JPH04218514A - Syndiotactic propylene copolymer, its production and resin composition containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer excellent in transparency, rigidity and impact resistance by copolymerizing propylene with an alkenylsilane in the presence of a catalyst composed of a transition metallic compound having specific ligands and an aluminoxane and then converting silyl groups into hydrox yl groups. CONSTITUTION:The objective copolymer is obtained by copolymerizing propylene with an alkenylsilane expressed by formula I (R<1> is H, halogen or 1-20C saturated hydrocarbon; n is an integer of 0-200) using a catalyst composed of a transition metal compound having asymmetric two ligands and an aluminoxane, then heating the produced copolymer in the presence of a trialkylamine oxide and KF.HF and converting groups SiR<1>3 into hydroxyl groups. The aforementioned copolymer contains recurring units expressed by formula II and 0.01-40mol% recurring units expressed by formula III and has a syndiotactic configuration in which the peak strength at 20.2ppm is >=0.3 based on that of the whole methyl groups assigned to the methyl group in propylene unit in an absorption spectrum according to <13>C-NMR.

Description

Description: [0001] The present invention relates to a propylene copolymer having a syndiotactic structure, a method for producing the same, and a resin composition containing the same. Specifically, -OH in the propylene unit and side chain has high syndiotacticity.
The present invention relates to a copolymer containing a group-containing olefin unit, a method for producing the same, and a resin composition containing the same. [Prior Art] Polyolefins are inexpensive polymers with relatively excellent physical properties, but because they do not contain polar groups, they have poor gas barrier properties and poor adhesion with polymers containing polar groups. There are problems such as the product being defective. A possible solution to this problem is to mix polymers containing polar groups, but polymers containing polar groups are usually difficult to mix with polyolefins, and the problem is that the mixture loses the original physical properties of polyolefins. . The existence of syndiotactic polypropylene has been known for a long time, but polypropylene obtained by the conventional low-temperature polymerization method using a vanadium compound, an ether, and an organoaluminum catalyst has poor syndiotacticity. It was hard to say that it exhibited the characteristics of geeky polypropylene. Further, with ordinary olefin polymerization catalysts, olefins containing polar groups such as -OH are hardly polymerized, and stereoregular polyolefins containing polar groups have not been known. On the other hand, J. A. Ewen et al. achieved a syndiotactic pentad fraction of 0.7 using a catalyst consisting of a transition metal compound with an asymmetric ligand and an aluminoxane.
(J. Am. Chem.
oc. , 1988, 110, 6255-6256). Also, T. C. Chung announced that a copolymer of isotactic propylene and alkenyl alcohol could be obtained by oxidative decomposition of an isotactic propylene copolymer of alkenylborane and propylene (Macromolecules, 1988, 2).
1,865). [0005] A copolymer having a substantially syndiotactic structure and containing an -OH group in the side chain has not been known so far, and such a polymer is expected to have unprecedented physical properties. Compositions containing such copolymers are expected to have unprecedented physical properties. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel propylene copolymer having a substantially syndiotactic structure containing -OH groups in its side chains. Another object of the present invention is to provide a method for producing the above propylene copolymer. A further object of the present invention is to provide an olefin resin composition containing the above propylene copolymer and having good physical properties. [0009] The syndiotactic propylene copolymer of the present invention comprises repeating units of the formula I [Image Omitted] and 0.01 to 40 mol% of the formula II 00
11] [In the formula, n is an integer of 0 or 1 or more], and among the peaks attributed to the methyl group of the propylene unit in the 13C-NMR absorption spectrum, approximately The intensity of the peak observed at 20.2 ppm is 0 of the peak intensity of all methyl groups belonging to the propylene unit.
．． 3 or more. The method for producing the syndiotactic propylene copolymer described above uses a catalyst consisting of a transition metal compound having two asymmetrical ligands and aluminoxane, and propylene and a compound of the formula III H2 C=CH-(CH2)n -SiR13
(III) (wherein, three R1's are independently hydrogen, halogen atom or carbon number 1-
20 saturated hydrocarbon groups, and n is an integer from 0-20. ) and then heating the obtained copolymer in the presence of trialkylamine oxide and KF/HF. Another method uses the catalysts described above to convert propylene and the formula IV H2 C=CH-(CH2)n -BR22
(IV) (wherein two R
2 is independently a hydrocarbon group having 1 to 12 carbon atoms, and n
is an integer of 0 or 1 or more. ) is copolymerized, and then the resulting copolymer is oxidatively decomposed. Further, the polyolefin resin composition of the present invention comprises the above propylene copolymer and another polyolefin. The method for producing a propylene copolymer having a syndiotactic structure according to the present invention will be described below. The transition metal compound having an asymmetrical ligand, which is one component of the catalyst used in the production of the copolymer of the present invention, includes those described in J. A. An example is the compound described in the literature of Ewen et al., but when a propylene homopolymer is produced even if it has a different structure, the syndiotactic pentad fraction of the resulting polymer (A. Zambelli et al., Macromolecules, vol.6,687
(1973), same vol. 8,925 (1970)
Any catalyst system that provides a polymer with a relatively high tacticity of about 0.7 or higher can be used. For example, the formula V [Image Omitted] (where A and B are different cyclic unsaturated hydrocarbon residues, R3 is a hydrocarbon residue having 1 to 20 carbon atoms connecting A and B, or silicon) The group X is a halogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and M is a metal atom selected from titanium, zirconium, or hafnium. In formula V, A and B each have 5 carbon atoms.
~30 monocyclic or polycyclic unsaturated hydrocarbon residues can be exemplified, specifically cyclopentadienyl groups or those in which part or all of the hydrogens are substituted with an alkyl group having 1 to 10 carbon atoms ( (Here, the alkyl group may have a structure in which its terminal end is bonded to the cyclopentadiene ring again.)
, a polycyclic unsaturated hydrocarbon residue such as an indenyl group or a fluorenyl group, or some or all of its hydrogen atoms have 1 carbon number
Examples include those substituted with ~10 alkyl groups. R3 is preferably a dialkylmethylene group, a dialkylsilylene group, or a dialkylgerylene group, for example, R4
Examples include groups represented by 2C<, R42Si<, R42Ge< (in the formula, R4 is hydrogen or an alkyl residue having 1 to 20 carbon atoms and may be the same or different), and -CR42-CR42 An example is an ethylidene group represented by - (in the formula, R4 is the same as above). X
Examples include fluorine, chlorine, bromine, iodine, alkyl groups such as methyl, ethyl, propyl, and butyl, and aromatic compounds such as cyclopentadienyl groups, with chlorine and methyl groups being particularly preferred. Among the above-mentioned transition metal compounds having an asymmetric ligand, the above-mentioned J. A. Isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride or isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride described in the literature of Ewen et al., or some of these hydrogens have been substituted with alkyl group residues Compounds are preferred. By using a highly purified transition metal compound as described above, a copolymer with higher stereoregularity can be obtained. Aluminoxane, which is the other component of the catalyst, has the formula VI [Image Omitted] and the formula VII [Image Omitted] (where R5 is a hydrocarbon residue having 1 to 3 carbon atoms). can be,
m is an integer from 1 to 50. ) is preferable, especially when R5 is a methyl group and m is 5 in the above formula.
The above are preferred. The ratio of aluminoxane used to the transition metal compound having an asymmetrical ligand is preferably 1 to 1,000,000 times by mole, particularly 10 to 5,000 times by mole. The alkenylsilane to be copolymerized with propylene is represented by the above formula III, and is vinylsilane, allylsilane, butenylsilane, pentenylsilane, hexenylsilane, or one of the H's of these silanes.
Examples include compounds in which ~3 atoms are substituted with halogen atoms or especially with saturated hydrocarbon groups having 7 to 20 carbon atoms. Further, alkenylborane compounds are those represented by the above formula IV, and compounds in which R2 in formula IV is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. 2
B-7-octenyl-9-borabicyclo[
3,3,1] nonane is exemplified. The method of copolymerizing propylene and the above-mentioned alkenylsilane or alkenylborane compound is not particularly limited, and may include a solvent polymerization method using an inert medium, a bulk polymerization method in which polymerization is carried out in the substantial absence of a solvent, or Gas phase method is adopted. [0028] The polymerization temperature is -100° to 200°C, especially -
The temperature is preferably 100° to 100°C, and the polymerization pressure is normal pressure to 10°C.
0kg/cm2 (gauge pressure), especially normal pressure to 50kg/cm2
cm2 (gauge pressure) is preferred. The amount of the alkenylsilane or alkenylborane compound is such that the repeating unit of the formula II is 0.01 to 40 mol%, preferably 0.05 to 40 mol%, based on the copolymer.
It is controlled to be 20 mol%, particularly 0.1 to 20 mol%. The resulting copolymer of propylene and alkenylsilane is then treated with trialkylamine oxide and K.
-SiR13 groups are converted to -OH groups by heat treatment in the presence of F.HF. This detailed condition is, for example, T
etrahedron Letter, 27, 75
(1986) (H. Sakurai et al.) can be employed. The trialkylamine oxide can be used in an alkyl group having about 1 to 6 carbon atoms, and the amount used is 0.01 to 100 carbon atoms per alkenylsilane unit.
0 mol times, preferably 0.1 to 100 mol times, KF・H
The amount of F used is from 0.01 to alkenylsilane unit.
The amount is 1000 times by mole, preferably 0.1 to 100 times by mole. It is preferable to use a solvent during this reaction,
Hydrocarbon compounds having 5 to 25 carbon atoms are preferably used. The reaction temperature is usually room temperature to 300°C, particularly preferably 5°C.
It is 0° to 200°C. The obtained copolymer of propylene and alkenylborane compound is then oxidatively decomposed. There are no particular restrictions on the conditions for oxidative decomposition, and the conditions employed when decomposing alkyl boron to synthesize alcohol can be used as they are. -BR22 group can be easily converted to -O by treatment with an oxidizing agent such as hydrogen peroxide under alkaline conditions.
It can be an H group. The copolymer thus obtained has 13
Approximately 20.2 ppm of the peaks attributed to the methyl group of propylene units in the C-NMR absorption spectrum
The intensity of the peak observed in is 0.3 or more of the peak intensity of all methyl groups belonging to the propylene unit. If this ratio is less than 0.3, problems such as the surface of molded products made from this copolymer will become sticky. [0033] If the content of alkenylsilane units or alkenylborane units is less than 0.01 mol%, -OH groups are present in the polymer even if all alkenylsilane units or alkenylborane units react to become -OH groups. If the amount exceeds 40 mol%, the physical properties of syndiotactic propylene will not be exhibited. Among the peaks attributed to the methyl groups of propylene units in the 13C-NMR absorption spectrum of the above polymer, the peak intensity of the peak observed at about 20.2 ppm is the peak of all methyl groups attributed to the propylene units. In order to further increase the ratio to strength, it is effective to conduct polymerization at a low temperature of 100°C or less using a catalyst containing a highly purified (90% or more) transition metal compound as described above. It is also effective to clean with a hydrocarbon solvent or the like. The above copolymer has a molecular weight of 0.05 or more as an intrinsic viscosity measured in a tetralin solution at 135°C;
Usually, it is preferably about 0.1 to 10 for its use. [0036] In addition, 1,2,
There is no particular restriction on the ratio of the weight average molecular weight measured in a 4-trichlorobenzene solution to the number average molecular weight, and a ratio of about 1.5 to 20 can be produced depending on the polymerization conditions, and the preferable range is selected depending on the application. It is about 2 to 10. [0037] The hydrocarbon solvent has 3 to 20 carbon atoms.
In addition to saturated hydrocarbon compounds such as propylene or propane, butane, pentane, hexane, heptane, octane, nonane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, or their hydrogen parts. Alternatively, it is also possible to use one in which all of the components are replaced with fluorine, chlorine, bromine, or iodine. Other solvents that can dissolve or disperse low molecular weight atactic components, such as alcohols having 1 to 20 carbon atoms, ethers and esters having 2 to 20 carbon atoms, can be used. There are no particular restrictions on the cleaning method, and it is usually carried out at a temperature of 0° to 100°C. The copolymer of the present invention is mixed with a polyolefin and used as a resin composition in order to improve its physical properties. As the polyolefin used in the resin composition of the present invention, a propylene homopolymer or a propylene copolymer is preferably used. Polypropylene includes commercially available isotactic polypropylene (including not only propylene homopolymers but also random or block copolymers with ethylene or α-olefins having 4 to 12 carbon atoms). Polypropylene having a syndiotactic structure obtained by copolymerizing propylene alone, ethylene, or an α-olefin having 4 to 12 carbon atoms with the above catalyst can also be used. There is no particular restriction on the molecular weight of the polyolefin to be mixed with the copolymer of the present invention, and polyolefins having a melt flow index measured at 230° C. of about 0.1 to 100 can be used. The mixing ratio of the copolymer of the present invention and the polyolefin is generally such that the content of alkenyl alcohol units in the resin composition is about 0.01 to 10% by weight, and the copolymer is 100-0.1wt% of
It is particularly preferable to adjust the content to 50 to 1 wt%. There are no particular restrictions on the mixing method, and dry mixing using a conventional Henschel mixer followed by melt granulation is sufficient. It is of course possible to add various known stabilizers, nucleating agents, etc. to the resin composition of the present invention. [Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Example 1 10 mg of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained by converting isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method into a lithium salt and purifying it by reacting it with zirconium tetrachloride. 1.36 g of methylaluminoxane with a polymerization degree of 16 manufactured by Toso Akzo Co., Ltd. was added to 100 ml of toluene.
The mixture was charged into a 300 ml autoclave with 20 ml of trimethylallylsilane and 60 g of propylene, and polymerized at 30°C for 2 hours. After the polymerization was completed, unreacted monomers were purged, and the powder obtained by filtration was washed four times with 1 liter of methanol and dried under reduced pressure at 80°C to obtain 26 g of polymer. According to elemental analysis, it contained 8.5 wt% trimethylallylsilane. The infrared absorption spectrum of this polymer is shown in FIG. Disperse 5 g of this polymer in 40 ml of toluene, add 40 ml of water, and 2 g of trimethylamine oxide.
, KF·HF2.5g were added and reacted at 100°C for 10 hours. After the reaction was completed, the toluene layer was separated, cooled, and filtered to obtain a polymer. According to silicon analysis, the polymer thus obtained contained 4.5w of unreacted allyltrimethylsilane units.
According to the infrared absorption spectrum in Figure 1, 3 t% remains.
-OH groups (approximately 2.
1 wt%) was observed, and when analyzed by 13C-NMR, the peak intensity observed at about 20.2 ppm was 0.69 of the peak intensity attributable to all methyl groups of propylene. The intrinsic viscosity (hereinafter referred to as η) measured with a tetralin solution at 135°C is 0.47, and 1
The ratio of the weight average molecular weight to the number average molecular weight measured in a 1,2,4-trichlorobenzene solution at 35°C (hereinafter referred to as MW/M
(denoted as N) was 2.3. Example 2 24g of copolymer was prepared in the same manner as in Example 1 except that trimethylvinylsilane was used instead of allyltrimethylsilane.
I got it. This copolymer, which contained 6.5 wt% of trimethylvinylsilane, was treated in the same manner as in Example 1 to contain 4.1 wt% of trimethylvinylsilane units, and -OH
A copolymer containing the group (approximately 1.1 wt%) was obtained. In this copolymer, η is 0.64 and MW/MN is 2.1
According to 13C-NMR, the peak intensity observed at 20.2 ppm was 0.72 of the peak intensity attributable to all methyl groups of propylene. Example 3 In an autoclave with an internal volume of 1 liter, 15 mg of isopropylene (cyclopentadienyl-1-fluorenyl)zirconium dichloride obtained in Example 1 and 2 g of methylaluminoxane were dissolved in 500 ml of toluene to prepare 7-octenyl-9-borabicyclo. [3,3,1]nonane 10g
, charged with 10g of propylene and heated at 30°C for 4 hours.
Polymerized for hours. After polymerization, add isopropyl alcohol 2
00 ml was added to precipitate 12 g of polymer. According to elemental analysis, this polymer is B-7-octenyl-9
- Contained 25 wt% of borabicyclo[3,3,1]nonane. Disperse 5 g of this polymer in 200 ml of tetrahydrofuran, and add 5 ml of 6N sodium hydroxide solution.
After cooling to 5℃, add 5℃ of 31% hydrogen peroxide solution.
．． 4 ml was added, the temperature was raised, and the mixture was stirred at 50°C for 4 hours. After the reaction was completed, petroleum ether was added to precipitate 2.5 g of polymer. The obtained polymer is B-7-octenyl-
Contains 9-borabicyclo[3,3,1]nonane, -O
It contained H groups (approximately 5.7 mol%). The infrared absorption spectrum of this polymer is shown in FIG. 3, and the 13C-NMR spectrum is shown in FIG. According to 13C-NMR, about 20.2 pp
The peak intensity observed for m was 0.68 of the peak intensity attributable to all methyl groups of propylene. 135
η measured in a tetralin solution at °C is 0.45 and 13
MW/MN measured in a 1,2,4-trichlorobenzene solution at 5°C was 2.5. Example 4 0.2 g of isopropylene (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained in Example 1
and 30g of methylaluminoxane in 80l of toluene
The mixture was charged into an autoclave having an internal volume of 200 liters, and propylene was polymerized at a polymerization pressure of 3 kg/cm2-G at 20°C for 2 hours. Methanol and methyl acetoacetate were added to the resulting polymerization mixture, treated at 30°C, washed with an aqueous hydrochloric acid solution, and then filtered to obtain 5.6 kg of syndiotactic polypropylene. This polypropylene is 13
According to C-NMR, the syndiotactic pentad fraction is 0.935, η is 1.45, and MW/MN is 2.
It was 2. To 100 parts by weight of this polypropylene, 5 parts by weight of the copolymer obtained in Example 3 and 0.1 parts by weight of a phenolic stabilizer were added.
parts by weight were added, granulated using an extruder, and then melt-pressed at 200°C to form a 1 mm sheet. The following physical properties were measured for this sheet. Bending rigidity: kg/cm2 AS
TM D-747 (23℃) Tensile yield strength: kg/cm
2 ASTM D-638 (23℃)
Elongation at break: % AS
TM D-638 (23℃) Izod (notched) Impact strength: kg・cm/cm ASTM D-638 (2
3℃, -10℃) Haze: %
ASTM D1003 result is bending stiffness 5100kg/
cm2, tensile yield strength 220 kg/cm2, elongation at break 540%, Izod impact strength 13.8, 3.5 (
23°C and -10°C, respectively), and the haze was 29%. [0048] Acrylic paint Uniloc (manufactured by Rock Paint Co., Ltd., trade name) was applied to this sheet with a brush, and the sheet was baked and dried in an air vent at 60°C for 30 minutes. About this test piece JIS K-5400
When the adhesion strength of the coating film was measured by the method (cross-cut cellophane tape test method), the number of remaining coating films in the grid pattern was 90, which was good. On the other hand, polypropylene alone containing no copolymer had a value of 0. Example 5 From the copolymer obtained in Example 3, the thickness was 0.5 m.
A press sheet of m was manufactured and its oxygen gas permeability was measured and found to be 100 ml/m2.atm.24 h. On the other hand, for comparison, the oxygen gas permeability of the syndiotactic polypropylene obtained in Example 4 was measured in the same manner.
m2・atm・24h. As is clear from the above results, molded articles made from the copolymer of the present invention have good gas barrier properties. Effects of the Invention The copolymer of the present invention has transparency and impact resistance, which are the characteristics of syndiotactic polypropylene, and has improved adhesion, paintability and It has properties such as gas barrier properties. Therefore, it is an extremely useful copolymer that has excellent transparency, rigidity and impact resistance, and has various functions. [0052] Furthermore, the resin composition comprising this copolymer and polyolefin can provide molded articles with good and well-balanced physical properties.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of syndiotactic polypropylene having -OH groups obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the copolymer of propylene and allyltrimethylsilane obtained in Example 1.

FIG. 3 is an infrared absorption spectrum of syndiotactic polypropylene having -OH groups obtained in Example 3.

FIG. 4 is a 13C-NMR absorption spectrum of syndiotactic polypropylene having -OH groups obtained in Example 3.

Claims (4)

[Claims] Claim 1: Repeating units of formula I [Chemical 1] and 0.01 to 40 mol% of formula II [Chemical 2]
] (where n is an integer of 0 or 1 or more), and observed at about 20.2 ppm of the peaks attributed to the methyl group of the propylene unit in the absorption spectrum by 13C-NMR. The intensity of the peak is 0 of the peak intensity of all methyl groups attributed to propylene units.
．． A propylene copolymer having a substantially syndiotactic structure of 3 or more. 2. Propylene and formula III H2 C=CH-(CH2)n -SiR13 using a catalyst consisting of a transition metal compound having two asymmetrical ligands and aluminoxane.
(III) (wherein, three R1's are independently hydrogen, halogen atom or carbon number 1-
20 saturated hydrocarbon groups, and n is an integer from 0-20. ) and the resulting copolymer was heated in the presence of trialkylamine oxide and KF/HF to convert -SiR13 to -OH.
A method for producing a propylene copolymer according to claim 1, which comprises converting the propylene copolymer into a propylene copolymer. 3. Propylene and the formula IV H2 C=CH-(CH2)n -BR22 using a catalyst consisting of a transition metal compound having two asymmetrical ligands and aluminoxane.
(IV) (wherein two R
2 is independently a hydrocarbon group having 1 to 12 carbon atoms, and n
is an integer of 0 or 1 or more. 2. The method for producing a propylene copolymer according to claim 1, which comprises copolymerizing an alkenylborane compound represented by the following: and then oxidatively decomposing -BR22 of the obtained copolymer into -OH groups. 4. A resin composition comprising the propylene copolymer according to claim 1 and a polyolefin, the content of the propylene copolymer being 0.1-100% by weight.