 * 10 up to pressure ⁵After this PaG, injects 0.5g triethyl aluminum, the ingredient of solid catalyst that 0.13g phenyltrimethoxysila,e and 418.2mg obtain and a spot of normal heptane in (B) in still under argon pressure.Feed ethylene/propene gas so that total pressure remains on 9.8 * 10 ⁵PaG, in gas phase, the copolyreaction of ethylene/propene was carried out 50/ minute simultaneously.

After polymerization is finished, remove unreacted monomer, remove polypropylene powder as dispersion agent with sieve sieve, obtain 151g have the good powder characteristic, neither contain the particle elastomerics that fine powder does not contain coarse particle yet.Do not find on autoclave inwall and agitator, to adhere to any polymkeric substance.

The total polymer (g) that every 1g catalyzer is generated is 360.The condition of polyreaction and result are shown in table 5 and table 6 respectively.

Comparative Examples 8

(A) synthesis of solid product

A volume is 1 liter and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, add the 600ml normal heptane, 7.6g (22.2mmol) four titanium butoxide and 78.1g (375mmol) tetraethoxysilane, make it to become uniform solution, at room temperature stirred 30 minutes.Then, in three hours, synthetic organo-magnesium compound 200ml among the embodiment 1 (A) slowly is added drop-wise in the flask, during this period the temperature in the flask is remained on 5 ℃ with dropping funnel.Dropwise, the material under room temperature in the stirred flask was at room temperature isolated solid product and with each 600ml part normal heptane washed twice and dry down in decompression, is obtained 64.5g brown solid product after one hour from liquid phase.

(B) synthesis of solid catalyst component

A volume is the flask of 200ml, through after the argon replaces, adds 13.8g by the reduction synthetic solid product in (A), and 69ml toluene and 10.1ml (37.7mmol) diisobutyl phthalate reacted one hour down in 95 ℃.

After the reaction, isolate the solid product in the liquid phase, and with twice of each 69ml part toluene wash.

Washing finishes, and adds 69ml toluene in flask, and 5.0ml (30mmol) n-butyl ether and 88.5ml (805mmol) titanium tetrachloride also reacted 3 hours under 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 69ml toluene wash.Adopt n-butyl ether and the formed mixture of titanium tetrachloride to repeat above-mentioned processing once, last one hour, wash this product twice with each 69ml part normal heptane afterwards and, obtain 10.4g brown solid catalyst component in the drying down that reduces pressure.

The titanium atom that contains 1.8% (weight) in this ingredient of solid catalyst, the magnesium of 21% (weight) and 6.5% (weight) phthalic ester.

(C) polymerization

The ingredient of solid catalyst that employing obtains above, and use the method identical to carry out the copolyreaction of ethene and propylene with embodiment 12 (C).The condition of polyreaction and result are shown in table 5 and table 6 respectively.

Because ingredient of solid catalyst does not flood the porous polymer support in this experiment, particle characteristics is very poor.Therefore, check that the autoclave open can see that polymer particle sticks on the polypropylene powder dispersion agent and forms piece.

Comparative Examples 9

(A) synthesis of solid product

A volume is 300ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, add 10.0g through 700 ℃ of silica gel of 8 hours of roasting (dvp=0.69ml/g) under nitrogen atmosphere, 50.0ml normal heptane, 1.31g (3.86mmol) four titanium butoxide and 13.8g (66.1mmol) tetraethoxysilane also stirred 45 minutes under 30 ℃.

Then, in 45 minutes,, the temperature in the flask is remained on 5 ℃ therebetween with synthetic organo-magnesium compound among dropping funnel Dropwise 35 .5ml embodiment 1 (A).Dropwise, the material in 5 ℃ of following stirred flask 45 minutes stirred 45 minutes down at 30 ℃ again, after this, with each twice of 50ml part normal butane washed product and dry down in decompression, obtained 21.0g brown solid product.

(B) synthesis of solid catalyst component

A volume is the flask of 200ml, after argon replaces, adds the solid product that 9.34g is generated by the reduction reaction in (A), and 31.1ml toluene and 3.53ml (13.2mmol) diisobutyl phthalate reacted one hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 31ml part toluene wash.Then, in flask, add 31.1ml toluene, 2.06ml (12.2mmol) n-butyl ether and 36.4ml (331mmol) titanium tetrachloride, reacted 3 hours down in 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 31ml part toluene wash.Then, adopt the mixture of forming by n-butyl ether and titanium tetrachloride in one hour, to repeat above-mentioned processing once, after this,, obtain 9.23g brown solid catalyst component with each twice of 31ml part normal heptane washed product and dry down in decompression.

So the ingredient of solid catalyst that obtains contains the titanium atom of 2.4% (weight), the phthalic ester of the magnesium atom of 5.0% (weight) and 2.5% (weight), and its median size is 60 μ m.

(C) polymerization

With top synthetic ingredient of solid catalyst, with embodiment 12 (C) in carry out the copolyreaction of ethene and propylene under the identical condition.

The condition of polyreaction and result are shown in table 5 and table 6 respectively.

Because in this experiment, ingredient of solid catalyst impregnated in the silica gel rather than impregnated on organic porous polymer carrier, so the particle characteristics of product is very poor.Find when therefore, checking the autoclave of opening that polymer particle is bonded in polypropylene powder dispersion agent and caking.

Comparative Examples 10

(A) synthesis of solid product

A volume is 200ml and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, add 5.0 gram vinylbenzene, one divinyl benzene copolymer (dvp=0.08ml/g, comprise that pore radius is 0.93ml/g less than 100 with greater than the pore volume in the hole of 5000 , under 80 ℃ through 1 hour drying under reduced pressure), 25.0ml normal heptane, 0.28g (0.67mmol) four titanium butoxide and 242g (11.6mmol) tetraethoxysilane, and under 30 ℃, stirred 45 minutes.

Then, the temperature in the flask is being remained in 5 ℃, in one hour, dripping synthetic organo-magnesium compound among 6.1ml embodiment 1 (A) with dropping funnel.After dropwising, stirred 45 minutes down,, after this,, obtain the brown solid product of 5.7g with each twice of 30ml part normal heptane washed product and in decompression drying down then in 30 ℃ of following restir 45 minutes in 5 ℃.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, after argon replaces, adds 5.6g by the reduction reaction synthetic solid product in (A), and 18.7ml toluene and 0.50ml (1.9mmol) diisobutyl phthalate reacted one hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 18.7ml part toluene wash.

After the washing, add 18.7 toluene in flask, 1.24ml (7.3mmol) n-butyl ether and 21.9ml (199mmol) titanium tetrachloride make its reaction 3 hours under 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and with each 18.7ml part toluene washed twice under this temperature.Then, adopt the mixture of n-butyl ether and titanium tetrachloride to repeat above-mentioned processing once, last one hour, after this, with each twice of 18.7ml part normal heptane washed product and dry down in decompression.Obtain 4.7g reddish-brown ingredient of solid catalyst.

The ingredient of solid catalyst that so obtains is analyzed, and the result shows, exists although detect the titanium atom of trace, and finds no magnesium atom and phthalic ester.

(C) polymerization

Adopt synthetic ingredient of solid catalyst in (B), under the condition identical, carry out the copolyreaction of ethene and propylene with embodiment 12 (C).Yet, do not obtain polymkeric substance.

Because, compare with organic Vesiculated polymer beads that example 1 is used, be used for this experiment, the pore radius scope has less pore volume (dvp) at the porous polymer particles of 100～5000 , therefore, there is the catalyst component of catalytic activity can't be bound in the porous polymer, so catalyzer in the present embodiment also just can't be brought into play the effect of catalyzer effectively in the ethylene/propylene copolymer reaction.

Embodiment 13 and 14

The ingredient of solid catalyst that adopts example 12 (B) to make, carry out the random copolymerization reaction of ethene and propylene according to the method identical with embodiment 12 (C), institute's difference is: the consumption of solid catalyst, the temperature of polyreaction, the dividing potential drop of hydrogen, the composition of ethylene/propene gaseous mixture and the time of polyreaction all change, and concrete the variation sees Table 5.The condition of polyreaction and result are shown in table 5 and table 6 respectively.

Embodiment 15

(A) synthesis of solid catalyst component

An appearance machine is the flask of 100ml, through after the argon replaces, add 2.74g by the reduction reaction synthetic solid product among the embodiment 12 (A), 9.1ml toluene, 0.60ml (3.5mmol) n-butyl ether and 10.6ml (96.4mmol) titanium tetrachloride reacted 3 hours down in 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 10ml part toluene wash.Then, adopt n-butyl ether and the formed mixture of titanium tetrachloride to repeat above-mentioned processing once, with each twice of 10ml part normal heptane washed product and dry down, obtain 2.47g brown solid catalyst component afterwards in decompression.It contains the magnesium atom of the titanium atom and 6.9% (weight) of 2% (weight), and its median size is 50 μ m.

(B) polymerization

Adopt the ingredient of solid catalyst that obtains among the 378.5mg (A), the method identical with example 12 (C) carried out the random copolymerization reaction of ethene and propylene.The condition of polyreaction and result are respectively shown in table 5 and table 6.

Embodiment 16

Adopt the ingredient of solid catalyst that obtains among the embodiment 15 (A), carry out the random copolymerization reaction of ethene and propylene with the method identical with embodiment 12 (C), institute's difference is: the consumption of solid catalyst, the dividing potential drop of hydrogen and the time of polyreaction have changed (as shown in table 5) and electron donor of no use.

The condition of polyreaction and result are respectively shown in table 5 and table 6.

Embodiment 17

Be 5 liters and be equipped with in the autoclave of agitator at a volume, adopt the ingredient of solid catalyst that obtains among the embodiment 12 (B) to carry out ethene, propylene and 1, the random copolymerization reaction of 9-decadiene.

In autoclave, add 50g polypropylene powder effect dispersion agent, reduce the pressure in the autoclave, its temperature to 60 that raises then ℃.Then, feed 4.0 * 10 ⁴The hydrogen of PaG feeds ethylene/propene gaseous mixture (by volume 50%/50%) and the still internal pressure is raise reach 9.8 * 10 ⁵After this PaG, adds 0.5g triethyl aluminum and 0.13g phenyltrimethoxysila,e and a spot of normal heptane to autoclave under argon pressure.Afterwards, under argon pressure, add 1 of 15ml to autoclave, the 9-decadiene, and under argon pressure, add the ingredient of solid catalyst that obtains and a spot of normal heptane among the 331.0mg embodiment 12 (B) in the still.Feeding the ethylene/propene gaseous mixture is 9.8 * 10 to keep total pressure ⁵PaG, ethene, propylene and 1, the random copolymerization reaction of 9-decadiene has been carried out 60 minutes.

After polymerization is finished, remove unreacted monomer, obtain 140g and have the good powder characteristic, neither contain the high-elastic gonosome of particle that fine powder does not contain coarse particle again.On the inwall of autoclave and agitator, do not find polymer attached fully.The condition of polyreaction and result are shown in table 5 and table 6 respectively.

Embodiment 18

Be 5 liters and be equipped with in the autoclave of agitator at volume, adopt the ingredient of solid catalyst that obtains among the embodiment 12 (B) to carry out the random copolymerization reaction of ethene and butene-1.

Adding the 50g polypropylene powder as dispersion agent and after reducing the still internal pressure, the temperature of autoclave is being increased to 60 ℃.Then, feed 3.3 * 10 ⁴PaG hydrogen, and feed ethylene/butylene-1 gaseous mixture (by volume 80%/20%) and make the still internal pressure be increased to 4.9 * 10 ⁵PaG afterwards, adds 0.5g triethyl aluminum, the ingredient of solid catalyst and a spot of normal heptane that obtain among 0.13g phenyltrimethoxysila,e and the 408.3mg embodiment 12 (B) to autoclave under argon pressure.Feed ethylene/butylene-1 gaseous mixture in order that keep total pressure 4.9 * 10 ⁵PaG, the copolyreaction of ethylene/butylene in gas phase-1 was carried out 60 minutes.

After polymerization finishes, remove and obtain 93g behind the unreacted monomer and have good particle characteristics, neither contain the particle elastomerics that fine powder does not contain coarse particle again.On autoclave inwall and agitator, do not find the deposition of any polymkeric substance.The condition and the result of polyreaction are shown on table 5 and the table 6 respectively.

Embodiment 19

In a volume is 26 liters the gas-phase polymerization reactor of fluidized bed type, adopt the ingredient of solid catalyst that obtains among the embodiment 12 (B) to carry out the random copolymerization reaction of ethene and butene-1.

After reactor is heated to 70 ℃, in reactor, add 300g in advance the polypropylene powder of drying under reduced pressure as dispersion agent, then, in rising pressure downhill reaction device, add 4.26g triethyl aluminum, the ingredient of solid catalyst and a spot of hexane that obtain among 1.11g phenyltrimethoxysila,e and the 1.2g embodiment 12 (B).Have mol ratio: the gaseous mixture of the ethene of ethylene/butylene-1/ hydrogen=53/26.5/20.5, butene-1 and hydrogen, in 6.9-7.4 * 10 ⁵Flow velocity with 0.3m/ second under the pressure of PaG circulates in reactor.When the mol ratio of ethylene/butylene-1/ hydrogen departs from this predictor, feed some gases again to regulate this mol ratio.Under this condition, the gas phase copolymerization of ethene and butene-1 carried out 7 hours on fluidized-bed.During this period, the height that keeps polymkeric substance in the reactor is 2～4 to the ratio (1/d) of reactor diameter.After polyreaction is finished, from reactor, take out the polymkeric substance of the amount of polymers be equivalent to form, stay the dispersion agent that polymkeric substance in the reactor is used as the polyreaction of carrying out later.When polyreaction repeated six times by above-mentioned technology, the initial used shared per-cent of polypropylene powder had become little of having ignored in polymkeric substance.

The polymkeric substance of Huo Deing has good powder characteristics like this, and it neither contains fine powder and does not also contain coarse particle.It contains 82% (weight) ethene, and its limiting viscosity [η] is 1.4, and bounding force is 4.6g/cm ²In six polymeric whole processes, the total polymer (P/cat) that every 1g solid catalyst is generated is 540.

Comparative Examples 11

(A synthesis of solid product

A volume is 100ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, add 6.00g styrene diethylene benzene copoly mer (dvp=0.75, median size=1,300 μ m, under 80 ℃ through 30 minutes drying under reduced pressure), the 30ml normal heptane, 0.27g (0.79mmol) four titanium butoxide and 2.88g (13.8mmol) tetraethoxysilane also stirred 45 minutes down in 30 ℃.

Then, in 45 minutes, drip synthetic organo-magnesium compound among 7.3ml embodiment 1 (A), the temperature in the flask is remained on 5 ℃ therebetween with dropping funnel.Dropwise, the material in 5 ℃ of following stirred flask 45 minutes stirred 45 minutes down at 30 ℃ again, after this, with each twice of 30.0ml part normal heptane washed product and dry down in decompression, obtained 7.45g brown solid product.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, after argon replaces, adds the solid product that 6.71g is obtained by reduction reaction in (A), and 22.4ml toluene and 0.92ml (3.44mmol) diisobutyl phthalate reacted 1 hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 22.4ml part toluene wash.Then, add 22.4ml toluene in flask, 1.48ml (8.74mmol) n-butyl ether and 26.2ml (238mmol) titanium tetrachloride reacted 3 hours down in 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 22.4ml part toluene wash.Then, the mixture that adopts n-butyl ether and titanium tetrachloride to form repeated above-mentioned processing once in 1 hour, after this, with each twice of 22.4ml part normal heptane washed product and dry down in decompression, obtained 5.73g brown solid catalyst component.

So the ingredient of solid catalyst that obtains contains the phthalic ester of the magnesium atom and 0.9% (weight) of 0.14% (weight) titanium atom 2.5% (weight).

(C) polymerization

Synthetic ingredient of solid catalyst above adopting carries out the copolymerization of ethene and butene-1 under the condition identical with embodiment 19.Yet because catalyzer fails fully to disperse, its flow state is along with polymeric becomes unstable, and this fluidized-bed gas phase copolymerization can not carry out continuously, and therefore resulting polymkeric substance contains many thick polymkeric substance and hollow polymer.

Because the median size of the used organic porous polymer carrier of ingredient of solid catalyst big than among the embodiment 19 in the present embodiment, so, in the fluidized bed gas-phase polymerization of ethene and butylene-l, can not obtain stable flow state.

Embodiment 20

(A) synthesis of solid catalyst component

A volume is 3000ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, add 299g in 110 ℃ of styrene diethylene benzene copoly mers of 360 minutes of following drying under reduced pressure (dvp=0.68ml/g) and 1, the 500ml normal heptane, 10.1g (29.9mmol) four titanium butoxide, 107.0g (514mmol) tetraethoxysilane also stirred 45 minutes under 30 ℃.

Then, in 70 minutes, drip the organo-magnesium compound that 272ml embodiment 1 (A) prepares, simultaneously the temperature in the flask is remained on 5 ℃ with dropping funnel.Dropwise, the material in 5 ℃ of following stirred flask 45 minutes is then in 30 ℃ of following restir 45 minutes.After this, with each 1.500ml part heptane wash product twice, use twice of each 1500ml part toluene wash then.

Subsequently, add 1240ml toluene and 99.2ml (371mmol) diisobutyl phthalate, it was reacted 30 minutes down in 95 ℃.

After the reaction, isolate the solid product in the liquid phase, and with twice of each 1240ml part toluene wash.

After the washing, in flask, add 1,100ml toluene, 73.0ml (431mmol) n-butyl ether and 1300ml (11.83mmol) titanium tetrachloride, it was reacted 3 hours down in 95 ℃, reaction finishes, and isolates the solid product in the liquid phase under 95 ℃, and uses twice of the toluene wash of 1200ml part under this temperature respectively.Then, adopt the mixture of butyl ether and titanium tetrachloride to repeat above-mentioned processing once, last one hour, use each 1200ml part heptane wash twice again, this is after drying under reduced pressure can obtain 345g brown solid catalyst component.

So the ingredient of solid catalyst that obtains contains the titanium atom of 0.20% (weight), the phthalic ester of the magnesium atom of 2.5% (weight) and 1.3% (weight).

The median size of this ingredient of solid catalyst is 40 μ m.

(B) prepolymerization catalyst is synthetic.

Volume is 2 liters and is equipped with the reactor of agitator, through behind the nitrogen replacement completely, imports the ingredient of solid catalyst that obtains among the 68g (A), the 1350ml hexane, and 1.33g triethyl aluminum and 0.35g phenyltrimethoxysila,e, and start stirring.Then, its temperature is transferred to 18-20 ℃, adds 340g propylene and polyase 13 hour, filter reaction mixture and in 40 ℃ of following drying under reduced pressure solid products obtains the 340g prepolymerization catalyst.

In addition, repeat above-mentioned steps twice again, can obtain the 1000g prepolymerization catalyst

(C) polymerization

The prepolymerization catalyst that employing obtains is above finished the random copolymerization reaction of ethene and butene-1 in a volume is the fluidized bed type gas-phase polymerization reactor of 1.5m.

At first, 70kg propylene polymerization composition granule is imported reactor as the dispersion agent of catalyzer, import the gaseous mixture of being made up of 55.2% (mol) ethene, 42% (mol) propylene and 2.8% (mol) hydrogen that recycles then, cycle rate is 140m ³/ hour, flow velocity is 0.2 meter per second, pressure is 9.8 * 10 therebetween ⁵Pa (gauge pressure), temperature is 70 ℃.

Then, with prepolymerization catalyst, triethyl aluminum and phenyltrimethoxysila,e be respectively with 9.6g/ hour, and the speed of 3.9g hour and 0.779/ hour is added in the reactor continuously, finishes copolyreaction.Subsequently the excess polymeric that produces is discharged reactor, proceeded polyreaction 61 hours.Polymerization process is stablized with interference-free carries out.

Polymerization quantity is 9.8 kilograms/hour, and the polymerization quantity of per unit weight solid catalyst is 5100g/g.So the polymkeric substance that obtains has good powder characteristics and neither contains fine powder and do not contain coarse particles again.Wherein contain 82% (weight) ethene, its limiting viscosity [η] is 2.9, and its bounding force is 2.2g/cm ²

Embodiment 21

(A) propylene polymerization

A volume is 130ml and the stainless steel autoclave that is equipped with magnetic stirrer, after argon replaces, import the 0.57mmol triethyl aluminum, the 0.057mmol phenyl triethoxysilane, 45.0mg implements the ingredient of solid catalyst and the 80ml liquefied propylene of acquisition among 1 (C).

In agitated autoclave, in the material, it was kept 1 hour down at 60 ℃.After emitting excessive propylene, make resulting polypropylene air dried overnight.Like this, can obtain the 11.7g polypropylene.

Therefore, the polypropylene productive rate (g) of each gram titanium is 52000 (pp/Ti) in the ingredient of solid catalyst.

If extracted the polypropylene powder that obtains like this 6 hours with the ebullient normal heptane, then the amount of the resistates that can not be extracted [represent with per-cent, below be called " IY (%) "] is 93.9%.Polyacrylic tap density [hereinafter being called BD (g/ml)] is 0.43g/ml.

(B) size distribution of mensuration polypropylene powder

By means of mesh size is that the JIS standard metal bolting silk net of 0.125-3.36mm can be with the polypropylene powder classification that obtains in (A).The polymkeric substance on each sieve is stayed in weighing then, and calculates its ratio with respect to total polymer weight.To pressing the particle diameter accumulation greatly, table 7 and Fig. 2 have described the running summary of the points scored [% (weight)] that screening produces to its result from childhood.Tap density (BD) also is shown in table 7.

Comparative Examples 12

(A) synthesis of solid product

A volume is 1 liter and is equipped with agitator and the flask of dropping funnel, after argon replaces, import the 600ml normal heptane, 7.6g (22.2mmol) four titanium butoxide and 7.81g (375mmol) tetraethoxysilane, form a uniform solution, under room temperature, it was stirred 30 minutes.Then, synthetic organo-magnesium compound among the 200ml embodiment 1 (A) was dripped to flask with dropping funnel lentamente through 3 hours, at this moment, the temperature in the flask remains on 5 ℃.Dropwise,, under room temperature, isolate the solid product in the liquid phase then,, can obtain 64.5g brown solid product with each 600ml part normal heptane washed twice and dry down in decompression with the restir 1 hour under room temperature of the material in the flask.

(B) synthesis of solid catalyst component

The flask that volume is 200ml adds 17.10g synthetic solid product in reduction process (A) in after argon replaces, 85.5ml-chlorobenzene and 3.76ml (14.0mmol) diisobutyl phthalate reacted 1 hour down in 80 ℃.

After the reaction, isolate in the liquid phase solid product and with each 90mol part normal heptane washed twice.

After this, add the 85.5ml-chlorobenzene in flask, 5.64ml (33.3mmol) n-butyl ether and 100.9ml (918mmol) titanium tetrachloride reacted 3 hours down in 80 ℃.Reaction finishes, under 80 ℃, isolate in the liquid phase solid product and under this temperature with each 90mol chlorobenzene washed twice.

Adopt the mixture of n-butyl ether and titanium tetrachloride to repeat above-mentioned processing once, last one hour, after this, with each twice of 90ml part normal heptane washing reaction product and dry down in decompression.Thereby can obtain 14.4g brown solid catalyzer.

So the ingredient of solid catalyst that obtains contains the titanium atom of 27% (weight), the phthalic ester of the magnesium atom of 21% (weight) and 9.7% (weight).

(C) polymerization

The ingredient of solid catalyst that employing makes is above finished the polymerization of propylene according to the method identical with embodiment 21 (A).Its result is as follows: PP/Ti=15300, IT=96.4%, BD=0.30g/ml.

The size distribution of consequent polypropylene powder can be measured by the method identical with embodiment 21 (B), to obtain being shown in the result among table 7 and Fig. 2.

In this test, because ingredient of solid catalyst is not to be carried on the Vesiculated polymer beads, thereby the tap density of polymkeric substance is significantly less than embodiment's 21.The polymkeric substance that obtains among this embodiment contains the fine powder that a large amount of particle diameters are lower than 500 μ m.

Embodiment 22

(A) solid product is synthetic

A volume is 200ml and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, add 9.9g styrene diethylene benzene copoly mer (dvp=1.05ml/g, under 80 ℃ through one hour drying under reduced pressure), 49.5ml normal heptane, 0.90g (2.6mmol) four titanium butoxide and 9.49g (45.5mmol) tetraethoxysilane stirs them 30 minutes under 30 ℃.

Subsequently, in one hour, synthetic organo-magnesium compound 24.0ml among the embodiment 1 (A) is dropped in the flask, during this period the temperature in the flask is remained on 5 ℃ with dropping funnel.Dropwise, the material in 5 ℃ of following stirred flask 45 minutes subsequently in 30 ℃ of following restir 45 minutes, after this, with each 50ml part normal heptane washed twice and dry down in decompression, obtains 15.9g brown solid product.

This solid product contains the magnesium atom of the titanium atom and 42% (weight) of 0.54% (weight).

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, through after the argon replaces, adds synthetic solid product among 6.8 (A), and 22.7ml toluene and 1.8ml (6.7mmol) diisobutyl phthalate also reacted 1 hour under 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 23ml toluene wash.

Washing finishes, and adds 22.7ml toluene in flask, and 1.5ml (8.9mmol) n-butyl ether and 26.5ml (241mmol) titanium tetrachloride also reacted 3 hours under 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 23mol part toluene wash.Then, adopt n-butyl ether and the formed mixture of titanium tetrachloride to repeat above-mentioned processing once, last one hour, wash this product twice with each 23ml part normal hexane afterwards and drying under decompression.Obtain 5.5g brown solid catalyst component.

The titanium atom that contains 0.46% (weight) in this ingredient of solid catalyst, the phthalic ester of the magnesium atom of 5.4% (weight) and 1.5% (weight).

(C) polymerization

Adopt the ingredient of solid catalyst of preparation in (B), under the condition identical, carry out the polymerization of propylene with example 21 (A).Its result is as follows: PP/Ti=23300, IT=95.7%, BD=0.35g/ml.

Measure the polyacrylic size distribution that so obtains according to the method identical with embodiment 21 (B), its result is in table 7 and Fig. 2.

Embodiment 23

(A) synthesis of solid product

A volume is 200ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, add 7.0g styrene diethylene benzene copoly mer (dvp=0.91ml/g, under 80 ℃ through one hour drying under reduced pressure) and 28ml n-butyl ether and stirring, stir on the limit, the limit was added dropwise to synthetic organo-magnesium compound among the 20.2ml embodiment 1 (A) with dropping funnel in 10 minutes, during this period the temperature in the flask is remained on 80 ℃, under this temperature, make the interior material reaction of flask 1 hour.Use each 28ml part normal heptane washed twice again with behind twice of each 28ml part n-butyl ether washing reaction product, obtain the product that 7.0g handles through organic-magnesium in the dry down back of decompression.

A volume is 100ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, add the product that synthetic is crossed through organic process above the 7.0g, the 36ml normal heptane, 0.62g (1.8mmol) four titanium butoxide and 6.31g (30.3mmol) tetraethoxysilane also stir 30 molecules under 30 ℃.

Then, in 1 hour, drip synthetic organo-magnesium compound among 160ml embodiment 1 (A), the temperature in the flask is remained on 5 ℃ therebetween with dropping funnel.Dropwise, after this material in 5 ℃ of following stirred flask 1 hour, with each twice of 35ml part normal heptane washed product and dry down in decompression, obtains l1.6g brown solid product.

The magnesium atom that contains the titanium atom and 5.1% (weight) of 0.46% (weight) in this solid product.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, after argon replaces, adds synthetic solid product among the 4.22g (A), and 14.0ml toluene and 0.94ml (3.5mmol) diisobutyl phthalate reacted 1 hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 20ml neighbour toluene wash.

Washing finishes, and adds 14.0ml toluene in flask, and 0.93ml (5.1mmol) n-butyl ether and 16.5ml (149mmol) titanium tetrachloride reacted 3 hours down in 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and under this temperature with twice of each 20mol part toluene wash.Then, adopt the mixture of forming by n-butyl ether and titanium tetrachloride in 1 hour, to repeat above-mentioned processing once, after this,, obtain 3.65g brown solid catalyst component with each twice of 210ml part normal heptane washed product and dry down in decompression.

So the ingredient of solid catalyst that obtains contains the titanium of 0.41% (weight), the phthalic ester of the magnesium of 5.2% (weight) and 0.1% (weight).

(C) polymerization

Synthetic ingredient of solid catalyst above adopting, with embodiment 21 (A) in carry out the polymerization of propylene under the identical condition, its result is as follows: PP/Ti=124000, IT=93.9%, BD=0.45g/ml.

Here the polyacrylic size distribution of Chan Shenging can be measured by the method identical with embodiment 21 (B), and it the results are shown in table 7.

The comparative example 13

(A) synthesis of solid product

A volume is 200ml and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, add 5.0g styrene diethylene benzene copoly mer (dvp=0.08ml/g, comprise that pore radius is 0.93ml/g less than 100 with greater than the pore volume in the hole of 5000 , under 80 ℃ through 1 hour drying under reduced pressure), 25.0ml normal heptane, 0.23g (0.67mmol) four titanium butoxide and 242g (11.6mmol) tetraethoxysilane, and under 30 ℃, stirred 45 minutes.

Then, the temperature in the flask is being remained in 5 ℃, in 1 hour, dripping synthetic organo-magnesium compound among 6.1ml embodiment 1 (A) with dropping funnel.Dropwise, in 5 ℃ down stir 45 minutes after in 30 ℃ of following restir 45 minutes, after this,, obtain the 5.7g solid product with each twice of 30ml part normal heptane washed product and in decompression drying down.

The magnesium atom that contains the titanium atom and 25% (weight) of 0.3% (weight) in this solid product.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, after argon replaces, adds the solid product that obtains among 5.6 (A), and 18.7ml toluene and 0.50ml (1.9mmol) diisobutyl phthalate reacted 1 hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 18.7ml part toluene wash.

After the washing, add 18.7ml toluene in flask, 1.24ml (7.3mmol) n-butyl ether and 21.9ml (199mmol) titanium tetrachloride make its reaction 3 hours under 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and with each 18.7ml part toluene washed twice under this temperature.Then, adopt the mixture of n-butyl ether and titanium tetrachloride to repeat above-mentioned processing once, last 1 hour, afterwards, with each twice of 18.7ml part normal heptane washed product and dry down in decompression.Obtain 4.7g brown solid catalyst component.

The ingredient of solid catalyst of acquisition like this is carried out analytical results show, exist although measure the titanium atom of trace, and find no magnesium atom and phthalic ester.

(C) polymerization

Synthetic ingredient of solid catalyst above adopting carries out the polymerization of propylene under the condition identical with embodiment 21 (A).Yet, do not obtain polymkeric substance.

Compare with 23 used Vesiculated polymer beads with embodiment 21,22, be used for this test, the pore radius scope has less pore volume (dvp) at the porous polymer particles of 100-5000 , therefore, catalyst component with polymerization activity can't be bound in the porous polymer, thereby also just can't bring into play the effect of catalyst for polymerization of propylene effectively.

Embodiment 24

(A) synthesis of solid product

A volume is 300ml and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, adds 20g polyvinyl chloride (dvp=0.27ml/g, under 80 ℃ through 1 hour drying under reduced pressure) and 68ml n-butyl ether.In one minute, drip synthetic organo-magnesium compound among 68ml embodiment 1 (A) in the material in flask with dropping funnel while stirring, meanwhile, the temperature in the flask is remained on 30 ℃ and reaction 1 hour under this temperature.

Then, with each 42ml part n-butyl ether washed product twice, and then with each 85ml part normal heptane washed twice, and, can obtain the product that 20.3g handles through organic-magnesium through drying under reduced pressure.

After this, a volume is 100ml and is equipped with agitator and the flask of dropping funnel, after argon replaces, adds the product that 9.3g handles through organic-magnesium, the 46ml normal heptane, 0.32g (0.94mmol) four titanium butoxide and 3.3g (16mmol) tetraethoxysilane also stirred 45 minutes under 30 ℃.

Then, temperature in the flask is being remained in 5 ℃, in 1 hour, drip synthetic organo-magnesium compound among 8.4ml embodiment 1 (A) with dropping funnel, dropwise, material in 5 ℃ of following stirred flask reaches one hour, restir 1 hour under room temperature can obtain 10.5g brown solid product with twice of each 46ml part normal heptane washed product and through behind the drying under reduced pressure then.

The magnesium atom that so contains the titanium atom and 2.4% (weight) of 0.2% (weight) in the solid product that obtains.

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, through after the argon replaces, adds the solid product that makes among the 5.1g (A) therein, and 17.0ml toluene and 0.43ml (1.6mmol) diisobutyl phthalate makes it react 1 hour down in 95 ℃.

After the reaction, isolate the solid product in the liquid phase, and with twice of each 17ml part toluene wash.

Washing finishes, and adds 17.0ml toluene, and 1.12ml (6.6mmol) n-butyl ether and 20.2ml (182mmol) titanium tetrachloride reacted 3 hours down in 95 ℃.After the reaction, under 95 ℃, isolate the solid product in the liquid phase, under this temperature with twice of each 17mol part toluene wash.Then, in 1 hour, adopt mixture to repeat above-mentioned processing once, after this,, obtain 3.8g brown solid catalyst component with each twice of 17ml normal heptane washed product and dry down in decompression by n-butyl ether and titanium tetrachloride.

So the ingredient of solid catalyst that obtains contains the titanium of 0.1% (weight), the phthalic ester of the magnesium atom of 1.5% (weight) and 0.4% (weight).

(C) polymerization

Adopt (B) synthetic ingredient of solid catalyst, in embodiment 21 (A), carry out the polyreaction of propylene under the same terms, its result is as follows: PP/Ti=100000, IY=95.5%, BD=0.34g/ml, the size distribution of the polypropylene powder that so makes can be by measuring by the method identical with embodiment 21 (B), and it the results are shown in table 7.

Embodiment 25

(A) polymerization in the liquefied propylene

Volume is 3 liters and is equipped with the stainless steel autoclave of agitator, through after the argon replaces, add the 2.6mmol triethyl aluminum, synthetic ingredient of solid catalyst among 0.39mmol phenyltrimethoxysila,e and the 31.9mg embodiment 22 adds hydrogen then and reaches 1.2 * 10 until its dividing potential drop ⁴Till the Pa.After this add the 780g liquefied propylene, the temperature in the autoclave is risen to 80 ℃, under 80 ℃, carried out polyreaction 2 hours.

After the polymerization, discharge unreacted monomer, in 60 ℃ in polymkeric substance that drying under reduced pressure produced 2 hours.Can obtain the 118g polypropylene powder like this.

Therefore, the PP/Ti value equals 804000.The ratio [hereinafter being called CXS (%)] that dissolves in the atactic component of cold xylene in the polymkeric substance ultimate production equals 2.0% (weight).In addition, BD=0.36g/ml.

(B) preparation biaxial stretching film

Use a portable proof press, by at 230 ℃ of following pre-thermopolymers 5 minutes, then up to 7.8 * 10 ⁶Under the pressure of Pa (gauge pressure) it was suppressed 3 minutes, and kept 1 minute under this pressure, the polymer processing that obtains in (A) can be become thickness is the sheet material of 500 μ m.The sheet material that so obtains is cut by the specification of 90 * 90mm, and under following condition, carry out biaxial stretching.Like this, adopt portable biaxial stretching machine, sheet material 155 ℃ of following predetermined thermal 3.5 minutes, then, longitudinally and laterally stretched respectively with 5 meters/minute speed, make its separately length be 5 times of its original length.So just, can obtain the biaxial stretching film.

Through this film of microscopic examination, the result shows that no flake exists.

The comparative example 14

(A) synthesis of solid product

A volume is 200ml and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, adds 15.0g silicic acid (dvp=0.83ml/g, process drying under reduced pressure under 100 ℃) and 45.5ml n-butyl ether.In the material, dripped synthetic organo-magnesium compound among 42ml embodiment 1 (A) with dropping funnel in 10 minutes in stirred flask, during this period, the temperature in the flask remains on 30 ℃, and it was reacted 2 hours under this temperature.

Use each 40ml part normal heptane washed twice again with after twice of each 20ml n-butyl ether washed product, can obtain the product that 14.8g handles through organic-magnesium behind the drying under reduced pressure.

Then, a volume is 300ml and is equipped with agitator and the flask of dropping funnel, through after the argon replaces, add the product that 13.3g handles through organic-magnesium, the 69ml normal heptane, 0.77g (2.3mmol) four titanium butoxide and 6.0g (38.6mmol) tetraethoxysilane also stirred 30 minutes under 30 ℃.

After this, in 2 hours, drip synthetic organo-magnesium compound among 22.6ml embodiment 1 (A), during this period, the temperature in the flask is remained on 5 ℃ with dropping funnel.Dropwise, the material in 5 ℃ of following stirred flask 1 hour stirred 1 hour under room temperature then, used each 60ml normal heptane washed product twice afterwards, through behind the drying under reduced pressure, obtained 21.1g brown solid product.

The solid product that so obtains contains the magnesium atom of the titanium atom and 5.9% (weight) of 0.53% (weight).

(B) synthesis of solid catalyst component

A volume is the flask of 100ml, through after the argon replaces, adds synthetic solid product among the 5.6g (A), and 18.8ml toluene and 0.74ml (2.8mmol) diisobutyl phthalate reacted 1 hour down in 95 ℃.

After the reaction, isolate in the liquid phase solid product and with twice of each 18.8ml part toluene wash.

Washing finishes, and adds 18.8ml toluene, and 0.65ml (3.8mmol) n-butyl ether and 11.6ml (106mmol) titanium tetrachloride reacted 3 hours down in 95 ℃.After the reaction, under 95 ℃, isolate in the liquid phase solid product and with each 18.8mol part toluene washed twice under this temperature.After this, in 1 hour, adopt the mixture of n-butyl ether and titanium tetrachloride to repeat above-mentioned processing once, use twice of each 18.8ml normal heptane washed product and drying under reduced pressure afterwards, obtain 4.8g brown solid catalyst component.

So the ingredient of solid catalyst that obtains contains the titanium of 1.1% (weight), the phthalic ester of the magnesium atom of 7.8% (weight) and 1.5% (weight).

(C) polymerization

The ingredient of solid catalyst that employing makes above, with embodiment 21 (A) in finish the polymerization of propylene under the identical condition.Its result is as follows: PP/Ti=153000, CXS=2.5% (weight), BD=0.42g/ml.

(D) preparation biaxial stretching film.

Adopt the polymkeric substance that makes in (C), can prepare the biaxial stretching film according to the method identical with embodiment 25 (B).Show at every 1cm through the microscopic examination result ²Film on 43 flakes are arranged.

In this test, because silica gel is used as carrier, the flake number that solid produces on this film is greater than the flake number on the film among the embodiment 25.

As mentioned above, select catalyst system of the present invention for use, can produce following effect:

(1) owing to each titanium atom in this catalyst system has very high catalytic activity, thereby can obtain only to contain (the alpha-olefinic polymer of seldom measuring halogen and titanium, the tinting strength of this and polymkeric substance, the solidity to corrosion of stability and equipment is closely related, and needn't take any step to remove catalyst residue.That is to say that the present invention does not remove necessity of catalyst residue in the equipment and reduced the productive expense of alpha-olefinic polymer.

(2) if use catalyzer of the present invention to reach the purpose of producing crystalline polymer, because catalyst system of the present invention only forms very a spot of by product---amorphous polymer, thereby need not remove amorphous polymer and just can produce alpha-olefinic polymer with excellent mechanical properties.

(3) select for use catalyst system of the present invention can produce alpha-olefinic polymer, can dwindle the size of production unit like this and reach very high throughput with very high tap density.

(4) in catalyst system of the present invention, the shape of porous polymer particles has determined the solid catalyst shape.This means according to the similarity relation between them, by shape and big or small shape and the size that is easy to control alpha-olefin that changes polymer beads.

(5) select for use catalyst system of the present invention fine powder quantity in the alpha-olefinic polymer can be reduced to minimum level, therefore can avoid the line clogging phenomenon that causes because of fine powder.

(6) select catalyst system of the present invention for use, can not make alpha-olefinic polymer be subjected to the pollution of inorganic oxide and quality product is descended (as flake occurring), and reach above-mentioned effect (4) and (5).

(7) by adopting catalyst system of the present invention and gaseous polymerization, can be efficiently and high stability production particle elastomerics and particle thermoplastic elastomer, therefore, compare with the whole bag of tricks of front, can reduce productive expense widely.

(8) select for use catalyst system of the present invention can obtain particulate state elastomerics and thermoplastic elastomer, help carrying out molding and procedure of processing like this.

Table 1

	Step 1					Step 2
										(A) ingredient of solid catalyst (mg)	(B) triethyl aluminum (g)	(C) electron donor (g)	Temperature (℃)	Time (minute)	C′ 2/ alpha-olefin compositions % (weight)	Temperature (℃)	Pressure (handkerchief (Pa))	Time (minute)
	Embodiment 1 Comparative Examples 1 " 2 " 3 " 4 " embodiment 2 " 3 " 4	????564.0 ????297.0 ????103.2 ?????31.8 ?????32.4 ????282.9 ????377.0 ????372.4	??0.5 ??″ ??″ ????″ ????″ ????″ ????″ ????″	Phenyltrimethoxysila,e 0.13 " " " methyl p toluate 0.2 phenyltrimethoxysila,e 0.13 " "	??75 ??″ ????″ ????″ ????″ ????″ ????″ ????″	??15 ??10 ??″ ????″ ????″ ????″ ????15 ??10	?C′ 2/C′ 3＝50/50 ????″ ???????″ ???????″ ???????″ ?C′ 2/C′ 3＝80/20 ?C′ 2/C′ 3＝50/50 ?C′ 2/C′ 4＝80/20	??70 ??″ ????″ ????″ ????″ ????″ ????″ ????75	???9.8×10 5?????″ ?????????″ ?????????″ ?????????″ ??????″(1) ???″(2) ???3.9×10 5										?420 ?390 ?400 ?360 ?240 ?540 ?480 ?420

Annotate: the charging of step 1: C ' ₃-1.3 * 10 ⁵Pa, H ₂-5.2 * 10 ⁴Pa; The charging of step 2: H ₂7.4 * 10 ³Pa[(1) 2.9 * 10 ⁴Pa, (2) 2.0 * 10 ⁴Pa] * in the process of step 2, the catalyzer complete deactivation.

Table 2

	Amount of polymers (g)	PP/Ti (g/g)	Produce ratio (step 1/ step 2) (weight)	CXS value % (weight) in the step 1	[η]p	[η]EP	[η]T	C in the step 2 2Content % (weight)	Bounding force (g/the cm of polymer beads 2)	The state of autoclave
											Embodiment 1 Comparative Examples 1 " 2 " 3 " 4 embodiment, 2 embodiment, 3 embodiment 4	????643 ????512 ????435 ????328 ????208 ????368 ????205 ????260	?228,000 ?157,000 ?220,000 ?547,000 ?257,000 ?260,000 ?109,000 ?140,000	????15/85 ????17/83 ????18/82 ????32/68 ????54/46 ????25/75 ????20/80 ????27/73	????3.8 ????2.5 ????1.8 ????2.8 ????4.4 ????3.7 ????3.5 ????4.0	?1.7 ?2.3 ?2.2 ?2.3 ?2.4 ?2.0 ?1.7 ?2.2	?3.8 ?3.8 ?3.7 ?3.0 ?3.9 ?3.5 ?2.6 (n)EB ?4.1	?3.5 ?3.6 ?3.5 ?2.8 ?3.1 ?3.1 ?2.4 ?3.6	????48 ????46 ????47 ????47 ????48 ????25 ????43 ????77	2.8 7.7 8.4 difficult mensuration " 2.1 4.8 2.4	The adhesion of polymer is the significantly adhesion of " " polymer beads remarkable " adhesion of polymer is remarkable " or not

Table 4

	Amount of polymers (g)	P/Cat (g/g)	Produce ratio (step 1/ step 2) (weight)	[η]E	[η]EP	[η]T	C in the step 2 2Content (% weight)	Bounding force (g/the cm of polymer beads 2)	The state of autoclave
										Embodiment 5 Comparative Examples 5 " 6 embodiment 6 " 7 " 8 Comparative Examples, 7 embodiment 9 " 10 " 11	????338 ????199 ????397 ????380 ????450 ????422 ????350 ????478 ????469 ????456	????1,080 ????1,570 ????1,110 ????900 ????1,190 ????1,020 ????2,430 ????1,580 ????910 ????1,230	????15/85 ????24/76 ????13/87 ????11/89 ????10/90 ????10/90 ????10/90 ????11/89 ????13/87 ????15/85	?1.7 ?2.6 ?2.3 ?2.4 ?2.4 ?2.4 ?2.6 ?2.0 ?2.5 ?1.8	??3.1 ??3.4 ??3.1 ??2.9 ??1.9 ??1.8 ??2.0 ??4.1 ??2.9 ??(n)EB ??3.0	?2.9 ?3.2 ?3.0 ?2.9 ?2.0 ?1.8 ?2.1 ?3.9 ?2.8 ?2.8	????48 ????46 ????48 ????47 ????49 ????47 ????47 ????79 ????47 ????80	" 2.4 3.2 2.6 can't measure 3.5 5.0 4.4 4.2 can't measure	The adhesion of the not obvious polymer beads of adhesion of polymer is " " " " " " " " significantly "

Table 5

	(A) ingredient of solid catalyst (mg)	(B) triethyl aluminum (g)	Electron donor: phenyltrimethoxysila,e (g)	C′ 2/ alpha-olefin compositions % (volume)	Temperature (℃)	????H 2Dividing potential drop (PaG)	Stagnation pressure (PaG)	Time (minute)
									Embodiment 12 Comparative Examples 8 " 9 embodiment 13 " 14 " 15 " 16 " 17 " 18	?418.2 ?144.1 ?237.5 ?310.0 ?271.5 ?378.5 ?315.0 ?331.0 ?408.3	??0.5 ??″ ????″ ????″ ????″ ????″ ????″ ????″ ????″	0.13 " " " " " do not have 0.13 "	C′ 2/C′ 3＝50/50 ??″ ????″ ????″ C′ 2/C′ 3＝70/30 C′ 2/C′ 3＝50/50 ??″ C′ 2/C′ 3＝50/50 (*)C′ 2/C′ 4＝80/20	??60 ??″ ????″ ????75 ??″ ????60 ??″ ????″ ????″	????6.0×10 4????″ ?????????″ ????????4.7×10 4????4.2×10 4????1.0×10 5????9.8×10 3????4.0×10 4????3.3×10 4	?9.8×10 5??″ ????″ ????″ ????″ ????″ ????″ ????″ ?4.9×10 6	????50 ????60 ????45 ????60 ????90 ????30 ????60 ????″ ???????120

(*) in 1, the 9-decadiene carries out polymerization under existing

Table 6

	Amount of polymers (g)	P/cat (g/g)	[η]	C 2Content (% weight)	1,9-decadiene content (% weight)	Bounding force (the g/cm of polymer beads 2)	The state of autoclave
								Embodiment 12 Comparative Examples 8 " 9 embodiment 13 " 14 " 15 " 16 " 17 " 18	?151 ?160 ?160 ?151 ?111 ?115 ?175 ?140 ??93	?360 ?1,110 ?670 ?490 ?410 ?300 ?560 ?420 ?230	?2.6 ?2.7 ?2.9 ?2.1 ?3.2 ?1.9 ?2.1 ?2.5 ?2.3	?77.0 ?72.8 ?67.0 ?61.0 ?82.3 ?54.7 ?33.6 ?61.6 ?79.6	????- ????- ????- ????- ????- ????- ????- ????9.7 ????-	2.1 can't measure 3.2 2.4 3.4 4.0 5.7 4.1	The not obvious polymer lumps of the adhesion of polymer " adhesion of polymer is not obvious " " " " "

Table 7

Mesh size (μ m)	Embodiment 21	Comparison example 12	Embodiment 22	Embodiment 23	Embodiment 24
						Running summary of the points scored % (weight)
	????3360 ????2830 ????2380 ????2000 ????1680 ????1410 ????1190 ????1000 ????710 ????590 ????500 ????420 ????350 ????297 ????250 ????177 ????125 ????Pan(125) ????ED(g/ml)	?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????99.9 ?????97.6 ?????80.4 ?????27.7 ?????0.8 ?????0.1 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.43	?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????99.8 ?????97.3 ?????88.4 ?????35.3 ?????19.8 ?????13.9 ?????9.5 ?????4.0 ?????2.0 ?????0.9 ?????0.3 ?????0.1 ?????0.30	?????100.0 ?????99.7 ?????98.9 ?????93.2 ?????79.1 ?????60.8 ?????44.5 ?????32.6 ?????14.7 ?????5.8 ?????0.6 ?????0.2 ?????0.1 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.35	?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????99.9 ?????98.0 ?????80.8 ?????35.7 ?????0.1 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.0 ?????0.45						?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????100.0 ?????99.4 ?????71.6 ?????32.6 ?????13.9 ?????1.5 ?????0.4 ?????0.1 ?????0.0 ?????0.0 ?????0.34

Claims (5)

1. one kind prepares the elastomeric method of particle, and this method comprises polymerization or the copolymerization of adopting the catalyst system that contains following component to finish alpha-olefin, and this catalyst system contains at least:

A kind of ingredient of solid catalyst (A), wherein contain titanium at least as catalyst component, magnesium and chlorine, they are immersed in median size is that 5～1000 μ m, pore volume are that 0.1ml/g or higher and pore radius are on organic porous polymer carrier of 100～5000 and a kind of organo-aluminium compound (B).

2. in accordance with the method for claim 1, comprising first step, prepare isotatic polypropylene by the polyreaction in liquid propylene and/or gas phase, carry out second step subsequently, ethylene content is 5～95% (weight) to preparation ethene-alpha-olefin random copolymers in the multipolymer that generates in second step so that make in gas phase, its limiting viscosity (135 ℃) 1,2,3, in the 4-tetraline is 0.3～10, and the multipolymer weight that forms in second step, in the polymkeric substance total amount is benchmark, is 60～97% (weight).

3. in accordance with the method for claim 1, comprising first step, in propane solvent or butane solvent the ethene of polymerisation slurry state or in gas phase polymerising ethylene, carry out second step subsequently, prepare the ethene-alpha-olefin random copolymers so that the ethylene content in the multipolymer that generates in second step reaches 5～95% (weight) by gas phase polymerization, it is 1,2,3, limiting viscosity in the 4-tetraline (135 ℃) reaches 0.3～10 and the weight of the multipolymer that forms in second step, in the total polymer is benchmark, is 60～97% (weight).

4. in accordance with the method for claim 1, comprising the gas phase random copolymerization of carrying out ethene-alpha-olefin, ethylene content reaches 5～95% (weight) in the multipolymer of generation like this so that make, and its limiting viscosity (135 ℃) 1,2,3, in the 4-tetraline is 0.3～10.

5. in accordance with the method for claim 1, wherein catalyst system also contains electron donor (C).

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