JP5567764B2 - Butene-1 (co) polymer with low isotacticity - Google Patents

Description

  The present invention relates to certain butene-1 (co) polymers having low isotacticity and elastomeric behavior. The present invention further relates to a polymer composition comprising the butene-1 (co) polymer.

Certain butene-1 (co) polymers with low isotacticity and elastomeric behavior are known in the art. They can be used as a component of blends with other polyolefins, or polymer products, to tailor certain properties, such as the sealing strength, flexibility and softness of plastic materials. In particular, these butene-1 (co) polymers can be used as additives in the production of field boards, road surface materials and sealant compositions, or as oil thickeners. For use in these purposes, an important property is the appropriate processability between plastic and elastomeric properties derived from good processability and a good balance between the crystalline and amorphous parts of the polymer. It's a compromise. German Patent DE 2224112 describes the preparation of a low stereoregular polybutene carried out by polymerizing butene-1 using a TiCl ₃ based catalyst. According to this document, the original stereospecificity of this catalyst has been reduced by using Al-trialkyl compounds as cocatalysts at specific Al: Ti molar ratios. Nevertheless, the contribution of the more crystalline part is still too high. In fact, considering the polymers with processable molecular weights, it can be seen that the elastomeric properties are not sufficient when focusing on the amount of ether solubles.

European Patent No. EP 186968 discloses a highly stereoregular thermoplastic polybutene-1 characterized by more remarkable elastomeric properties compared to conventional isotactic polybutene-1. This polybutene-1 comprises (a) a solid component comprising a Ti compound and a benzoate internal donor supported on MgCl ₂ ; (b) an alkylaluminum compound as a co-catalyst, and (c) as an external electron donor compound. Obtained by use of a Ziegler-Natta catalyst system containing ethyl p-anisate. However, even in this case, a high content of isotactic sequences still affects the properties of the polymer, as evidenced by a small amount of ether soluble fraction and a relatively high yield point tensile strength.

US Pat. No. 4,298,722 describes an organic compound of the formula (RCH ₂ ) ₄ M where M is Ti, Zr or Hf and R is aryl, aralkyl or tertiary alkyl. Butene-1 in the presence of a catalyst that is the reaction product of a metal compound and a partially hydrated surface of a metal oxide such as Al ₂ O ₃ , TiO ₂ , SiO ₂ or mixtures thereof. The preparation of a fractionable elastomeric polybutene-1 obtained by polymerization has been reported. Polymers obtained directly from polymerization have a very high intrinsic viscosity that cannot be processed by conventional equipment and cannot be used arbitrarily in the preparation of polymer compositions. Intrinsic viscosity is reduced by heating and grinding the polymer, but at the same time, the ether soluble portion is reduced, resulting in worse elastomeric properties. Thus, in order to meet both the proper viscosity range and final elastomeric properties, the polymer prior to milling must contain a very large amount of ether-soluble moieties. However, at those levels, certain mechanical properties may no longer be appropriate for certain applications.

  Thus, with an appropriate balance of low isotacticity and elastomeric properties (compression set, elongation at break) and elastomeric properties (breaking tensile stress or yielding tensile stress) related to more crystalline parts There still remains a need for polybutene-1 (co) polymers having

Applicant has a good balance and has the following characteristics:
A content of butene-1 units in the form of isotactic pentads (mmmm) of 25-55%;
An intrinsic viscosity [η] measured in tetralin at 135 ° C. of 1 to 3 dL / g;
-The content of xylene insoluble part at 0 ° C is 3-60%; and
-ES ₂ / ES ₁ ratio (ES ₁ is the amount of boiling diethyl ether soluble portion measured with respect to the polymer itself, ES ₂ is the boiling diethyl ether content measured after grinding the polymer according to the method described below. The butene-1 (co) polymer was found to be 1 or more in terms of the amount of dissolved portion).

In particular, the butene-1 (co) polymer that is the object of the present invention has the following characteristics:
- content (total weight, based on the) 20 to 75% of the boiling diethyl ether soluble portion (ES _1), preferably 30 to 65%, especially 35% to 60%;
A content of butene-1 units in the form of isotactic pentads (mmmm) of 30 to 50%, preferably 32 to 45%;
An intrinsic viscosity [η] measured in tetralin at 135 ° C. of 1.5 to 3 dL / g, preferably 1.7 to 2.8 dL / g;
A content of xylene insoluble part at 0 ° C. (based on the total weight of the polymer) of 5 to 50%.

In a preferred aspect of the invention, the butene-1 (co) polymer has the following properties:
-Molecular weight distribution (Mw / Mn) measured according to the following method 3.5-9; more preferably 4-8, and especially 4-7;
A heat of fusion (ΔH) measured by differential scanning calorimetry (DSC) of less than 10 J / g and a melting temperature (Tm) of less than 106 ° C., preferably less than 103 ° C. and more preferably less than 100 ° C. (in some cases No melting point)
Compression set (25% -22 hours) less than 90%, preferably less than 80%, and more preferably less than 50%, and Tensile stress at break above 6 Mpa, preferably 6.5-20 Mpa
One or more of the above.

Shore A values are generally less than 80, and in some cases less than 60.
In view of these properties, the butene-1 (co) polymers of the present invention can be used as a component in polymer compositions used in applications that require a certain level of softness.

As indicated by the intrinsic viscosity range described above, the molecular weight of the polymer of the present invention is substantially in a range that allows the butene-1 copolymer to be processed on conventional equipment.
Preferably, the melt index measured according to ASTM D1238 Condition E comprises 0.1 to 100 g / 10 min, more preferably 0.1 to 10 g / 10 min.

The butene-1 (co) polymers of the present invention comprise other olefins of the formula CH ₂ ═CHR, where R is H or a C1-C10 alkyl different from ethyl. Can do. Particular preference is given to using ethylene, propylene and hexene-1 or mixtures thereof as comonomer (s). The amount of the additional olefin (s) in the polymer of the present invention is preferably 0.1 to 20 mol%, more preferably 0.5 to 15 mol%.

  The butene-1 (co) polymers of the present invention are also characterized by the fact that no signals of 4,1 intervening butene units are observed when analyzed by NMR with the following apparatus and procedure.

  As noted above, the polymers of the present invention can be used on their own or in polymer compositions for use at low seal initiation temperatures, ie, compositions for textile applications, field boards and road surface materials. In such a wide range of applications, it can be preferably used as a component of blends with other polymers. Because of their elastomeric properties, it is even possible to use soft vinyl polymers, such as highly plasticized poly (vinyl chloride) or some SEBS compounds, without plasticizers.

  Thus, a further object of the present invention is: (A) 1-99% by weight of the butene-1 (co) polymer of the present invention; and (B) 99-1% by weight of another polymer component % By weight is based on the sum of (A) + (B)).

In particular, (A) can be present in an amount of 10-90% and (B) can be present in an amount of 90-10%.
Preferably component (B) comprises an olefin (co) polymer. In particular, component (B) can be selected from ethylene (co) polymers, propylene (co) polymers, butene-1 (co) polymers and mixtures thereof.

Of particular interest are: (A) 5-40% by weight of the butene-1 (co) polymer of the invention; and (B) 1-30 mol% of ethylene and / or the formula CH ₂ ═CHR, where R is C 2 A polymer composition comprising 60 to 95% by weight of a propylene copolymer containing an α-olefin represented by —C10 hydrocarbon group ”(the weight percent is based on the sum of (A) + (B)). .

  Preferably, the α-olefin is butene-1. (B) a propylene copolymer comprising both ethylene and butene-1 having (a) an ethylene content of 1-10% and a butene-1 content of 1-10%, and (b) butene-1 Of particular interest are compositions selected from propylene copolymers containing from 2 to 15 mol%.

The composition, which is particularly useful in applications where low seal initiation temperature (SIT) is required, maintains acceptable mechanical properties and exhibits good flowability and clarity.
The butene-1 copolymers and compositions that are the object of the present invention can be vulcanized or crosslinked to produce thermoplastic elastomer blends having enhanced elastomeric behavior.

  The terms vulcanization and crosslinking include actual crosslinking or vulcanization and reactions that occur as a result of the reaction in which the grafting in the chain of butene-1 (co) polymer is promoted by the crosslinking system used.

  Of the various vulcanization techniques known in the art, the preferred technique is dynamic vulcanization. When working with this technique, the polymers of the present invention are exposed to kneading or other shear forces in the presence of cross-linking agents and, where appropriate, their adjuncts. Surprisingly, the normal temperature range for vulcanization is 140-240 ° C., but for polybutenes having a Shore D of less than 50, preferably less than 40, especially for the polybutenes of the present invention, the crosslinking process. Has been found to be carried out at a temperature of 100-150 ° C. Thus, the crosslinkers that can be used are preferably crosslinkers known in the art, such as organic peroxides, such as 1,1-di (tert. Butyl peroxy) -3,3,5-trimethylcyclohexane; dicetyl peroxydicarbonate; tert. Butyl-per-2-ethylhexanoate). The polymers or compositions of the present invention can be impregnated with an extender oil to adjust their hardness before the addition of the crosslinking agent or at the beginning or end of vulcanization. The extender oil used can be of various types, for example aromatic, naphthene or preferably paraffin. As auxiliary compounds for crosslinking, liquid 1,2-polybutadiene or preferably triallyl cyanurate compounds and trimethylolpropane-trimethacrylate type compounds can be used.

The butene-1 (co) polymer of the present invention comprises (A) a solid component containing a Ti compound supported on MgCl ₂ and an electron donor compound; and (B) a low stereospecific catalyst containing an alkylaluminum compound. It can be prepared by polymerizing the monomer in the presence. In a preferred aspect of the method for preparing the (co) polymer of the present invention, the external electron donor compound is not used so as not to increase the stereoregularity adjusting ability of the catalyst. If an external donor is used, its usage and mode of use should not produce too much polymer with high stereoregularity.

  Active form of magnesium dichloride is preferably used as the carrier. It is known from the patent literature that activated magnesium dichloride is particularly suitable as a support for Ziegler-Natta catalysts. US Pat. Nos. 4,298,718 and 4,495,338 described for the first time the use of these compounds in Ziegler-Natta catalytic reactions. An active form of magnesium dihalide used as a support or auxiliary support in a catalyst component for olefin polymerization has a maximum intensity diffraction line appearing in the spectrum of inactive halides, and the intensity is reduced and halogen ( It can be seen from these patents that the maximum intensity of the halogen is characterized by an X-ray spectrum that is displaced by a lower angle compared to the stronger intense spectrum.

Preferred titanium compounds used in the catalyst component of the present invention are TiCl ₄ and TiCl ₃ ; furthermore, the formula Ti (OR) _ny X _y , where n is the valence of titanium, X is halogen, It is also possible to use Ti-halo alcoholates, preferably chlorine and y being a number from 1 to n.

The internal electron donor compound is preferably selected from esters, more preferably monocarboxylic acids such as benzoic acid, or polycarboxylic acids such as alkyl, cycloalkyl or aryl esters of phthalic acid or succinic acid (the alkyl, cycloalkyl Or the aryl group has 1 to 18 carbon atoms). Examples of the electron donor compound are diisobutyl phthalate, diethyl phthalate and dihexyl phthalate. Generally, the internal electron donor compound, 0.01 to MgCl ₂ as a reference, is preferably used in a molar ratio of 0.05 to 0.5.

The preparation of the solid catalyst component can be carried out by several methods.
According to one preferred method, the solid catalyst is a titanium compound of the formula Ti (OR) _ny X _y , where n is the valence of titanium and y is a number from 1 to n, preferably TiCl ₄ , the formula MgCl ₂ · pROH, where p is a number from 0,1 to 6, preferably a number from 2 to 3.5, and R is a hydrocarbon having from 1 to 18 carbon atoms. The group can be prepared by reacting with magnesium chloride derived from an adduct represented by the following formula: The adduct is in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon that is immiscible with the adduct and operating under stirring conditions at the melting temperature of the adduct (100-130 ° C.). Can be prepared appropriately. The emulsion is then rapidly quenched, thereby coagulating the adduct in the form of spherical particles. Examples of spherical adducts prepared by this procedure are described in US Pat. Nos. 4,399,054 and 4,469,648. The adduct thus obtained can be reacted directly with the Ti compound or an adduct with an alcohol mole number of generally less than 3, preferably 0.1 to 2.5 is obtained. As previously, it can be exposed to heat controlled dealcohol (80-130 ° C.). The reaction with the Ti compound involves suspending the adduct (dealcoholized or neat) in cold TiCl ₄ (generally 0 ° C.); heating the mixture up to 80-130 ° C. and This can be done by keeping the temperature for 0.5 to 2 hours. The treatment with TiCl ₄ can be performed one or more times. An internal electron donor compound can be added during treatment with TiCl ₄ . The treatment with the electron donor compound can be repeated one or more times.

  The preparation of the catalyst component in spherical form is, for example, European patent applications EP-A-395083, EP-A-553805, EP-A-553806, EP-A-601525 and WO98 / 44001. It is described in.

The solid catalyst components obtained according to the method, more than generally 20 to 500 m ² / g, preferably a surface area of 50 to 400 m ² / g (by B.E.T. method) and 0.2, preferably 0 , 2 to 0,6 cm ³ / g of total porosity (according to the BET method). The porosity (Hg method) of pores having a radius of 10.000 mm or less is generally in the range of 0.3 to 1.5 cm ³ / g, preferably 0.45 to 1 cm ³ / g.

The alkyl-Al compound (B) is preferably selected from trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. The Mixtures of trialkylaluminum with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt ₂ Cl and Al ₂ Et ₃ Cl ₃ can also be used.

When used, the external donor (C) preferably has the formula R _a ⁵ R _b ⁶ Si (OR ⁷ ) _c , where a and b are integers from 0 to 2 and c is from 1 to 3 And the sum (a + b + c) is 4; R ⁵ , R ⁶ and R ⁷ are alkyl, cycloalkyl or aryl groups having 1 to 18 carbon atoms optionally containing heteroatoms) It is selected from silicon compounds represented by A particularly preferred group of silicon compounds is that a is 0, c is 3, b is 1, R ⁶ is a branched or cycloalkyl group optionally containing heteroatoms, and R ⁷ is methyl. This is a silicon compound. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and texyltrimethoxysilane. The use of texyltrimethoxysilane is particularly preferred.

When used, the external electron donor compound (C) is supplied in such an amount that the weight ratio of the organoaluminum compound to the electron donor compound is more than 500, preferably more than 700.
The catalyst can also be prepolymerized in the prepolymerization step. The prepolymerization can be carried out in a liquid (slurry or solution) or in a gas phase, generally at a temperature of less than 100 ° C, preferably 20 to 70 ° C. The prepolymerization step is carried out with a small amount of monomer for the time necessary to obtain an amount of 0.5-2000 g, preferably 5-500 g, and more preferably 10-100 g of polymer per gram of solid catalyst component.

  The polymerization process can be carried out according to known techniques, for example by slurry polymerization using liquid inert hydrocarbons as diluent or solution polymerization using eg liquid butene-1 as reaction medium. Furthermore, the polymerization process can be carried out in the gas phase and is operated in one or more fluidized bed reactors or mechanically stirred bed reactors. Polymerization carried out using liquid butene-1 as the reaction medium is highly preferred.

  In general, the polymerization is carried out at a temperature of 20 to 120 ° C, preferably 40 to 90 ° C. The polymerization can be carried out in one or more reactors that can operate under the same or different reaction conditions such as molecular weight modifier concentration, comonomer concentration, external electron donor concentration, temperature, pressure, and the like. When using more than one reactor, the arrangement can be in a cascade mode where the monomer / catalyst / polymer reaction mixture from the first reactor is fed to a continuous reactor. Alternatively, in a parallel arrangement, two or more reactors with their own feed systems are operated independently and the monomer / catalyst / polymer reaction mixture resulting from those reactors is collected together and finally Oriented to section. Operation in at least two reactors under different conditions can lead to the preparation of butene-1 (co) polymers having different average molecular weights and / or different stereoregularities in the two reactors. Furthermore, operation in multiple reactors under different conditions has the advantage that the various polymerisation stages can be appropriately adjusted to appropriately adjust the properties of the final polymer. This technique can be employed when it is necessary to produce a product having a very high amount of xylene soluble moieties. In practice, these products can cause problems during certain operations, for example during granulation. Applicants have determined that the production derived from a single polymerization stage with the same amount of final xylene insoluble part by producing two polymers with different contents of xylene insoluble part in two different reactors in series It was noted that the final polymer could be processed better than the product. This can be accomplished, for example, by using a small amount of external donor that renders the catalyst more stereospecific only in one or more selected reactors. The (co) polymer obtained from the two-stage polymerization can have the same use as the copolymer obtained by a single set of polymerization conditions.

  As noted above, the copolymers of the present invention are suitable for use in many applications. As a general practice, for each of these applications, those skilled in the art will find additional polymer components, additives (eg, stabilizers, antioxidants, rust inhibitors, nucleating agents, processing aids, oils, etc.) and specific Both organic and inorganic fillers that can provide these properties can be added without departing from the spirit of the invention.

Hereinafter, the present invention will be illustrated in more detail without limiting the present invention with reference to examples.
Characterization
Two deuterated 1,1,2,2-tetrachloro in ¹³ C NMR analysis 120 ° C. comonomer content - was measured ¹³ C-NMR spectrum of ethane in the polymer solution (8-12 wt%). ^{In the 13} C-NMR spectrum, a 90 ° pulse and a 15 second delay between the pulse and CPD (WALTZ 16) were used to eliminate ¹ H- ¹³ C coupling, and at 120 ° C. in Fourier transform mode. Obtained by a Bruker DPX-400 spectrometer operating at .61 MHz. About 1500-2000 intermediates were stored at 32K data points using a spectral window of 60 ppm (0-60 ppm).

Comonomer content in butene / propylene copolymer The propylene content is: BBB = M / Σ BBP = L / Σ PBP = I / Σ
BPB = 0.5D / Σ BPP = [A + 0.5 (B + E)] / Σ
Obtained from triad distribution ([P] = [PPP] + [PPB] + [BPB]) calculated as PPP = (C + 0.5B) / Σ.

In the above formula, Σ = M + L + I + 0.5D + [A + 0.5 (B + E)] + (C + 0.5B), and A, B, C, D, E, I, L, M are peaks in the ¹³ C-NMR spectrum. (The peak at 27.73 ppm due to the CH ₂ carbon in the branch of the isotactic BBBBB pentad is used as an internal standard). The assignment of these peaks is N. Cheng, Journal of Polymer Science, Polymer Physics Edition, 21, 573 (1983) and shown in Table A.

Assignment of the pentad signal in the region of mmmm% quantitative branched methylene carbon by ¹³ C NMR is given by Five Polyolefins Determined from the Chemical Shift Calculation and the Polymerization Mechanism, T .; Asakura and others, Macromolecules 1991, 24 2334-2340. Based on the overlap between sterically irregular pentads, mmmm pentads were developed using the Two-site model analysis of ¹³ C NMR of polypropylene polymerized by Ziegler-Natta catalyst with external. Chujo, Y .; Kogure, T .; It was obtained by fitting the experimental pentad distribution with the two-site model described in Vaananen, Polymer, 1994, 35, 339-342. The mmmm% recorded in Table 1 is a value obtained by best fit.

Determination of 4,1 intervening butene units In the case of butene homopolymers or butene / propylene copolymers, the amount of 4,1 intervening butene units is investigated by ¹³ C-NMR spectroscopy under the above experimental conditions. The attribution of 4,1 intervening units is Busico, R.A. Cipullo, A.M. Borriello, Macromol Rapid Commun. 16, 269, (1995) and the results are shown in Table B.

Quantification of MWD by Gel Permeation Chromatography (GPC) MWD is 1 of solvent (stabilized with 0.1 volume of 2,6-di-t-butyl p-cresol (BHT)) at a flow rate of 1 ml / min. Quantify using a Waters 150-C ALC / GPC system equipped with a TSK column set (GMHXL-HT type) operating at 135 ° C. with 2-dichlorobenzene (ODCB). The sample is dissolved in ODCB by continuous stirring at a temperature of 140 ° C. for 1 hour. The solution is filtered through a 0.45 μm Teflon membrane. The filtrate (concentration 0.08-1.2 g / l, injection volume 300 μl) is applied to GPC. A monodispersed fraction of polystyrene (commercially available from Polymer Laboratories) was used as a standard. Universal calibration for PB copolymer is Mark for PS (K = 7.11 × 10 ⁻⁵ dl / g; α = 0.743) and PB (K = 1.18 × 10 ⁻⁴ dl / g; α = 0.725). -Performed by using a linear sum of Houwink constants.

Thermal Properties The melting point of the polymer (Tm) was measured by differential scanning calorimetry (DSC) using a Perkin Elmer DSC-7 measuring instrument according to standard methods. A weighed sample (5-7 mg) obtained from the polymerization was enclosed in an aluminum pan, heated in increments of 10 ° C. over 1 minute and heated to 180 ° C. The sample was held at 180 ° C. for 5 minutes to completely melt all the crystallites and then cooled to 20 ° C. at 10 ° C./min. After standing at 20 ° C. for 2 minutes, the sample was again heated to 180 ° C. at 10 ° C./min. In this second heating, the peak temperature was considered the melting point (Tm) and the peak area was considered the melting enthalpy (ΔH _f ).

Quantification of Shore A and D was measured according to ASTM D2240.
Tensile properties A polymer composition obtained by mixing the corresponding copolymer sample with 1% 2,6-di-tert-butyl-4-methylphenol (BHT) in Brabender at 180 ° C. is compression molded (at 200 ° C. , Then 307 minutes cooling), the tension was measured according to ISO 527-Tensile on 1.9 mm thick plaques. Unless otherwise noted, all mechanical measurements were made after holding the specimens for 10 minutes in an autoclave at room temperature and pressure of 2 kilobars.

Compression set was measured according to ASTM D395B Type 1 for compression molded samples treated in an autoclave for 1 minute at room temperature and 2 kilobars. The specimen so obtained was compressed to 25% of its original thickness and then placed in an oven at 70 ° C. or 23 ° C. for 22 hours.

Quantification of the xylene-insoluble part In order to quantify the part insoluble in xylene at 0 ° C., 2.5 g of polymer are dissolved in 250 ml of xylene at 135 ° C. with stirring and then cooled to 0 ° C. after 20 minutes. After 30 minutes, the precipitated polymer is filtered and then dried in vacuo at 80 ° C. until a constant weight is reached.

Intrinsic viscosity [η]
Measurements were made in tetrahydronaphthalene at 135 ° C. (ASTM 2857-70).
Quantification of diethyl ether soluble part To quantify the soluble part in diethyl ether, the polymer was extracted according to the Kumagawa procedure. In an inert atmosphere, 2 g of polymer is transferred to a cellulose cylinder filter paper and then hung with a glass barrel on top of 300 mL of diethyl ether. The ether is warmed to reflux temperature and the vapor is condensed with a bubble condenser and continuously dropped onto the polymer. In this way, the polymer is always coated with a solvent and the extraction temperature is substantially equal to the ether reflux temperature.

  Extraction is performed for 15 hours. The soluble fraction is recovered by adding methanol (600 mL) to the ether solution. After 30 minutes, the precipitated polymer is filtered and then dried in vacuo at 80 ° C. until a constant weight is reached.

Milling Procedure 40 g of polymer is placed in a Brabender 2100 having a chamber size of 55 cm 3 and exposed to mixing conditions at 90 rpm for 5 minutes at a temperature of 140 ° C. The polymer is then released and subjected to additional testing.

Example Preparation of Solid Catalyst Components A 500 ml four-necked round bottom flask purged with nitrogen was charged with 225 ml of TiCl ₄ at 0 ° C. While stirring, 6.8 g of microspherical MgCl ₂ .2.7C ₂ H ₅ OH (US Pat. No. 4,399,054 except that it was operated at 3,000 rpm instead of 10,000 rpm). Prepared as described in Example 2). The flask was heated to 40 ° C. and 4.4 mmol of diisobutyl phthalate was then added. The temperature was raised to 100 ° C. and maintained at that temperature for 2 hours, then the stirring was stopped and a solid product precipitated. The supernatant liquid was sucked up and removed.

200 ml of fresh TiCl ₄ is added and the mixture is allowed to react at 120 ° C. for 1 hour, then the supernatant is siphoned off and the resulting solid is washed 6 times with 60 ° C. anhydrous hexane (6 × 100 ml) And then dried under reduced pressure. The catalyst component contained 2.8 wt% Ti and 12.3% wt phthalate.

Example 1
In a 4 liter autoclave, purged with a nitrogen flow of 70 ° C. for 1 hour, 75 ml of anhydrous hexane containing 7 mmol of AliBu ₃ and 20 mg of the solid catalyst component prepared as described above were introduced with a nitrogen flow of 30 ° C. The autoclave was closed and then 1.3 Kg of liquid butene-1 was fed under stirring. The temperature was raised to 70 ° C. in 5 minutes, and polymerization was conducted at that temperature for 2 hours. After stopping the reaction, unreacted butene-1 was evacuated, and then the polymer was recovered and dried at 70 ° C. under reduced pressure for 6 hours. The polymerization activity was 13 Kg polymer / g catalyst. The final polybutene-1 product had the properties recorded in Table 1. 4,1-butene intervening units were not detected by ¹³ C NMR.

Example 2
The preparation method described in Example 1 was repeated except that 100 cm ³ of H ₂ was supplied to the polymerization bath. The final polybutene-1 product had the properties recorded in Table 1. 4,1-butene intervening units were not detected by ¹³ C NMR.

Example 3
The preparation method described in Example 1 was repeated except that 250 cm ³ of H ₂ was supplied to the polymerization bath. The final polybutene-1 product had the properties recorded in Table 1. 4,1-butene intervening units were not detected by ¹³ C NMR.

Example 4
The preparation method described in Example 1 was repeated except that the polymerization temperature was set to 80 ° C. The final polybutene-1 product had the properties recorded in Table 1. 4,1-butene intervening units were not detected by ¹³ C NMR.

Example 5
The preparation method described in Example 4 was repeated except that 100 cm ³ of H ₂ was supplied to the polymerization bath. The final polybutene-1 product had the properties shown in Table 1. 4,1-butene intervening units were not detected by ¹³ C NMR.

Example 6
Preparation of Butene-1 Homopolymer by Sequential Polymerization Sequential polymerization was carried out in two liquid phase stirred reactors connected in series with liquid butene-1 constituting a liquid medium. The same catalyst as described in the previous examples was used. The catalyst component (Al-alkyl / catalyst weight ratio 38) was pre-contacted at 10 ° C. and then injected into the first reactor operating at 75 ° C. without supplying hydrogen. After 170 minutes of polymerization, the contents of the first reactor were transferred to the second reactor where polymerization was continued under the same conditions. After 100 minutes, the polymerization was stopped and the final polymer was collected and characterized. Based on the polymerization activity, about 70% of the total polymer was produced in the first polymerization step and the xylene insoluble portion was 30%. The results of the characterization performed on the final copolymer are shown in Table 1.

Example 7
Preparation of butene-1 homopolymer by sequential polymerization The same setup and catalyst as described in Example 6 were used. In this example, the Al-alkyl / catalyst weight ratio was 40, and the first reactor was operated at 75 ° C. without supplying hydrogen. After 150 minutes of polymerization, the contents of the first reactor were transferred to the second reactor where texyltrimethoxysilane was used as the external donor at a Tibal / donor weight ratio of 950. The polymerization was continued for 100 minutes in the second reactor and then stopped, the final polymer was collected and characterized. Based on the polymerization activity, about 75% of the total copolymer was produced in the first polymerization step and the xylene insoluble portion was 28%. The xylene-insoluble portion of all polymers was 35%. The results of the characterization performed on the final copolymer are shown in Table 1. The Shore D value was less than 30.

Example 8
Preparation of Butene-1 / Propylene Copolymer The preparation method described in Example 1 was repeated except that 10 g of propylene was supplied after butene-1 was supplied. During the polymerization, the pressure was kept constant by feeding propylene. The final polymer whose characterization was shown in Table 1 contained 2.6% by weight of propylene (quantitative by NMR).

Example 9
Preparation of Butene-1 / Hexene Copolymer The preparation method described in Example 1 was repeated except that 125 g of hexene-1 was fed before butene-1 was fed and the polymerization temperature was 75 ° C. The final polymer, whose characterization is shown in Table 1, contained 4.3% by weight of hexene-1 (quantified by NMR). DSC analysis showed no melting peak.

Example 12
Preparation of Butene-1 / Ethylene / Propylene Terpolymer The preparation method described in Example 10 was repeated except that 3 g of ethylene and 5 g of propylene were supplied after supplying butene-1. During the polymerization, the pressure was kept constant by feeding a 2/1 g / g ethylene / propylene mixture. The final polymer whose characterization was shown in Table 1 contained 1.1 wt% ethylene and 0.9 wt% propylene. DSC analysis showed no melting peak.

Example 13
Preparation of Butene-1 / Propylene / Hexacentre Polymer The preparation method described in Example 13 was repeated except that 5 g of propylene was supplied after butene-1 was supplied. During the polymerization, the pressure was kept constant by feeding propylene.
The final polymer, whose characterization was shown in Table 1, contained 5.6% by weight of propylene (quantitative by NMR) and 4% by weight of hexene. DSC analysis showed no melting peak.

Example 14
10% of a propylene terpolymer containing 5.5 wt% ethylene, 6% bw butene-1 and MFR (230 ° C., 2.16 kg) 5.5 and having a melting point of 133 ° C. A mechanical blend containing 90% bw of -1 homopolymer was prepared. The film obtained from this composition was transparent and had a flexural modulus of 13 Mpa, an MFR of 1.2 (230 ° C., 2.16 kg) and an elongation at break of 512%.

Example 15
38 g of the polymer obtained as disclosed in Example 7 was placed in a Banbury closed mixer at a temperature of 90 ° C. together with 2 g of dicetyl peroxydicarbonate. The mixture was mixed at 60 rpm for 6 minutes to dynamically crosslink the product. 30 g of the mixture was then molded into plates (compression molding at 180 ° C. for 7 minutes) and subjected to compression set testing according to the method set described above (no autoclave curing was performed). The compression set was 39%.

Example 16
38 g of the polymer obtained as disclosed in Example 7 were added 1.6 g of triallyl cyanurate / silica blend (50/50) and 0.4 g of 1,1-di (tert.butylperoxy)- Together with 3,3,5-trimethylcyclohexane / silica blend (40/60), it was placed in a Banbury closed mixer at a temperature of 140 ° C. The mixture was mixed at 60 rpm for 6 minutes to dynamically crosslink the product. 30 g of the mixture was then formed into plates (7 minutes compression molding at 180 ° C.) and subjected to compression set testing according to the method set described above (no autoclave curing was performed). The compression set was 48%.

Claims (7)

The following characteristics:
A content of butene-1 units in the form of isotactic pentads (mmmm) of 25-55%;
An intrinsic viscosity [η] measured in tetralin at 135 ° C. of 1 to 3;
-The content of xylene insoluble part at 0 ° C is 3-60%; and
ES ₂ / ES ₁ ratio (ES ₁ is the amount of boiling diethyl ether soluble part measured with respect to the polymer itself, where the amount of solubles in boiling diethyl ether was extracted according to the Kumagawa procedure In an inert atmosphere, measured in terms of polymer, 2 g of polymer is transferred to a cellulose cylinder filter paper, then hung with 300 mm diethyl ether together with a glass shell, warmed to reflux temperature, and the vapor is bubbled ( condensed in a bubble condenser) and dropped continuously onto the polymer for 15 hours, after which the soluble fraction was recovered by adding methanol (600 mL) to the ether solution, and after 30 minutes, the precipitated polymer was filtered, then are those dried under reduced pressure at 80 ° C. until a constant weight is reached, ES _2, the milling hand The amount of boiling diethyl ether soluble part measured after crushing the polymer in turn, where the crushing procedure puts 40 g of polymer in a Brabender 2100 with a chamber size of 55 cm ³ at 90 rpm. Butene-1 homopolymer or copolymer, characterized in that it is exposed to mixing conditions for 5 minutes at a temperature of 140 ° C., after which the polymer is released and tested.   The butene-1 homopolymer or copolymer according to claim 1, wherein the content of butene-1 units in the isotactic pentad (mmmm) form is 30 to 50%. The content of boiling diethyl ether soluble portion (ES ₁₎ is 20 to 75% and is claim 1 butene-1 homopolymer or copolymer as claimed.   The butene-1 homopolymer or copolymer of claim 1 having a tensile stress at break of greater than 6 MpA and a Shore A of less than 80.   (A) 1 to 99% by weight of the butene-1 (co) polymer according to any one of claims 1 to 4; and (B) 99 to 1% by weight of another polymer component (the weight% is (A) + Based on the sum of (B)). (A) a solid component containing a Ti compound supported on MgCl ₂ and an internal electron donor compound; (B) a step of polymerizing butene-1 in the presence of a catalyst system comprising an alkylaluminum compound. Process for the preparation of the described butene-1 copolymers.   A butene-1 homopolymer or copolymer according to any of claims 1 to 4 having a Shore D of less than 40 or a polymer composition according to claim 5 in the presence of a crosslinking agent and at a temperature of from 100 to 150C. Cross-linking method.