KR830001194B1 - How to prepare propylene copolymer - Google Patents

Abstract

No content.

Description

How to prepare propylene copolymer

The figure is a propylene copolymerization process diagram of the present invention.

The present invention relates to a method for industrially and efficiently producing a high purity propylene copolymer.

More specifically, the present invention relates to a method for industrially efficient production of propylene copolymers using Ziegler-Natta catalysts having a special composition for producing films having good transparency, flexibility barrier properties, and heat adhesiveness.

Isotactic propylene produced using a stereoregular catalyst is widely used in various moldings because of its excellent properties such as flexibility, strength, formability, appearance and heat resistance. Polypropylene films have been used in various packaging materials because of their good transparency and high hardness. However, these polypropylenes have some drawbacks. One of them is that the impact strength is greatly affected by temperature. So-called cold resistance is bad. In other words, the impact strength is significantly reduced at temperatures between room temperature and 0 ° C. Another drawback is the high thermal bonding temperature. For example, when the two-side culture film is used, the temperature at which the heat-adhesive effect is very high is impaired. As a result, in most cases, thermal bonding of these films becomes impossible.

To overcome the above drawbacks, random copolymers containing small amounts of αolefins such as ethylene or butene-1, such as propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene- The butene-1 copolymer is used alone or in combination with other resins or rubbers as a heat-adhesive layer such as a biaxially cultivated polypropylene film, a shrink wrap, a film, or a cold resistant film. However, there are some problems in the production and purity of these polymers. As a by-product of polypropylene production, a large amount of unnecessary amorphous polymers are dissolved which are dissolved in a polymerization solvent, resulting in a loss of monomer. These by-products are not only economically inefficient, but also impede many production of copolymers. For example, the viscosity of the slurry is increased to increase the stirring force, thus causing a phenomenon in which the thermal conductivity of the polymerization reactor falls. This phenomenon is more remarkable when the comonomer content such as ethylene, butene-1, etc. in the copolymer is increased to produce a copolymer having good cold resistance and heat adhesion. On the other hand, when comparing the physical properties, the copolymer has a weaker anti-slip property and a longer time than the polypropylene.

Catalysts generally used in the production of polypropylene contain organoaluminum compounds such as titanium trichloride and diethyl aluminum chloride. The molecular ratio of titanium trichloride to the organoaluminum compound in the catalyst is from 1: 1 to 1: 20 (see Polypropylene Resin, p. 26 (published by Nikkan Kogyo Shinbun Sha)). If it is below 1, the catalytic activity and stereoregularity (as pointed out in n-heptane insolubility or crystallinity) are drastically reduced, while the catalytic activity and stereoregularity are reduced when the Al / Tl molecular ratio is above about 10. This includes several texts and quotes, such as L. Reich and A. Schnindler, Polymerization by Organometallic Compounds, Chapter IIID (published by Interscience publishers), T. Keii, Kinetcs of Ziegler-Natta Polymerization, Chapter 4.2 (published by Kodanska), It is reported in Japanese Patent Application No. 34478/72 ("OPI" used here is "Published unexamined Japanese patent application").

For example, in Japanese Patent Application No. 35487/74, the molecular ratio [(B) / (A)] of the organoaluminum compound (B) to the titanium compound (A) in the production of the propylene copolymer is about 0.5. 20 to 20, preferably 1 to 10. It is therefore common knowledge to use catalysts having a molecular ratio of (B) / (A) within the ranges described above.

However, the above-described problems in the preparation of propylene copolymers containing about 80 to 99 mol% propylene and 1 to 20 mol% ethylene and / or α-olefins having 4 to 18 carbon atoms, which are the end products of the present invention. I haven't solved them yet.

Various investigations have been made to solve the above-mentioned problems with regard to the production and purity of propylene copolymers, and the results have been solved simultaneously by using Ziegler-Natta catalysts, which have a novel composition of both manufacturing and purity problems.

Another object of the present invention is to define a process for producing propylene copolymers with reduced amounts of by-product amorphous polymers.

Another object of the present invention is to define a method for producing a propylene copolymer having improved cold resistance and heat adhesion.

Another object of the present invention is to define a process for the preparation of propylene copolymers which are very stable in transparency and color, i.e. not easily damaged by heat or fade with time.

According to the present invention, the titanium trichloride and the (B) organic aluminum compound prepared by reducing the (A) titanium tetrachloride organoaluminum compound and activating the product are prepared so that the (B) / (A) molecules are about 20 to 100. A method for producing a propylene copolymer containing about 80 to 99 mol% propylene and 1 to 20 mol% ethylene and / or an α-olefin having 4 to 18 carbon atoms is defined using the Ziegler-Natta catalyst.

It is obtained by reducing titanium tetrachloride used as catalyst component (A) in the present invention to an organoaluminum compound and continuously reacting the reduced solids with the complexing agent and the halogen compound simultaneously.

The organoaluminum compound used to reduce titanium tetrachloride is represented by the following structural formula.

AlRℓX _3- ℓ

ℓ

3의 수이다. 유기 알루미늄 화합물의 예로는 메틴 알루미늄 디클로라이드, 에틸 알루미늄 디클로라이드, n-프로필 알루미늄 디클로라이드, 에틸 알루미늄 세스퀴클로라이드, 디메틸 알루미늄 클로라이드, 디에틸 알루미늄 클로라이드, 디-n-프로필 알루미늄 클로라이드, 트리메틸 알루미늄, 트리에틸 알루미늄, 트리이소부틸 알루미늄, 에틸 디사이클로헥실 알루미늄, 트리페닐 알루미늄, 디에틸 알루미늄 하이드라이드, 디이소부틸 알루미늄 하이라이드, 디에틸 알루미늄 브로마이드 및 디에틸 알루미늄 이오다이드가 포함된다.In the above formula, R represents a linear, branched or cyclic alkyl group or an aryl group having up to 18 carbon atoms, X is a halogen atom or a hydrogen atom, and ℓ is 1

ℓ

It is a number of three. Examples of organoaluminum compounds include methine aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, ethyl aluminum sesquichloride, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, trimethyl aluminum, tri Ethyl aluminum, triisobutyl aluminum, ethyl dicyclohexyl aluminum, triphenyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum bromide and diethyl aluminum iodide.

Of these compounds, diethyl aluminum chloride and ethyl aluminum sesquichloride give particularly preferred results.

The reduction reaction is carried out at about -60 ° to 60 ° C, preferably at -30 ° C to 30 ° C. There is no particular limitation on the reaction time, but the reaction time is usually about 1 to 10 hours. In order to complete the reduction of the titanium tetrachloride to titanium trichloride, it is preferable to post-react at a high temperature not exceeding about 150 ° C. Preferably the reduction reaction is carried out in an inert hydrocarbon solvent such as pentane, hexane, heptane, octane or decane. The reduced product is run in an inert hydrocarbon solvent. The reduced product is optionally heat treated in the presence or absence of an inert hydrocarbon solvent. Suitable heat treatment temperatures are about 100-180 ° C. There is no particular limitation on the heat treatment time, but usually 30 minutes to 5 hours is convenient.

Preferred complexing agents are ether compounds of the formula: R ¹ -OR ² wherein R ¹ and R ² are each linear side chain or cyclic alkyl groups having 1 to 10 carbon atoms. Representative ethers include diethyl ether, di-n-propyl ether, diiso propyl ether, di-n-butane ether, diiso subether, dinepentyl ether, di-n-hexyl ether, methyl n-butyl ether, Methyl isoamyl ether, ethyl isobutyl ether, and the like. Of these ether compounds, di-n-butylether and diisoamyl ether are particularly preferred.

The reaction of the reducing material with the ether compound is carried out efficiently in the presence of a diluent. Suitable diluents which may be used include inert hydrocarbons such as hexane, heptane, octane, decane, decalin, benzene, toluene and xylene.

In the present invention, the ether compound is added to a solid treated with a reducing solid or a halogen compound in a reaction mixture or to dilution with an inert hydrocarbon solvent during a reduction reaction of titanium tetrachloride during reduction.

The amount of ether compound used is about 0.05 to 3.0 moles, preferably 0.5 to 1.5 moles per mole of titanium trichloride. The reaction temperature is preferably about 0 to 150 캜. There is no particular limitation on the treatment time but it takes about 20 minutes to 5 hours.

Preferred halogen compounds are:

(1) the following structural halogen or halogen compounds:

X ¹ X ² a

Wherein X ¹ and X ² are each chlorine, bromine or urethra and a is 1-3.

(2) Titanium halides:

(3) Alkyl aluminum halides of the formula:

AlR ³ nX ³ _3-n

n＜1.5이다 :Wherein R ³ is an alkyl group having 1 to 18 carbon atoms, X ³ is chlorine, bromine or urethral and n is 1

n is less than 1.5:

(4) There is an organic allogene compound.

Specific examples of the halogen or interhalogen compound include chlorine, bromine, urethra, boromin chloride, iodide chloride, iodine trichloride, iodide bromide and the like. Of these compounds, iodidine is particularly preferred.

Titanium halides include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and mixtures thereof. Of these compounds, titanium tetrachloride is particularly preferred.

Ethyl aluminum dichloride is commonly used as alkyl aluminum halide.

As the organic halogen compound, a compound having 1 to 18 carbon atoms and 1 to 38 halogen atoms is preferable. Especially halogen-substituted alkanes such as carbon tetrachloride, chloroform, hexachloroethane, ethyl iodide, butyl iodide and the like.

Preferably the reaction with a halogen compound is carried out in an inert hydrocarbon solvent such as hexane, heptane, octane, decane, benzene, toluene or xylene.

This reaction can be carried out in several ways. For example, (i) ether treated solids are reacted with halogen silver compounds. (ii) The reduced solid is reacted with a halogen compound followed by ether. (iii) The reduced product is reacted with an ether compound and a halogen compound. (iv) A halogen compound is added to the reduced reaction mixture obtained by reaction with an organoaluminum compound in the presence of a titanium chloride ether compound. The catalytic activity of the solid catalyst differs depending on the type of halogen compound used and the reaction method. Methods (i)-(iv) apply when halogens, interhalogen compounds or organic halogen compounds are used as the halogen compounds, but methods (i)-(iii) should be applied when titanium halides or alkyl aluminum halides are used. Thus, by selecting the appropriate halogen compound and method, it is possible to easily prepare the required solid catalyst.

The amount of halogen or halogen compound used is usually about 0.001 to 2.0 moles, preferably 0.005 to 1.0 moles, more preferably 0.03 to 0.5 moles per mole of titanium tetrachloride, but there is no limitation thereto. The reaction temperature may be arbitrarily selected but is preferably about -30 ° to 200 ° C, more preferably 0 to 150 ° C, most preferably 0 to 100 ° C. The reaction time is also not particularly limited but usually takes about 5 minutes to 5 hours.

Specific examples of preferred titanium trichloride are

(1) Japanese Patent Application (OPI) No. 74595/1975 and US Patent No. 3,960,765,

(2) United States Patent No. 4,123,387 and

(3) Titanium chloride is disclosed in Japanese Patent Application (OPI) Nos. 33289/1978 and 512815/1978.

Titanium trichloride in (1) is prepared by reducing titanium tetrachloride with an organoaluminum compound, followed by reaction with a complexing agent and an alkylaluminum dihalide, and optionally with a complexing agent.

The titanium trichloride in (2) is prepared by reacting titanium tetrachloride with an organoaluminum compound, followed by reaction with titanium tetrachloride and an organoaluminum compound, followed by reaction with carbon tetrachloride and an ether mixture. The titanium trichloride in (3) is prepared by reacting titanium tetrachloride with an organoaluminum compound and then with an ether and a halogen or an interhalogen compound or a mixture of mono halogenated hydrocarbons.

Also preferred are (4) British Patent No. 1,391,068 (5) Japanese Patent Application (OPI) 46,598 / 1976 and (6) United States Patent Application No. 920,888 (filed June 30, 1978). Is used.

The titanium trichloride in (4) is prepared by reacting titanium tetrachloride with an organoaluminum compound, followed by treatment with a complexing agent and titanium tetrachloride. Titanium trichloride in (5) is prepared by reacting titanium tetrachloride with an organoaluminum compound in the presence of an urethral or urethral compound, followed by contact with a release agent (ruwis acid). Titanium trichloride in (6) is prepared by reacting titanium tetrachloride with an organoaluminum compound in the presence of ether followed by induction.

Organoaluminum compounds which are preferably used as component (B) in the present invention are represented by the following structural formula:

AlR ⁴ _3-m X ⁴ _m

m＜3 만족하는 숫자이다. 여기에는 예를들면, 트리알킬 알루미늄, 알킬 알루미늄 할라이드, 알킬 알루미늄 하이드라이드, 알킬 알루미늄 알콕사이드, 알킬 알루미늄 알콕시 할라드 등이 있다. 이중 디메틸 알루미늄 클로라이드, 디에틸 알루미늄 클로라이드, 디이소부틸 알루미늄 클로라이드, 디에틸 알루미늄 브로마이드, 디에틸 알루미늄 이오다이드, 에틸 알루미늄 세스퀴클로라이드, 트리에틸 알루미늄과 디에틸알루미늄의 혼합물이 바람직한 화합물이고 디에틸 알루미늄 클로라이드가 특히 바람직하다.Wherein R ⁴ is an alkyl group having 1 to 18 carbon atoms, X ⁴ is hydrogen, chlorine, bromine or urido or an alkoxy group having 1 to 8 carbon atoms and m is 0

m <3 is a satisfying number. These include, for example, trialkyl aluminum, alkyl aluminum halides, alkyl aluminum hydrides, alkyl aluminum alkoxides, alkyl aluminum alkoxy halides and the like. Dual dimethyl aluminum chloride, diethyl aluminum chloride, diisobutyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, ethyl aluminum sesquichloride, a mixture of triethyl aluminum and diethyl aluminum are preferred compounds and diethyl aluminum Chloride is particularly preferred.

In the present invention, it is important that the molecular ratio [(B) / (A)] of the catalyst (B) to the catalyst (A) is in the range of 20/1 to 100/1, preferably 30/1 to 70/1. Do. When this ratio is outside this range, the amount of the low-molecular-weight amorphous polymer is not reduced because it is contained in the unwanted amorphous copolymer and the resulting copolymer which are dissolved in the polymerization solvent, so that the present invention described in Examples and Comparative Examples will be described later. The effect of the invention cannot be obtained.

-카프로락톤 등의 포화 또는 불포화의 지방족, 지환족 또The catalyst used in the present invention may basically contain an electron donor known as the third component in addition to the two components described above having the specific ratios described above. The electron donor as such a third component contains oxygen, nitrogen, sulfur or phosphorus atoms and aromatic compounds may also be used as is well known. Specific examples thereof include ethyl acetate, methyl methacrylate, ethyl benzoate,

Saturated or unsaturated aliphatic, cycloaliphatic or

Since the effects of the electron donor vary depending on their properties, the molecular ratio of the electron donor to the two catalyst components described above may allow for a decrease in catalytic activity and to determine the amount of atactic polymer that can be produced. Although appropriately selected, the electron donor is generally used at a molecular ratio of about 0.01 to 100 for the catalyst (A).

When the catalysts (A) and (B), or (A), (B) and the electron donor are fed to the polymerization vessel, they are fed separately or as a mixture of two or three components.

The process of the present invention is a copolymer containing about 80 to 99 mole percent propylene and 1 to 20 mole percent ethylene and / or 4 to 18 α-olefins, preferably 85 to 97.5 mole propylene and 2.5 to 15 moles It applies to the preparation of copolymers containing% ethylene and / or α-olefins having 4 to 18 carbon atoms. If the propylene content is larger than in the above-described range, the effect of the present invention is not remarkable. On the other hand, when it is less, the industrial production of the copolymer becomes difficult because the amorphous polymer soluble in the polymerization solvent is increased.

The monomers supplied to the polymerization system are propylene, ethylene, and / or α-olepin having 4 to 18 carbon atoms. α-olefins include butene-1, pentene-1, 3-methyl-pentene-1,4-methylpentene-1, octene-1, deken-1, dodecene-1, tetradecene-1, hexadeken-1 , Octadeken-1, and mixtures of two or more are used. Particular preference is given to double butene-1. Preferred examples of the copolymer include propylene ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene-1 copolymers, and the like.

The molecular ratio of the monomer supplied to the polymerization system can determine the activity of the monomer, which can be measured by a known method, so that a copolymer having a desired composition can be obtained in the production state (temperature, pressure, type of polymerization solvent, catalyst, etc.). Should be chosen.

The polymerization can be carried out inert organic such as aliphatic hydrocarbons (e.g. butane, pentane, hexane, heptane, etc.), alicyclic hydrocarbons (e.g. cyclohexane, methylcyclohexane, etc.) or aromatic hydrocarbons (e.g. benzene, roluene, etc.) In solvents, it is carried out in liquid monomers containing no inert organic solvent or in gaseous monomers.

The polymerization temperature is about 0 to 200 ° C., preferably about 30 to 100 ° C., more preferably about 40 to 80 ° C. The polymerization pressure may be arbitrarily selected according to the polymerization method without being limited, for example, at atmospheric pressure to 100 kg / cm ² .

The molecular weight of the resulting copolymer can be controlled using various molecular weight modifiers, often using hydrogen as modifier. The polymerization can be carried out continuously or in batches. It is economical to adjust the reaction conditions such that the polymerization time or average residence time in the polymerization vessel can be arbitrarily maintained, or to maintain the polymerization time or average residence time that can produce more than 8,000 parts of copolymer per weight of catalyst (A). And thus eliminating or simplifying the step of removing catalyst residues.

The copolymer obtained by polymerization is actually used after conventional treatment.

Preferred embodiments of the invention copolymerize propylene, ethylene and / or C ₄ -C ₁₈ α-olephine in a liquid solvent with a solubility parameter δ of 7.0 (Cal / c) 1/2 or less and wash the stopped polymerization slurry in countercurrent washing. The technique is introduced into the top of the tower to countercurrent the slurry. The technique is to contact the liquid solvent with δ of 7.0 (cal / cc) ^1/2 or less and pass the bottom of the tower to wash the slurry. Solubility parameter δ is defined by JH Hildebrand, Thc Solubility of Non-Electrolytes, Reinhold Publishing Corporation (1950):

E/V)^1/2 δ = (

E / V) ^1/2

E는 증발에너지이고 V는 분자용적이다. 이 방법으로 매우 만족스러운 열접착성, 내한성, 투명도, 윤활성, 차단성등을 지닌 프로필텐 공중합체가 공급될 수 있으며 원료 중합에서의 경제적 및 산업적 장점을 망치지 않고 필름으로 성형된다. 본 발명에 적합한 공중합체의 조성은 상기에 기술된 바와 같으나 바람직하게는 약 80내지 99중량% 프로필렌, 0.5내지 5중량% 에틸렌 및 0.5 내지 15중량% 부텐-1이고 가장 바람직하게는 약 86내지 98중량% 프로필렌, 1 내지 4중량% 에틸렌 및 1 내지 10중량% 부텐-1이다. 상기 기술된 세가지 조성의 공중합체로 특히 괄목할만한 효과 얻어질 수 있으며 열접착성, 내한성, 투명도, 윤활성 및 항-차단성이 양호한 필름을 공급하는 공중합체가 얻어질 수 있다.Above

E is the evaporation energy and V is the molecular volume. In this way propylene copolymers with very satisfactory thermal adhesion, cold resistance, transparency, lubricity, barrier properties, etc. can be supplied and molded into films without spoiling the economic and industrial advantages of raw material polymerization. The composition of the copolymers suitable for the present invention is as described above but is preferably about 80 to 99% by weight propylene, 0.5 to 5% by weight ethylene and 0.5 to 15% by weight butene-1 and most preferably about 86 to 98 Wt% propylene, 1-4 wt% ethylene and 1-10 wt% butene-1. Particularly remarkable effects can be obtained with the copolymers of the three compositions described above and copolymers can be obtained which supply films with good thermal adhesion, cold resistance, transparency, lubricity and anti-blocking properties.

In addition, the weight ratio of ethylene to butene-1 in the copolymer is about 1:30 to 10: 1, preferably about 1:10 to 4: 1, more preferably about 1: 5 to 3: 1.

The feedstock at the bottom of the countercurrent wash tower preferably has a solubility parameter of 7.0 (cal / cc) ^1/2 or less. Characteristic examples of this liquid use include n-propane, n-butane, isobutane, isopentane, propylene, butene-1, cis- and trans-butene-2, isobutylene and the like and mixtures thereof. In addition, these and a small amount of a large amount of solvent tangerine such as hexane, heptane, roluene and the like can be preferably used when the δ of the tangerine does not exceed 7.0 (cal / cc) ^1/2 or more.

The liquid solvents used in the polymerization system and the countercurrent wash tower feed are the same or different or a mixture of both. Particularly preferred liquid media are monomers that are free of inert solvents such as Propylene or Butene-1.

The polymerization conditions of the liquid monomers such as propylene and butene-1 should be appropriately selected in view of the polymerization system, the pressure and temperature of the catalyst crab, the concentration of the molecular weight regulator and the stabilizer, the stirring conditions, the cooling and heating conditions, and the like. As is generally known, the properties of the polymerization system (eg polymerization rate, polymerization time, residence time, etc.) and the properties of the resulting copolymer (eg composition, melt viscosity, cooled xylene-dissolution, etc.) The conditions are chosen to take into account the monomer mixture in the liquid phase.

The figure shows a process diagram showing one embodiment of the method of the invention. Liquid propylene, ethylene and butene-1 are introduced into polymerization tank 1 through pipes 2, 3 and 4, respectively, and a molecular weight modifier such as hydrogen is introduced through pipe 5 to the catalyst through pipe 6. If an inert solvent such as propane or butane is used, it is introduced via tubing 2 like any other tubing or mixture with liquid propylene.

The polymerization reaction proceeds under pressure such that the monomer mixture or mixture of monomers with an inert solvent such as propane or butane is maintained in the liquid phase. The resulting polymer slurry is then continuously or batch-by-batch, preferably continuously, collected from polymer tank 1 through the valve 7 and introduced into the upper nine parts of the counter-flow scrubber 8. A liquid medium having a δ of 7.0 (cal / cc) ^1/2 or less and containing no polymers (mainly amorphous polymers) soluble in the polymerization slurry is introduced into the washing tower 8 through the bottom of the countercurrent washing tower.

The polymer soluble in the polymerization slurry and the catalyst remaining in the slurry are selectively released through the outlet pipe 11 at the top and introduced into the amorphous polymer recovery apparatus. The polymer slurry was brought into contact with the liquid bottom feed in the washing tower 8 and the polymer insoluble in the slurry was reduced to approximately atmospheric pressure by a valve 13 attached with a concentration regulator, LC, to precipitate the slurry at the bottom of the tower. It is selectively discharged through pipe 12 and introduced into flash tank 14.

Under normal pressure, the volatile monomer is evaporated in the flash tank 14 and the piping 15 is transferred to the purification step. On the other hand, the polymer separated in the flash tank 14 is either directly or through post-treatment such as catalysis, if necessary, through valve 16 and then transferred to a funnel or pelletizer.

One function of the backwash tower in the process of the present invention is to separate the liquid medium in the top feed and release the liquid medium through the outlet tube at the top of the tower along with the bottom feed rising from the bottom of the tower. Another function is to wash the insoluble polymer in the top feed with the bottom feed and discharge the soluble (amorphous) polymer along with a portion of the bottom feed through the bottom of the tower.

Conventional countercurrent wash towers may be used. For example, those described in Japanese Patent Application (OPI) No. 139,886 / 76 are suitable.

The following examples and comparative examples are set forth to aid in understanding the process of the present invention. However, the present invention is not limited to this, and specific values in the examples are measured by the following method.

[1] dissolution index [MI]:

It measures by JISK6758.

[2] thermal bonding temperature:

The two films are compressed and bonded by applying a 2kg / cm ² load for 2 seconds using a heat sealer at a given temperature, and the resulting 25 mm wide sample is peeled off at a peel rate of 200 mm / min and a peel angle of 180 °. It's adventurous. The temperature at which the measured peeling resistance is 300 g / 25 mm is regarded as the thermal bonding temperature.

3. Transparency:

Measured by ASTM D1003

4. Blocking:

A barrier tester manufactured by Shimatsu Seisakusho Co., Ltd. measures the barrier property of a test piece when a load of 40 g / cm ² is applied at 60 ° C. for 3 hours.

5. Strength:

Measured by ASTM D 747.

6. Cold resistance:

의 시험편을 0℃에서 수평으로 고정시키고 여러가지 중량의 핀(충격 부위가 1/2인치 R 인 반구형)을 지정된 높이에서 떨어뜨려 시험편의 50%가 파괴되었을 때의 운동에너지를 측정한다. 얻어진 에너지를 시험편의 두께로 나누고 이값을 저은 충격강도 즉 내빙성으로서 측정한다.40 mm

Hold the test specimens at 0 ° C horizontally and drop the pins of various weights (half-spherical with 1/2 inch R of impact) at the specified height and measure the kinetic energy when 50% of the specimens are destroyed. The energy obtained is divided by the thickness of the test piece and this value is measured as low impact strength, ie ice resistance.

Transparency, thermal bonding temperature, barrier and cold resistance are 0.1% by weight 2,6-di-t-butyl-p-cresol, 0.1% by weight tetramethylene 3- (3,5-di-t-butyl-4-hydride A copolymer made of hydroxyphenyl) propionate methane, 0.1% by weight of erucic amido, 0.1% by weight of calcium stearate, and 0.1% of SiO ₂ fine powder and made into a 30μ thick film Measured against the film.

Example 1

1. Preparation of catalyst:

1) Process I (Preparation of Reduced Product)

After washing the 200 L reaction vessel and filling with argon, 40 L dehydrated hexane and 10 L titanium tetrachloride were injected. The solution is kept at -5 ° C and a solution consisting of 30 L dehydrated hexane and 23.2 L ethyl aluminum sesquichloride is added dropwise under reaction conditions such that the temperature of the reaction system does not exceed -3 ° C. Stirring is continued for 2 hours at the same temperature. After reaction, the di-mix is left to stand and the reduced product formed is obtained by solid-liquid separation at 0 ° C. and washed with 40 L of hexane for 2 hours. At this time 16 kg of reduction product are obtained.

2) Process II

The reduction product obtained in Process I is slurried with n-decalin to a slurry with a concentration of 0.2 g / cc and heat treated at 140 ° C. for 2 hours. After the reaction, the supernatant was removed and washed twice with 40 L of hexane to obtain a titanium trichloride composition (A).

3) Process III

11 kg of titanium trichloride composition prepared according to Process II was slurried with 55 L of toluene and iodine and dia were added so that the molar ratio of titanium trichloride composition (A) / I ₂ / diisoamyl ether was 1 / 0.1 / 1.0. Add pediatric wheat ether. Thereafter, the mixture was reacted at 80 ° C. for 1 hour to obtain a titanium trichloride solid catalyst (B).

2. Production method of propylene copolymer

After 200 liters (internal capacity) of the polymerization vessel equipped with a stirrer was completely filled with propylene, 68 liters of heptane, 13.6 kg of propylene and 0.08 kg of ethylene were added thereto. After raising the temperature of the vessel to 60 ° C., ethylene and hydrogen were added so that the pressure was 10 kg / cm 2 and the concentration of ethylene and hydrogen in the gas phase was 2.2 mol%, respectively.

Copolymerization is initiated by adding 0.02 mole (3.1 g) of the titanium trichloride solid catalyst (B) and 0.7 mole (84.4 g) of diethyl aluminum chloride (EDAC) followed by washing with 2 L of heptane. The copolymerization is then continued for 8 hours while the monomer is continuously added to maintain the temperature, pressure and gaseous composition at a constant concentration.

Butanol was added thereto to terminate the copolymerization, followed by 70 l of heptane at 60 ° C., followed by stirring for 30 minutes.

The powdery copolymer is separated by centrifugation and dried to give 26.5 kg of powdery copolymer. 2.0 kg of non-crystalline polymer is obtained at the concentration of the remaining butane separated from the powdery copolymer.

The weight percent (HIP%) of the powdered copolymer based on the total polymer produced is 93% and the weight of the total polymer produced per unit weight of the titanium trichloride toxin component is 9,200 g / g.

The production and properties of powdered copolymers are described in Table 1.

Example 2

Except for adding the calculated amount of butene-1, the method of Example 1 is repeated to obtain the desired copolymer composition instead of ethyl in Table 1. The results are shown in Table 1.

Example 3

The procedure of Example 1 is repeated except that the calculated amounts of ethylene and butene-1 are added to obtain the desired copolymer composition instead of ethylene in Table 1. The results are shown in Table 1.

Example 4

Example 3 is repeated except changing the desired copolymer composition shown in Table 1. The results are shown in Table 1.

Example 5 and Comparative Example

Example 3 is repeated except changing the amount of diethylaluminum chloride shown in Table 1.

Comparative Examples 2 and 3

Example 3 is repeated except that 10 g of titanium trichloride, a product of Toho Titanium Corporation, is added instead of the titanium trichloride solid catalyst (B) prepared in Example 1 (1), and the amount of diethylaluminum chloride introduced is changed. The results are shown in Table 1.

TABLE 1

* 1 Propylene * 2 Ethylene * 3 Butene-1

Example 6

(1) Preparation of Catalyst

1) Process 1 (Preparation of β-type titanium trichloride)

Fill the argon in a 200 liter reactor, add 40 liters of anhydrous hexane and 10 liters of titanium tetrachloride to it, and leave it at -5 ° C. Then, add 30 liters of anhydrous hexane and 116l of diethylaluminum chloride. Do not After the dropwise addition, the mixture was stirred for 30 minutes, the temperature was raised to 70 ° C., and then further stirred for 1 hour. The reaction mixture was left to stand and the β-type titanium trichloride obtained by solid-liquid separation was washed three times with 40 L of hexane to obtain 15 kg of reduction product.

2) Process II (Preparation of Solid Treated with Lewis Base)

The β-type titanium trichloride obtained according to the above step I was suspended in 40 L of anhydrous hexane, and 1.2 times (molar ratio) of β-type titanium trichloride was added to the diisoacetic ether, followed by stirring at 40 ° C for 1 hour. Upon completion of the reaction, the supernatant was removed, washed three times with 40 L of hexane and dried.

3) Process III

10 kg of the solid treated with Lewis base prepared according to the above step II was added to 30 l of anhydrous heptane and 20 l of titanium tetrachloride and heated to 70 ° C. for 2 hours. After the reaction, the supernatant was discarded, washed three times with 30 L of hexane, and then dried to obtain a titanium trichloride solid catalyst (C).

(2) Production method of propylene copolymer

A 200 L polymerization vessel with a stirrer was charged with propylene, and 50 kg of pyrostyrene and 0.075 kg of ethylene were added thereto. 0.013 mol (2.0 g) of titanium trichloride (C), 0.54 mol (65 g) of diethylaluminum chloride (DEAC) and 0.02 (2.0 g) of methyl methacrylate were added to the vessel, and the temperature of the vessel was immediately raised to 60 ° C. Up. The monomers are fed to maintain a constant amount of temperature, pressure and gas composition while continuing to react for 4 hours. In addition, the molecular weight is adjusted using hydrogen.

Isobutanol was added to stop the copolymerization, and the slurry was washed twice with 50 kg of liquid propylene to obtain 2.4 kg of a powdered copolymer. 0.4 kg of the amorphous polymer dissolved in the propylene washing solution is recovered. The ratio of the recovered amorphous polymer to the total copolymer prepared was 1.6 weights and the amount of the total copolymer prepared per weight unit of titanium trichloride was 12,100 g / g-TiCl ₃ . The composition and properties of the obtained powdery copolymer are described in Table 2.

Example 7

Performed according to Example 6, but here the calculated amount of butene-1 is added to obtain the desired copolymer composition in place of ethylene as described in Table 2. The results obtained are described in Table 2.

Example 8

Performed according to Example 6 but here the calculated amounts of ethylene and butene-1 are added to obtain the desired copolymer composition in place of ethylene as shown in Table 2. The results obtained are described in Table 2.

Example 9

Example 8 is repeated except changing the intended copolymer composition shown in Table 2. The results obtained are shown in Table 2.

Example 10 and Comparative Example 4

Example 8 is repeated except that the amount of diethylaluminum chloride introduced is shown in Table 2. The results obtained are shown in Table 2.

TABLE 2

^* 1 propylene ^* 2 ethylene

^* 3butene-1 ^* 4 Percentage of recovered AP (%)

Example 11

Liquid propylene 900 kg / hr, ethylene 11 kg / hr, butene-1,80 kg / hr, solid catalyst (B) described above, 40 g (0.26 mol) / hr 1100 g (9.1 mol) of diethylaluminum chloride (DEAC) / hr and 40 g (0.40 mol) hr of methyl methacrylate were continuously injected into a 30 m3 copolymerization tank in the presence of hydrogen, and the copolymerization reaction between ethylene, propylene and butene-1 was carried out in an effluent method while maintaining the temperature in the tank at 60 ° C. Follow the instructions.

The polymerization slurry is continuously drawn down to the lower portion of the tank to maintain a constant liquid level in the tank and injected into the upper portion 9 of the countercurrent multistage contact wash tower 8 shown in the figure. Isobutanol is injected into the tank at a rate of 1 kg / hr through the central portion 17 of 2 as a deactivator.

On the other hand, the purified liquid layer propylene maintained at 50 to 52 ° C. was continuously added through the lower portion 10 of the column at an outflow rate of 1100 kg / hr and the contents of the column were stirred at an extremely low speed of 12 rpm.

The insoluble polymer precipitated in the lower part of the column continues to be drawn down through the pipe 12 into the flash tank 14 via a reducing valve 13 connected to the level meter LC. The powdery copolymer is thus obtained at a rate of 450 kg / hr.

On the other hand, a liquid monolith containing a soluble material in a monolith such as a catalyst and a reaction product between isobutanol and a soluble amorphous polymer is released from the top 11 and injected into the atactic polymer recovery apparatus. Thus, the crystalline polymer is recovered at a rate of 7.3 kg / hr. The loss of the fine powdery solid copolymer contained therein does not exceed 1%. The proportion of recovered atactic polymer (AP-recovery ratio) based on the pre-produced copolymer was 1.6%.

In addition, the countercurrent wash tower used here is 600 mm in diameter, 8200 mm in height, and has a ten-stage conical rotating plate.

The ash content of the powdered copolymer washed in the washing step and recovered by the flash tank is very small as follows. Starch content: 500 ppm; TiO ₂ : 34 ppm, Al ₂ O ₃ : 10 ppm, and the volatile content corresponds to 20 ppm.

The powdery copolymer thus obtained is a white transparent powder and does not cause problems such as foaming and corrosion when pelletized and peeled off. The composition and properties of this copolymer are shown in Table 3.

[Example 12 and Comparative Example 5]

Example 11 is repeated except that the amount of syrup DEAC is changed in Table 3. The results obtained are shown in Table 3. If the molar ratio of DEAC / Ticl ₃ is less than 20, Example 11 is repeated except changing the amount of recovered DEAC as shown in Table 3. The proportion of recovered AP is greatly increased and the loss of micropowdered solid copolymer contained therein is increased to 3 to 4%. The ash content of the resulting powdery copolymer is as follows.

The copolymer is a yellow powder. The composition and properties of the obtained copolymer are shown in Table 3. Transparency, robustness, heat dissipation and barrier properties are reduced, in particular barrier properties are greatly reduced. Therefore, the commerciality of the copolymer is low. It can be seen from Table 3 that this catalyst does not provide the effect of the present invention even when the molar ratio of DEAC / TiCl ₃ is 20 to 100.

[Examples 13 and 14]

Example 11 is repeated except that the solid catalyst (C) is used instead of the solid catalyst (B) and the desired copolymer composition is changed as shown in Table 3. The results are in Table 3.

TABLE 3

* 1 Ethylene (wt%) * 2 Butene-1 (wt%) * 3 Percentage of recovered AP (wt%)

Since the present invention has been described in detail with specific embodiments, various changes and modifications may be made to the starch in the art without departing from the spirit and scope of the invention.

Claims (1)

An improved Ziegler-containing titanium trichloride (A) and an organoaluminum compound (B), produced by reacting titanium tetrachloride with an organoaluminum compound and activating the product, at a molecular ratio (B) / (A) of about 20 to 100. A process for preparing a propylene copolymer containing from about 80 to 99 mol% propylene and about 1 to 20 mol% ethylene and / or an α-olefin having 4 to 18 carbon atoms using a Ziegler-Natta catalyst.

Images