CS235518B2 - Method of propylene polymers production - Google Patents

Abstract

In the suspension polymn. of propene or a propene-olefin mixt. in the presence of the TiCl3 and an organoalumnium compd., part or all of the polymn. solvent, i,e., hexade or liq. propene, is sepd. from the polymer and reused without purifin. as the polymn. solvent. The polymn. catalyst is used (10-80oC during<=24hr) to prep. 0.1-500.0g polymer/g TiCl3 before addn. to the recycled polymn. solvent. The amt. of polymer sol.in refluxing hexane does not increase when the resysled solvent and the pretreated catalysts are used.

Description

The invention relates to a process for the production of propylene polymers by suspension polymerization. More particularly, the invention relates to a process for the slurry polymerization of propylene or a mixture thereof with alpha-olefin in an inert hydrocarbon or liquefied propylene in the form of a polymerization solvent, wherein a major part of the inert hydrocarbon or liquefied propylene used as polymerization solvent is fed directly to the polymerization stage and used without further processing of the solvent for purification.

So far, the processes for producing polypropylene, a1, have been carried out continuously or discontinuously, from the degree of polymerization, polymer purification, drying and granulation and solvent purification. The polymerization solvent after use in the polymerization stage contained alcohols, water, decomposition products, etc. admixed in the polymer purification stage. Due to the content of these impurities, it has not yet been possible to circulate the solvent for reuse in the polymerization step without prior purification in the solvent purification step. At the same time, it is known that the cost of solvent cleaning constitutes a significant part of the cost of producing polypropylene. Nowadays, the issue of reducing the cost of propylene production due to the energy price has become significant.

A process in which the cost of solvent cleaning is greatly reduced is described in Japanese Patent Application Publication No. 83784/1974. In this process, after the polymerization is complete and before the catalyst decomposes, the solvent-insoluble polymer and the thus removed solvent are recycled in the required amount without purification, while the purified solvent and fresh catalyst are fed, and the polymerization is carried out.

Japanese Patent Application Publication No. 79589/1975 discloses a process for homopolymerizing or copolymerizing propylene in liquid propylene. The resulting polymerization slurry is then removed and contacted in countercurrent with liquid propylene and the resulting liquid propylene containing the active catalyst is recycled to the polymerization stage and reused.

The disadvantage of these processes is that, as a result of the recycling and reuse of the polymerization solvent, the proportion of the solvent-soluble polymer formed (hereinafter referred to as the soluble polymer) increases.

The present inventors have conducted careful studies of this and have suggested a method in which the same ratio of soluble polymer formed can be maintained through recylization and reuse of the polymerization solvent as when the solvent is used only once.

The present invention provides a process for the production of polypropylene by homo- or copolymerization of propylene in the presence of a catalyst comprising titanium tetrachloride and an organic aluminum compound, in which the content of soluble polymer formed is not increased despite recycling and reuse of the polymerization solvent.

The invention further relates to a process in which the polymerization solvent is completely recycled after polymerization and reused without purification.

In a process for producing propylene polymers by homopolymerizing propylene or copolymerizing it with another alpha-olefin in the presence of a catalyst system comprising titanium tetrachloride and an organic aluminum compound and recycling and re-using some or all of the solvent obtained by separating the solvent-insoluble polymerization polymer ( referred to as insoluble polymer) from the slurry after polymerization, an improvement is achieved by using a catalyst system obtained by subjecting a catalyst comprising a titanium tetrachloride compound and an organic aluminum compound to a propylene polymer in an amount of 0.1 g or more to form a catalyst. 1 g of the titanium trichloride compound, before proper polymerization.

The following are examples of titanium tetrachloride mixtures used in the present invention:

A product obtained by reduction of TiCl 2 with metallic aluminum and removal of excess TiCl 2 and subsequent activation and grinding;

2. the reaction product of the product 1. with an electron donor;

3. the reaction product TiCl ^, organic ether compounds and organic aluminum compounds;

4. the product obtained by reacting the reaction product TiClCl with an organic aluminum compound and an organic ether and subsequently treating the resulting reaction product with TiCl ^; and

5. a reaction product of a magnesium-containing magnesium compound with an electron donor and TiCl 2.

The organic aluminum compounds used in the present invention correspond to the general formula

A1R _{3 n} Cl _n

3-n n wherein β denotes alkyl having 1 to 8 carbon atoms and

N = 0 or 1.

Examples of such compounds may be tri-yl, diethyl chloride, tri-isobutyl aluminum, isobutyl-aluminum chloride, etc., and mixtures thereof.

In addition to said components, a third sloika may be added, for example various compounds containing N, O, P, Si and the like.

in

The catalytic system used in the process according to the invention for the production of propylene polymers is fed to a system obtained by mixing a catalyst containing titanium chloride and an organic aluminum compound for processing prior to polymerization to form a polymer in an amount of 0.1 g or more. based on 1 g of the titanium tetrachloride compound. Specifically, the system is prepared by admixing a tic chloride compound and an organic aluminum compound with an inert hydrocarbon or the like to form a liquid catalyst to which hydrogen and propylene are fed at a temperature of from 10 to 80 ° C to form 0.1 g or more of propylene. % of polymer, based on 1 g of titanium tetrachloride.

It is advantageous to set the amount of this propyl-polymer formed in the catalyst system according to the invention (such a propylene polymer will hereinafter be referred to as a pre-polymer) to a value in the range of 0.1 to 500 g, preferably 0.5 to 300 g, optionally 1 to 100 g. g per 1 g of titanium tetrachloride. If this amount corresponds to values lower than 0.1 g, the desired efficacy of the process according to the invention cannot be achieved, while it can be recovered. Exceeding 500 g are not practical since the efficiency of the present invention reaches equilibrium and, moreover, it is necessary to increase the catalyst treatment apparatus prior to polymerization.

The processing conditions of the catalyst of the present invention prior to proper polymerization, i.e., the propylene polymer propylene polymer formation reaction conditions, may be as follows: temperature from 10 to 80 ° C, preferably from 30 to 60 ° C; residence time from 1 minute to 24 hours.

Temperatures below ¹ no ⁰ not pr ^ t ^^ and temperature převyltajcí ^80C are also ^{of the} side-oats or ^3! there is an increase in the content of amoophene propylene polymer (AlP) formed during the polymerization of the invention. Said treatment can be carried out in the presence or absence of hydrogen as a moleicule moleicifier.

Propylene can be used as a propylene to treat the catalyst prior to polymerization, i.e. to form a pre-polymer, with a 0.5 mole coating. % or less of an alpha-olefin, including ethylene. Preference is given to using propylene alone.

Amounts of alpha-olefin, including ethylene, in excess of 0.5 mole% are undesirable because the density of the insoluble polymer, i.e. propylene, formed in the polymerization of the invention is varied.

The rate of formation of the propylene polymer (pre-polymer) in the treatment of the catalyst by the proper polymerization of the invention is not critical; generally, lower iChhlosSi · is preferred

The pretreatment can be carried out continuously or discontinuously in the gas phase or in the liquid phase. In the case of the gas phase, the treatment may be carried out in propylene gas and, in the case of the liquid phase, in an inert hydrocarbon such as pentene, hexane, heptane, etc., or in liquefied propylene. In any case, it is necessary to purify the resulting product in order to remove the inhibitory substances in the propylene polymerization, whereby the resulting catalyst system is subsequently subsequently polymerized.

The final (orderly) polymerization according to the invention can be carried out as part of the process according to the invention using the catalyst system and also using an unpurified polymerization solvent separated from the suspension after the polymerization, as described below. Polcmeeizační temperature ranging from room temperature okooí to 100 ° C, preferably ⁰ 3 and ⁸⁰ ° C. ^p ol ^{y No} mmeiza the pressure ^{P y} Buje sh about atmo ^d ^ ^d rickětoo pressure of ^{5 0>} MPa. When conducting the polysaccharide in the presence of hydrogen, the molar value can be set to. a predetermined boundary, without adversely affecting the crystalline structure of the resulting polymer.

The polymerization of the present invention is not limited to the production of propylene homopolymers, but is useful for a wide range of propylene / ethylene block copolymers and / or alpha-salanes different from propylene.

The slurry obtained after degassing is degassed as necessary to separate the insoluble polymer and polymeric solvent from the slurry. This separation can be carried out by means of a centrifugal separator, vertical countercurrent extraction column, hydrocyanone, etc. The polymerization solvent separated from the suspension comprises soluble polymers, propylene oligomers, a small amount of insoluble polymer and a third polymerization catalyst component and others.

^p o ^ i ^r d ^p and ^DE entire MNN žtví parted by ^ ^ o. ^Ed ouět extended ^p Ia being reviewed by ^d ^ tymeeizáčního step and reused as polymeeizečního rozpouutěďla in závislsstS on the quality of the resulting polymer.

The insoluble polymer separated from the suspension, on the other hand, can itself be neutralized to obtain the product, or it can be mixed in the purification step with a cleaning solvent, such as a polymerization solvent, an alcohol, etc., to obtain the desired product.

Referring now to the accompanying Figures ¹ and 2, an apparatus for carrying out the process of the invention will be described in which the polymerization solvent separated from the suspension is completely recycled and reused without purification. It is to be understood, however, that the present invention is not limited to this example.

Both Figures 1 and 2 represent a continuous process for the polymerization of propylene in which the polymerization solvent is completely recycled and reused.

Giant. 1 illustrates a case in which an inert hydrocarbon such as hexane, heptane, etc. is used as the polymerization solvent in the polymerization step.

An inert hydrocarbon such as n-hexene or n-heptane is fed into the reaction vessel 6 provided with a stirrer. line 2, feeds an organic aluminum compound such as diethyl aluminum chloride, line 3 also titanium trichloride, and line 3 feeds the third sloika. While keeping the reaction vessel at the desired temperature, propylene is fed through line 2 with stirring and, if necessary, hydrogen is also fed in line with line 6 to form pre-propylene polymer to form the catalyst system of the present invention. This process may be carried out continuously or by dithcontoscopy.

The catalyst system is accompanied by a pump 8 into a polymerization vessel 8 equipped with a stirrer and a device for removing polymerization heat. The polymerization vessel is fed with hydrogen, the solvent solution is fed through line 11 through line 12 ^of petroleum and, if necessary, line 13 is fed with ethylene and / or an alpha-olefin different from propylene to produce a series of copolymers. The residence time in the polymerization vessel 2 ranges from 1 to 8 hours. The slurry concentration in the polymerization vessel 2 ^is set to a value of 50% by weight or less. In the case of continuous block copolymerization, it is necessary to use two or more polymerization vessels in series and control the respective hydrogen concentrations and monomer composition in the polymerization vessels.

The resulting slurry, after polymerization, is discharged from the vessel receiver 2 via the control valve 14 to the evaporator drum 15. This slurry comprises a soluble polymer, an insoluble polymer, a catalyst, an inert hydrocarbon, propylene, etc. Unreacted piopylene separated in the evaporator The slurry is, after separation of unreacted propylene, transported through a pump 40 to a centrifugal separator 17 in which it is separated into a wet cake of an insoluble polymer containing a small solvent and a solvent. It comprises a catalyst and a soluble polymer.

The solvent containing the catalyst and the soluble polymer is a pump 18 via line 18 into the polymerization vessel 2, whereby, if necessary, a portion of the solvent is discharged via line 20 outside the system. The wet cake, on the other hand, is brought into contact with heated nitrogen, dried by a stream of gas in line 21 and fed to cyclone 22. in which the insoluble polymer is separated in the form of a powder. The stream of nitrogen gas containing the solvent is passed through line 23 to the scrubber 24, where it contacts countercurrent with the solvent cooled in the heat exchanger 25. The solvent obtained is returned to the polymerization vessel.

Since the polypropylene powder separated in the cyclone 22 contains the remaining active catalyst, it is further processed and stabilized in the stabilization vessel 26 in which it is contacted by the stabilizer, through a feed line 27, for example epoxide, alcohol, water and the like. Since the polypropylene powder contains traces of stabilizer and its reaction product or traces of solvent, it is further fed to the dryer 28, dried sufficiently here, passed through line 29 and separated as the final product.

The fluidized heated nitrogen gas used in the fluidized bed 28 is cleaned in a scrubber 30 prior to use and subsequently heated in a heat exchanger 31. A non-agglomerating agent, such as aqueous potassium hydroxide solution, is passed through a line 32 to a scrubber in which the nitrogen gas is fluidized. of the dryer 28 neutralized for hc.

Giant. 2 illustrates the case where liquefied propylene is used as the polymerization solvent.

An inert hydrocarbon such as n-hexane or n-heptene is fed into the reaction vessel 6 equipped with a stirrer via line 7, line 2 'of an organic aluminum compound such as diethyl aluminum chloride, line 2 of a titanium tetrachloride compound and line 3 if necessary. . While keeping the contents at a predetermined temperature and from stirring, propylene is fed through line 2 and, if necessary, hydrogen via line 6, both in the required amount to form a propylene prepolymer, to form a catalyst system. This process may be carried out continuously or discontinuously.

The catalytic system is led by means of a pump 8 to a polymerization vessel 2 equipped with a stirrer and a device for removing the polymerization reaction heat. Hydrogen is supplied to this polypeering vessel 2 'via line 10 to control the co-ocular supplemental liquefied propylene via line 12 and, if necessary, ethylene and / or an elpholefin different from propylene to produce a series of copolymers via line 13'.

The residence time within the polymerization vessel 2 ranges from one to 8 hours.

The suspension concentration within the polymerization vessel 2 is determined to be 65 wt.% Or less.

In the case of the production of block copolymers in a continuous manner, it is necessary to add two or more polypolisation vessels 2 in series and to control the hydrogen concentration and monomer composition in the subsequent polymerization vessels. At the same time, the purified liquefied propylene is passed through line 34 to the hydrocyclone 33, and the stream of liquefied propylene, containing most of the organic aluminum compound and the soluble polymer, is removed from the topsheet. cyclone.

From the bottom of the cyclone, a stream of polypropylene containing a quantity of liquefied propylene is removed. The stream of liquefied propylene, discharged from the top, is returned to the polypeering vessel. a part of the flow can be discharged via a pipeline. The liquefied propylene removed from the bottom of the cyclone is heated and dried in a heat exchanger 37 and passed to the cyclone. separated in the cyclone is compressed and liquefied ^ ρϊμ :! ^ ρ ^ πτ ^ ™ 39 and returns to the Polymerization Container 2 ·

The polypropylene powder, dried in cyclone 38, is stabilized in the same manner as shown in Figure 1 to give the desired product.

EkonomPčnoot present invention lies in the top, the p-di-ZL formed amorphous polypropylene · ENI match if the recycling and reuse of impure rozpouutědla, separated from the suspension after гoC · ^m У Peizeei. Thus, according to the present invention, it is possible to provide a complete polymerization solvent recycling process and to reduce solvent cleaning costs and to considerably reduce polypropylene manufacturing costs.

The production method of the present invention will be further elucidated by way of examples, comparative examples and reference examples. Reference examples apply to manufacturing examples in the case of using a purified solvent. The values given in the examples, comparative examples and reference examples are as follows:

The formation of the prepolymer in the treatment of the catalyst prior to the deposition: the amount of (prep) polymer formed (g) per g of the titanium trichloride compound (hereinafter referred to as the compound in the following description) is expressed in terms of "g / g- The value corresponds to the value obtained in a separate example.

Amount of polymer formed: expressed as the amount of polymer (g) formed, insoluble in the polymerization solvent.

Yield of polymer formed: expressed as the yield of insoluble polymer (g) per g of titanium tetrachloride compound, obtained by subtracting the prepolymer from the total amount of polymer.

Proportion of soluble polymer formed (hereinafter abbreviated as APP formed): in the case of polymerization using an inert hydrocarbon such as hexane, the proportion is expressed as the proportion of polymer soluble in the inert hydrocarbon after polymerization relative to the total amount of polymer formed (soluble polymer plus insoluble polymer) in the case of liquefied propylene polymerization, this is the proportion of hexane soluble polymer based on the total amount of polymer formed, obtained by extracting the soluble polymer from the insoluble material with a Kumagawa type n-hexane at reflux for 6 hours, calculated from the resulting value of extraction. In calculating the APP formed, the soluble polymer of the polymer obtained by subtracting the soluble polymer contained in the reused solvent from the total amount of soluble polymer.

MFI: melt flow index (g / min) according to ASTM-D 1238-70

Bulk density: powder density of insoluble polymer Bending modulus: according to ASTM-790-70 Tensile strength: according to ASTM-638-68

Hardness: according to ASTM-785-65

Preparation of the titanium tetrachloride compound (a) used in the following examples:

2.7 1 of n-hexane and 0.69 TiCl ^ 1 was charged into the reactor 151 equipped with a stirrer speed: ¹ 200 rpm, the inside of which was kept under nitrogen and cooled to 0 ° C. Subsequently, 3.4 L of n-hexane and 0.78 L of diethyl aluminum chloride (hereinafter referred to as DEAC) were added at 0 ° C for 4 hours, and the reaction was stirred under stirring at 65 ° C for one hour, after which the reaction mixture was cooled to ambient temperature and left to stand. The resulting liquid phase as the upper layer was separated and the solid phase as a deposited layer was washed five times with hexane. Subsequently, 9.8 L of hexane and 1.37 L of diisoamyl ether were allowed to react with the solids at 35 ° C for ,0 minutes, after which the reaction mixture was left to stand and the liquid supernatant separated to give a second precipitate which was collected. followed by washing with hexane.

3.9 L hexane and 1.0 L TiCl 2 were added to the precipitate for 60 minutes, the reaction mixture was stirred at 65 ° C for 2 hours, allowed to stand and the liquid supernatant was separated to give a third the precipitate was then washed with hexane and dried under reduced pressure to give the titanium tetrachloride compound (1 kg).

Reference Example 1

1. Catalytic system.

A 61 L polymerization vessel equipped with a stirrer and purged with nitrogen gas was charged with 0.8 L of purified n-hexene, 0.20 DEAC, and the titanium tetrachloride compound (a) (0.123 g) to give a liquid catalyst mixture. Subsequently, propylene was fed to the reaction mixture and the contents were subjected to processing to obtain the propylene polymer under stirring and at 50 ° C at a total pressure of 1.0 kg / cm 2 and a residence time of 30 minutes to obtain the propylene polymer (propylene polymer). (7.2 g / g compound).

2. Polymerization

The katelytCckmniu system indicating obtained by said process were added 2.2 1 of purified n-hexane as polymeeizační solvent, 0.48 g of DEAC and 780 ml of hydrogen was temperature e Vol ^{characterized} Šena not ⁷⁰ ° C. Násletoě ^butyl-p ropylen operational status and ^p ol ^y meeizace ^p ro ^py ene ^o f ^p s ^p te lo ^{I 80 C c} of cel s ^kh tlat of ^{8 kg} / cm ² and ^P s real ^{d b} of about 4 hours. ^M o ^{d y} Mink ^yp ol polymerizece isomerisation and the results are shown in Table 1.

Peaks to 3

1. Treatment to obtain the precursor polymer is carried out in a stent manner as in Reference Example 1 and under similar conditions to those shown in Table 1 to obtain a catalyst system.

2. Polymerization of propylene tulle in the same manner as in the Reference Example. 1 and under the conditions given in Table 1, with the exception that the corresponding hexanes obtained by removing the insoluble polymer from the post-slurry suspension mentioned in the previous Reference Example 1 or Example 1 or 2, the tulles are reused as p). The solvent solvents for the catalytic system obtained by the above procedure are as shown in Table 1. The conditions and results are shown in Table 1.

Comparative treasure

The catalyst system was obtained by preparing a catalytic liquid sieve according to the procedure described in Example 1 and as shown in Table 1, with the exception that no processing was performed to form a precursor polymer.

2. Propylene polymerization was carried out in the same manner as in Example 1 and under the same conditions as in Table 1, except that the tulle was removed from the slurry obtained after polymerization after the catalyst system had been prepared as described above. The product of claim 3 and the resultant hexane thus recovered are reused as the olefinic solvent for the catalyst system obtained by the process described above. The results and conditions are shown in Table 1.

Example 4

Process to form a pre-polymer (0.5 g / g-socyanenyl) is carried out as described in Example 4, except that the amount of hydrogen is changed and the propylene feed conditions are changed. In this way, a catalyst system was obtained.

2. The polymerization of the propylene tulle was carried out as in Example 1 and under the conditions set forth in Table 1, except that the insoluble polymer was removed from the suspension obtained after the hydrolysis according to Comparative Example 1, and the resulting hexane thus separated was reused in in the form of a polyrismic solvent for the catalyst system obtained by the process described in Table 1. The reaction conditions and the results obtained are shown in Table 1.

The values shown in Table 1 demonstrate that when the insoluble polymer is removed from the suspension obtained after polymerization and the resulting hexane separated in such a manner is again in the form of a straight-through catalyst, the formation of the pre-polymer in the Cyttlytic system prevents the content increase. created by APP.

Catalytic liquid composition Preforming polymer conditions

EXAMPLE READED DEAC Compound H? temperature pressure time pre-n-hexane * polymer formed g g N1 ° C MPa min. g / g of the mixture

00 oo o o * * * «* o o o o o o o

- (M 1 H OF 0 0 Ό and <6 <8 WHAT X X r4 • • M Л4 '<4 X Ф * 4 * 4 * 4 and O. . л

AND

Table continuation

H • H β

o H co

hOK>

ьо

KO WHAT O what 04 / 04 / 04 / LT \ 04 / 00 04 / O O O

IA WHAT t- WHAT CM ко

if\ 00 Ό b- KO b ~ lA lA LT4

C-

CM o

b »bblA

O <41 · »<n

CM MKO

o M <M

WHAT

O * o b-

O O O oo O O b- 00 00

O O O СП if\ M · 00 00 oo

CM

CM

CM

CM

CM

CM

Φ Ό Ч Ч ХЗ Л -И Ό О ХМ Ф KD гЧ Я Ό Р Ό О КС ОАО. О Л- Я Ό о О Я * Ф Ф * о. ЧС Ф XI) Я ы <н Я N Св ЧС Р Ф Я ф> ф . Я Р КП гЧ Ф я я Я • č XD £ Х Р КР О, ХМ ю I.E W · к » 0 (0 · Я) >> Ό Я4 <л Я Я> Я О > О со о. о О со О. О.

cn +

<M

CM

CM

CM

CM

Ф> Ф ф> ф ф * ф <-Ч Я гЧ Я гЧ Р Ό Р TJ Р Ч Ф <гЧ Ό О> Ф К о КС *О * 4 О О. О, о о. о. N О.— Я О о о >1> Ф * ф ф XС Φ · (X 0 К (ВХ2) Я N (В 'Ф Я N> Я • я «D -р Я Я Ах » гЧ Ф СМ · Η гЧ ФСП-И Ч ф Я и »а * 4 > ф о, хм > Ф <Х · Р Ό СО · я Ό СО · я Ф СО й> ф . Я> Я О Т5 я> Я О О Я О О. о »аа о со о. а о и а о

I.E

lac Ό β - -М гЧ F> fc А 1 1 И 1 й й хз СМ Ό СП Ό > й О. м- Ό а а (0 C0 • <в г-4 г-Ч гЧ > Η Чч Ф И 'И> fc '4 4ч Л1 S4> й О й о ΛΙ \ Ч 1 ад А А Сц А £

mg of propylene was fed for 30 minutes · Contained in reused solvent (applies to the following tables)

CM СП ♦ +

Reference Example 2

1. The processing for preparing the prepolymer in the catalyst was not carried out.

2. 3.0 L of purified n-hexane, 0.68 g DEAC and the titanium tetrachloride compound (a) (0.122 g) were fed to a 6 L reactor equipped with a stirrer and flushed with nitrogen gas. The reaction mixture was stirred, then 800 ml of hydrogen were introduced and the temperature was raised to 70 ° C. Propylene was then added and polymerization of propylene was carried out at a total pressure of 0.8 MPa, at 80 ° C and a reaction time of 4 hours. The polymerization conditions and results are shown in Table 2.

Comparative Examples 2 and 3

1. A liquid catalyst mixture was prepared in the same manner as in Example 1 and as shown in Table 2, and was discharged to form a prepolymer.

2. After the preparation of the liquid catalyst mixture, the propylene polymerization was carried out in the same manner as in Example 1 'and under the conditions given in Table 2, except that the hexane separated from the slurry of Reference Example 2 and hexane separated from the slurry of Comparative Example 2 of Example 2 were reused as the solvent for the comparative Example 2 and Comparative Example 3 (see Table 2). The results are shown in Table 2.

Table 2 shows that when the polymer was re-used as a polymerization solvent after polymerization without purification, the yield of insoluble polymer (polypropylene) per g of the titanium tetrachloride compound remained at the same value, i.e. unchanged but the content of soluble % of the polymer (content produced by APP) has increased considerably. This proves that re-use of the solvent after polymerization without purification is far from practical.

Table 2

Example Liquid catalyst mixture

Formation of prepolymer purified n-hexane

DEAC compound

S g

Reference example 2 - - 0,122 none Comparative example 2 0.8 0.20 0.125 none Comparative Example 3 0.7 0.20 0.120 none

Ρ η ο mj α χ й «ρ а α οχ № ъо ΧΟ Й ^а ъ • č φ 0 « «* 4 <8 0 Ο η> о г * • ДРД о Ο> » * ф 0 > а Μ А fa AND о 0 and Д4 О Я Ф X> » Η & Ж α 0 > ф Х_ X ьой Й Оъ + X Ф ъ φ > Μ X 5 >> φ А Η ο 0 h > 0 а > Ь * ф X йх ο ф> > fa Р О «0 > Ж М) Р о >> й > а

г- O t- -чТ 4fr <n о O O А O cu σχ . - οχ СП O AI А | Γ- cn ΧΟ αι O- Γ- Г- -4f ΧΟ 40 AND xo -чГ Ό O what O Γ- XO xo А AND LA O O O Φ Φ · Φ AI AI AI 00 what oo O O O O O ο t— Γ- Γ * O O O O LA OO WHAT Γ- Γ- what 40 O BYE BYE + + O AI cn сП AI AI Ф Φ H X O 0 0 O 0 ti P 0 O P 0 OXO) o Aai x ABOUT AU ti Ж 0 O > ф O Φ • 0 O Φ> P d e> fa o d N’0 0 O xn φ d A A φ q d p • H X Φ X Φ> AI Ή Ю > Φ A • P XD АО Ж Ф 0 ΦΧΧ » 0 <0 fa · 0 * 4 0 0 Φ A 0 0 O> fa O AND O 01 fa O O 0 A A A X Ή AI O ϋ <8 A | ФСП > > > fa OJ Ό 'ΛΌ O. 0 0 0 0 $ > H > H • OM O Λ4 X fa Ή fa Ή Ф O f O> fa X f CX (fa and

Reference Example 3

1. The pre-polymer (7.2 g / g compound) treatment was carried out in an attenuated manner as in Example 1 and under the same conditions as shown in Table-3 to obtain a catalyst system.

2. Using this catalyst system, propylene polymerization was carried out as described in Reference Example 1. The conditions and results are shown in Table 3.

Comparative example 4 -

A similar liquid catalyst mixture was prepared as in Example 1 and the preform polymer formation was carried out under altered propylene feed conditions to obtain 0.05 g / g compound outside the scope of the present invention and was prepared in this manner. catalytic system.

2. Polymerization of propylene was carried out in the same manner as in Example 1 under similar conditions except that it was a polymerization solvent. using the hexane obtained by removing the insoluble polymer from the suspension after polymerization according to the process described in Reference Example 3, for the catalyst system obtained in this way. The reaction conditions and results are shown in Table 1.

Table 3 shows that even when processing to produce. % of the pre-polymer, the results obtained are unfavorable due to the significant increase in the APP content if the pickling of the pre-polymer falls outside the scope of the present invention.

Reference example 4

1. The pre-polymer processing was carried out in a tear-like manner as in Reference Example 3, Example 1 etd., From the autumn mentioned in catalog 3 so as to obtain a catalyst system of 9.1 g / g compound.

2. Reference Example 1 was repeated except that the catalyst system obtained in this manner was carried out. . when pouužtí polymerization of mixtures of propylene with ^ethylene, at a temperature of 60 ° C and ^- ^ MRC in your Cart ^{870 d} 1 whereby ^'- obtain irregular rtylenlvý propylene copolymer (ethylene content: 2.4% hmoOaootiO. reaction conditions and results are shown in Table 3.

Example 5

1. Processing. in order to prepare the prepolymer, it was carried out in the same manner as in Reference Example 4, Example 1, etc., to obtain. 3.1 g / g compound to give a catalytic system.

2. The Reference Example was repeated except that hexane was obtained by removing the insoluble polymer from the suspension after polymerization according to Reference Example 4 to obtain a random propylene-4-methyl-copolymer (ethylene content: 2.6 wt%). 3 ·

As can be seen from Table 3, the content of the APP produced does not increase in the process of the present invention. in case of copolymers.

ГН r-l х>

А

Ό 0 r-l ‘rl * 4

О rn

ООО ко m -

о о о о см см см см *> о о о о

со 00 со оо о о о о

m no 0 М * ► > й ХВ Ό а а 0 > 1-ол! IU'rl ф 0 * 4 X х а

235516

’Ф

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СО *

СМо φф оо

СП кО со г-

σ \ со * г00 о

О ф СМ

If\ if\ ’Ф CM CM со СП φ сП

о ф кО О г • ф о <о LT4 Ф ’Ф ’Ф

- сп

Г-CXJ <гх ш

О о φ ф

СМ см

1ГЛ ten

Table 3 (continued)

оо о °° м о о о г— г— о о 00 ď \ Γ- Ф ’ф г- θ ' сП +

CM C4J см см ω

’Ф N • 1 я ^ 4 3 χυ XV Φ Ф о 4J я N Я СО о. ХО ф Я • г4 г-1 Ф ФСП 3 ю XI) ан > * ф ω Ю W Ю · О 4-> > я Ό 3 О * 4 Я-н о. О СО (X о. N> Ь)

со ОО о О о О 40 Ό о О Γ- ел ΟΟ оо со ф о сП + см см см ф СМ XV N • 1 я Ή 3 хв XV Φ Ф о 4- » Я N-й СО <х ХО ф Я • г4 гЧ φ φ ф 3 XJ XD СХгЧ > XD ф Ό и ю · О 4-> > ь Ό 3 О> й Я-č я. О И о. О. N> Ы

Т) СО г-4

Ή> й СЬ

Reference Example 5

1. 20 ml of purified n-hexane, 0.278 g of DEAC and 0.048 g of the titanium tetrachloride compound (a) were mixed in a 100 ml rector equipped with a stirrer and purged with nitrogen gas to give a liquid solution. sm ^ s. After the temperature was raised to 60 ° C, propylene was fed to a total pressure of 1.0 MPa and then processed. to obtain a pre-polymer for 30 minutes until a value of 9.2 g / g compound was reached. The catalyst system was obtained.

2. The purified liquefied propylene (1,600 g) was fed to the. a 5 liter polymerization vessel equipped with a stirrer and purged with nitrogen gas, 98 ml of hydrogen was added, followed by 0.274 g of DEAC and the catalyst system obtained as described above, and polymerized at 70 ° C for 3 hours. The reaction conditions and the results obtained are shown in Table 4.

Examples 6 to 8 and Comparative Example 5

1. The processing to obtain the precursor polymer was carried out as described in Reference Example 5 under the reaction conditions described in Table 4. (In Comparative Example 5, only a catalytic liquid mixture was prepared without being carried out).

2. The polymerization was carried out as described in Reference Example 5-2 except that instead of liquefied propylene according to Reference Example 5-2. , the respective mixed liquids of purified-liquefied propylene with the corresponding liquefied propylenes were reused by removing the insoluble polymer from the suspension after polymerization according to the previous Reference Example 5, Example 6, Example 7 or Comparative Example 5, in the form of a polymerization solvent for catalytic aylate as described in Table 4, and no DEAC was added (but only in Comparative Example 5, the liquid catalyst mixture was used alone as the catalyst system). Conditions and results are shown in Table 4.

As can be seen from Table 4, if the treatment to obtain the precursor polymer in the Catalyst is carried out according to the method of the present invention, the content of the extracted AβR, i.e. the content of the APP formed does not increase, however. of Example 5, the range generated by APP is increased.

Catalytic system

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what

tJO

Д • H 6

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Д ил υ ю  о > - сб ил со Д Ό > Ф со Ό Ό OJ TJ Ό Й Ή Сб Сб Д сб Сб Ф 24 гЧ í-Ч ►> 1 — С гЧ Сн 'И л: 24 О 24 ф> Й '* 4 Ή Й * <Ч ^ч Ч W ÍX > Й > Й О> й > ÍH о < CL, о, CL,

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Table 4 (continued)

> Ф Р а -ч 4->> К Ά> Ф 3 4 ею я а о о а Ф л- гЧ> э а Я о ни Я «-> ко • č ьо ю ф > я а

TJ o

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. Í • Ж • .2 o .2 Я .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2

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1А * г- > я а оо Ό Ό Я Я Я гЧ > гЧ .5tí о м * 4 я Ή > Я < о > я а а а

the liquefied propylene phase after the polymerization of the previous example was reused

LA

Reference Example 6

1. The processing to obtain the prepolymer was not carried out.

2. 1600 g of purified liquefied propylene were fed into a 5 L oolynizer, purged with nitrogen gas, and 0.552 g of DEAC and 0.050 g of titanium tetrachloride (a) and 960 Nml of hydrogen were added. This was followed by polymerization of propylene at ⁷⁰ ° C and contacting for ¹⁸⁰ minutes. These are shown in Table 5.

Comparative Examples 6 and 7

1. 20 ml of purified n-hexane, 0.281 DEAC and a certain amount of titanium tetrachloride compound (a) (shown in Table 5) were fed into a 100 ml reactor equipped with a stirrer and purged with nitrogen gas to prepare a liquid catalytic catalyst. The processing was carried out to form a prepolymer.

2. Polymerization of propylene was carried out in the same manner as described in Reference Example 6 and under the conditions of operation shown in Table 5, except that. instead of the purified liquefied propylene according to Reference Examples 6-2, the corresponding liquid network of the purified liquefied propylene with the corresponding liquefied propylene phases after the polymerization according to the previous Reference Example 6 (in the case of Comparative Example 6) or Comparative Example 6 ( Comparative Example 7) as shown in Table 5, with no DEAC.

Table 5

Example Liquid catalyst mixture Formation of pre-polymer Purified n-hexane 1 DEAC G Compound mg Reference example 6 50 none Comparative example 20 May 0.281 53 none Comparative example 7 20 May 0.281 51 none

23551S

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Polymerization conditions Polymerization results

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it it

г- о см СП чГ СМ IA • м · СП о <м m о о м · о сп LTK - ао СП СМ ш с- о о (М кО * о  КО о о о 00 00 00 о о о с- с— ί- о о ο ко м- 00 СП СП СП СМ LTK Ά о СП <П ♦ 4 ф ф гЧ '>> гЧ 0 3 Л Л <-> Л Л> Ό О -и Ό о Н О О О CX <O> N о о.и flt- «3 Ф N С— '>> о ф> о 9 3 * · ° · а N 'св ф * >> ф а а ф а а гЧ Ф 3 Ч>> 0 · · > Ф о. ·> > ф СХ О> ы Ф Ф «н О С— Л (Л ti · 3 Ό 3 Ф доо Ό 3 О> ti О О СО ΝΓ- о со о.а сх

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Ή 'г4 ко о о секо ФФ * · > > Ό > й 'Φ Ό 40 Ό ф а а ф а ф гЧ > гЧ гЧ М « ОМ ом Ή <й Й'Н Ь'гЧ * · ф О> ti О> ti £ « сч о » 04 СХ I

Preparation of the titanium tetrachloride compound (b) used in the following examples:

12.16 g of anhydrous Mg (OH) ₂ and 27.84 g of anhydrous AlCl 2 were ground in a ball mill at ²⁰⁰ ° C for ²⁴ hours. Them up followed ^{d b} t was added 13.3 ml of ethyl benzoate and ^6, 6ml ^ SiCl and milling continued for 48 hours. The resulting milled product (40 g) and 250 ml of TiCl 2 were allowed to react in a stirrer reactor at 80 ° C for 3 hours. The resulting product was washed five times with purified n-hexane (300 mL) and dried to give 42 g of the titanium tetrachloride compound (b).

Reference Example 7

1. The processing to obtain the prepolymer in the catalyst was not carried out.

2. In a 51a polymerization vessel equipped with a stirrer and flushed with nitrogen gas, 2.5 L of purified n-hexane, 5 m &lt; 3 &gt;

0.5 mmml of methyl p-toluylate and 64 mg of the titanium tetrachloride compound (b) and 0.37 mmml of methyl p-olate. Subsequently, 600 Nml of hydrogen and polymeeizace propylene was carried out at ^70C battery ^ ^0, 8 MPa for ^{2 h} o'clock. ^In hese ^Z e ^to 6 53 ⁰ g / g-compounds-created content APP: 3.4

Example 9

1. To a 5 liter polymerization vessel equipped with a stirrer and flushed with nitrogen gas was added 1.0 L of purified n-hexane, 0.3 M of methyl- ^p -ol-butylate, 59 mg of the thioium chloride compound. (b) and 0.2 mmml oetyl p-tplžllatu, to prepare a liquid catalyst smměi then treatment was carried out to form ^p ředběžného ^p ol ^y mer ⁽¹ 5 ⁶ g / g of composition ^{No. eěiě-l) P} s temperature ³⁰ ° ^C , a total pressure of ^1.0 kg / cm ² G and a reaction time of 10 minutes to obtain a catalyst system.

2. For this catalyst system was added 1.3 1 of the hexane phase obtained after poly- mer; ^ i ^ (^ i. In Reference Example 7 to 2 US January were fed 600 Nml of hydrogen and the ^{P and} D ^of Equation on ^p ol ^y meeizace propylene at ⁷⁰ ° C ato ^ ⁰ ° 8 MPa ^ad b ^e hours. Yield: 6580 g / g-compound. APP created content: 3.6%.

Comparative example 8

A liquid catalyst mixture was prepared according to the procedure of Example 9, without the preparation of the prepolymer.

2. Example 9 was repeated except that the hexane phase (1.3 L) obtained after similar polymerization to that described in Reference Examples 7 - 2 was used for the catalyst liquid. Yield: 6 475 g / g of compound. Content created by APP: 7.8% ·

PPExampleio

Propylene homopolymerization was carried out using the continuous apparatus shown in Figure 1.

Purified n-hexane at a rate of 30 kg / hour was fed into the 100 L reaction vessel equipped with a stirrer, followed by ducted aluminum chloride (180 g / h) and ducted titanium tetrachloride compound (a) (91). g / h). The treatment to obtain a prepolymer (7 g / g compound) was carried out with stirring at 50 ° C. Propylene and hydrogen were fed through line J so that the gas phase hydrogen concentration in the reaction vessel 7 was 4.0% by volume. The process was used for the continuous preparation of the catalyst system. '

Into the polymerization vessel 2 ⁰ content was 30 m @ 2 from the reaction vessel fed by means pump 8 catalyst, then through line 10 to hydrogen concentration of hydrogen in the gas phase 2.5 vol. Fc propylene duct 12, the catalyst pipe 18 and n-hexane (1 596 kg / h) containing a soluble polymer to be reused after the polymerization reaction, and n-hexane (570 kg / h) separated in scrubber 24. The polymerization was carried out at a total pressure of 20 bar and a temperature of 70 ° C. The resulting slurry containing soluble polymer, insoluble polymer, catalyst, n-hexane, propylene, etc. was removed from polymerization vessel 2 via control valve 14 to evaporator drum 15.

The unreacted polymer, separated in the evaporation drum 15, was recycled by heat exchanger 16. to the polymerization vessel 2. kg / h) and the n-hexane phase (600 kg / h) containing the soluble polymer (9 kg / h) and n-hexane (1596 kg / h) containing the soluble polymer (23.9 kg / h) ). The wet cake was contacted with heated nitrogen gas, countercurrent dried in line 21, and dried in cyclone 22. to obtain dried polypropylene powder. The latter n-hexane was recycled through pump 19 via line 18 to polymerization vessel 2 where it was reused as polymerization solvent.

Nitrogen gas containing n-hexane. separated in cyclone 22, was fed to scrubber 21 and the resulting n-hexane (570 kg / h) was fed back to polymerization vessel 2 where it was reused for polymerization. Polypropylene powder, containing n-hexane (30 kg / h), separated in cyclone 22, was fed to stabilization vessel 26 where the polypropylene powder was stabilized at 90 ° C with propylene oxide vapor (265 g / h) through line 27. Polypropylene powder. After stabilization treatment, it was fed to a fluidized bed dryer 28 where the traces of volatiles were removed from the powder at 100 ° C. Polypropylene powder (1000 kg / h) containing 500 ppm n-hexane was fed through line 29.

The stabilizer was mixed with polypropylene and the resulting mixture analyzed in relation to physical properties (injection molded sample). The results are shown in Table 6.

Comparative example 9

The procedure was carried out under the same conditions as described in Example 10, except that 180 g / h DSAC and 95 g / h of the titanium tetrachloride compound (a) were directly fed to the polymerization vessel 9 without using a reaction vessel 2 equipped with a stirrer. and the hydrogen phase concentration in the gas phase was set in polymerization vessel 2 and * 2.0%. The physical properties of the resulting polypropylene were also evaluated on the injection molded sample. The results are shown in Table 6.

Comparative Example 10

The procedure was carried out in the same manner as in Example 10, except that 0.60 kg / h of DEAC and 92 g / h of the titanium tetrachloride compound (a) were fed directly to the polymerization vessel (J), without the use of reaction vessel 2 equipped with a stirrer. Purified n-hexane (2166 kg / h) was fed through line 11 and line 18 µl of exane containing the re-usable polymer was added via line 11. N-hexane, o Rounded in scrubber 24, was not recycled to polymerization vessel Д. The physical properties of the resulting polypropylene were also evaluated on the injection molded sample. The results are shown in Table 6.

Claims (3)

A process for the production of propylene polymers by homopolymerizing propylene or copolymerizing a mixture thereof with another alpha-olefin in the presence of a catalyst system comprising a titanium trichloride compound and an organic aluminum compound, with recycle and reuse of some or all of the polymerization solvent used in the polymerization without purification; after separation of the propylene polymer in the solvent insoluble from the suspension obtained after polymerization, characterized in that the catalyst system is treated such that 0.1 g or more of propylene polymer per g of titanium tetrachloride compound is formed prior to polymerization. 2. The process of claim 1 wherein the amount of propylene polymer is in the range of from about 0.1 to about 500 grams per gram of titanium trichloride compound. 3. The process according to claim 1, wherein the treatment is carried out at a temperature of from 10 to 80 [deg.] C. for a period of from one minute to 24 hours.