JPS587440A - Polypropylene composition - Google Patents

Abstract

PURPOSE:A composition having improved mechanical properties, especially capable of providing high modulus of rigidity and impact resistance by combination with a filler, obtained by blending a specific polypropylene composition with a specified modified polyethylene. CONSTITUTION:A composition comprising (A) preferably 50-95wt% polypropylene, (B) 2-20wt% rubber-like random copolymer of ethylene and propylene (preferably having an intrinsic viscosity of >= 3dl/g), (C) 3-35wt% modified polyethylene having an instrinsic viscosity of 0.5 <=-<4.3dl/g obtained by grafting an unsaturated caboxylic acid(derivative) onto polyethylene, and (D) 0- 25wt% polyethylene having an intrinsic viscosity of >=1.5dl/g, having >=50wt% based on total composition amount of the component A and >=0.005wt% caboxylic acid (derivative). A block copolymer consisting of the components A and B or A, B, and C is prepared by the stepwise polymerization using a single catalyst system, and it is preferably blended with the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polypropylene compositions, and more particularly to partially modified polypropylene compositions.

Due to its excellent properties, polypropylene resin is used in a wide range of fields, including the film and injection molding fields. However, polyolefin resins have disadvantages in that they have poor adhesion to other substances, paintability, dyeability, and the like. Various proposals have been made to improve this drawback, and a well-known improvement method is to graft-react polypropylene with monomers having various unsaturated groups. The improved compatibility of these improved polypropylenes with other materials has also been applied to the production of composite films and compositions containing various fillers, resulting in improved adhesion and strength compared to unmodified polypropylene. Improvements will be made.

As a result of various studies on such improved polypropylene compositions, the present inventors have found that even greater effects can be obtained by mixing a specific modified polyethylene component with a polypropylene resin of a specific composition to create a composition. This discovery led to the present invention.

The gist of the present invention is that (A) a polypropylene component, (g) a rubbery random copolymer component of ethylene and propylene, and (C) an intrinsic viscosity of θ, jdl'l1 or more≠, J
Consisting of three components of modified polyethylene components grafted with unsaturated carboxylic acids or derivatives thereof, less than dl/y,
Or a polypropylene composition consisting of a component (A), (ε), (0) and (B) a polyethylene component having an intrinsic viscosity of 7.0 dl'9 or more, )
A polypropylene composition characterized in that the polypropylene component is present in an amount equal to or more than IO weight of the total amount of the composition.

The polypropylene composition of the present invention has superior mechanical properties compared to conventionally known modified polypropylene resins, and has the advantage of having both high rigidity and impact strength, especially when combined with a filler to form a composition. be.

The present invention will be explained in more detail below.

As the polypropylene component (hereinafter sometimes simply referred to as component (2)), a propylene homopolymer or a propylene copolymer containing a small amount of comonomer component is used. Examples of comonomer components include m-olefins such as ethylene, butene-1, and octene-7, and their content is! Less than weight% Surname 1 Shigukeko Weight%
less than Intrinsic viscosity (deca, -b~medium/measured at 131℃. The same applies below →/~3di/1
1 is particularly preferred.

Rubbery random copolymer component of ethylene and propylene (
The component (hereinafter sometimes simply referred to as component (g)) mainly consists of ethylene and propylene, but may also contain small amounts of other α-olefins and diene monomers. The ratio of ethylene units to propylene units is preferably 30 to 70 mol of the former and 70 to 30 mol of the latter. Further, it is particularly preferable that the intrinsic viscosity is J dll1 or more, and if it is too small, the impact strength, which is the object of the present invention, will not be improved.

Modified polyethylene component (hereinafter referred to simply as (c
f) Component) is polyethylene modified by grafting an unsaturated carboxylic acid or a derivative thereof (hereinafter sometimes referred to as a graft component), and has an intrinsic viscosity of o , s dV9 or higher 4
', ,? 41717 are used. If the intrinsic viscosity is too small, it will have little effect on impact strength, and if it is too large, it will be difficult to cross wires, resulting in poor practicality. ■When no ingredients are used: Fi/, j d14! When using component (2), it is preferable that the average value of the (to) component and the 0 component is /, jdI/g or more.

Examples of the unsaturated carboxylic acid include α/unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and V-ray acid.
Derivatives include acid anhydrides of these, such as maleic anhydride, and alkyl esters, such as methyl esters. Among these, maleic acid or maleic anhydride is preferred. The amount of grafting is appropriate. As base polyethylene, ethylene homopolymers or ethylene copolymers containing small comonomer components are used. Examples of comonomer components include α-olefins such as propylene and butene-1, and the content thereof in the ethylene copolymer is preferably 20 or less, preferably 10 or less by weight.

Its intrinsic viscosity is 0. J dt19 and above also j 4171
Preferably it is less than 7. Grafting can be carried out by a known method, such as a method in which the grafting reaction is carried out by melt-kneading both components in the presence or absence of a radical reaction initiator, or a method in which the grafting reaction is carried out in a state dissolved in a solvent such as xylene. I can do it.

The polyethylene component (hereinafter sometimes referred to as a single K (D) component) includes the same ethylene homopolymer or ethylene copolymer as the base polyethylene in the (CF) component, but the comonomer in the ethylene copolymer It is preferable that the content Fij is below the weight ratio.

It is preferable that the intrinsic viscosity is /, j di19 or more.

Regarding the content of each component, component (A) is 1% of the total composition.
The content should be 0% by weight or more. If it is less than 50% by weight,
Rigidity decreases□. (K: & 0 ~ ri! weight - is preferable. The content of component (B) should be at least ttix weight%, but preferably ~20% by weight. (As mentioned above, the content of component Q is as follows: Any amount is sufficient as long as the amount of the graft component in the entire composition is 0.001% by weight or more.Usually, the content of the (1) component is 3 to 1% by weight. The amount may be O. Therefore, the composition of the present invention may consist of the three components (A), (I3), and O, but it may also be a component (G) with the addition of component (2). In this case, the content is about 2 to 50% by weight.

Therefore, the melt flow index (hereinafter abbreviated as MIF) of all compositions was determined by the melt flow index (hereinafter referred to as MIF).
7) measured at 230℃) is o, i~! Ofl/10
It is preferable that it is configured so that it is a minute.

The polypropylene composition of the present invention can be produced by separately manufacturing each component, blending and kneading using a mixing device such as an extrusion kneader or a Banbury mixer, or by multi-stage polymerization.
A polymer can be produced by a so-called block copolymerization method that produces the co-component (2) or the three components (2), (2), and (2), and this can be produced by mixing the K (3) components. (A) obtained by a stepwise polymerization reaction using a catalyst system
It is particularly preferable to mix the co-components (and) or the block copolymer consisting of the three components (A), (to), and (2) with the separately produced modified polyethylene component (0) and melt-knead the mixture. The block copolymer is JP-A-Sho rt-so O
ri issue, Tokukai Shou st-! j//l, and j4-A/
It can be produced by the known method described in Ko 1j.

When the propylene composition of the present invention is combined with fillers, a composition with a better balance of rigidity and impact resistance can be obtained than the polypropylene compositions containing fillers obtained by the conventional methods. It will be done. Fillers for making such compositions include glass-based fillers such as glass fiber, glass powder, and glass flakes, natural minerals such as mica, talc, kaori, and clay, calcium carbonate, magnesium decide, and silica. , various metal salts and oxides such as alumina, organic fillers such as cellulose fiber, and wood powder, among others, glass fiber.

Better results are obtained with silicate-based fillers such as mica. For the formulation of these fillers, known techniques related to the production of filler-containing plastics are applied, such as the formulation of different types of fillers, the pretreatment of fillers with various processing agents, and the formulation of various additives including stabilizers. I can do it.

Below, the present invention t1! This will be explained in more detail with reference to Examples, but in the following, the amount of grafted unsaturated carboxylic acid or its derivative (grafting amount) is determined by the content (weight 5) in the molding material as determined by t-infrared absorption spectroscopy. measured and expressed as grafting percentage.

Also, the intrinsic viscosity of the polymer is Decalin/J! Measured at °C, the melt flow index (MF engineering) is
This is a value measured at 230°C in accordance with D-/231-j7T.

Regarding the mechanical strength of filler compounded compositions.

Then, the values of bending rigidity and engineering moa impact strength were measured.

Example 1 (1) Production of block copolymer A solid titanium trichloride catalyst complex was synthesized by precipitating a heptane solution obtained from titanium tetrachloride, dioctyl ether, and ethylaluminum monochloride at elevated temperatures.

Using this solid titanium trichloride catalyst complex and diethylaluminium monochloride, (a) propylene homopolymerization in the presence of hydrogen at a first stage polymerization temperature of 70°C; ω) second stage polymerization in the coexistence of ethylene and hydrogen at a polymerization temperature of jO°C. Ethylene-Propylene Random Copolymerization (C) A three-stage polymerization of ethylene homopolymerization was carried out in the coexistence of hydrogen at a third-stage polymerization temperature of 70°C. The first stage and the λ stage were polymerization in liquid propylene, and the third stage was gas phase polymerization. Sampling of the polymer and gas replacement were performed at an intermediate stage of each stage.

From the analysis of polymerization conditions and sample analysis, the obtained block copolymer was found to be M? , -m-' 111/// (2) Production of modified polyethylene Obtained by polymerizing ethylene containing a small amount of butene-/i with a catalyst containing components of magnesium and titanium, [da) = J
, j dl/El, density θ, 100 parts by weight of polyethylene of g/CC, 47904 parts by weight of anhydrous male, e1
a' and stachybutylperoxyadiisopropylbenzene o, oaz parts by weight were mixed at 210°C using an extruder equipped with a full-flight screw having a diameter of 3ofi and a length/diameter ratio of Lμ = 23. Melt-kneaded maleic anhydride raft amount 0. /I weight [16 (wl = 3
−! A di/Fl modified polyethylene was obtained.

(3) Manufacture of polypropylene composition To 100 parts by weight of the block copolymer produced in (1), add 2j parts by weight of the modified polyethylene of (2) (in the case of /-mu) and 11 parts by weight (/-
In the case of B) they were mixed and kneaded at 23θ°C.

(4) Manufacture of mica-filled composition Mica (Sugilite 3isS Sugilite is a trademark of Clan ■) z-
1 part by weight of pO was added and kneaded for about 3 minutes using a Bamba'Jz mixer. The kneading temperature was /10 to 19 (7'C).

(5) Molding of mica-filled composition and measurement of mechanical strength The mica-filled composition of (4) was molded at 230°C in a small injection molding machine.
A sample piece was cut out from a flat plate of injection molded ROM, XIom x/-3KM thick, and the bending elastic modulus and bending yield strength were determined according to EITMD-7 and ASTM DJJJ.
The impact strength was measured according to K. Each physical property value is shown in Table/GC.

Example λ Polyethylene made with Ziegler type catalyst (Tubatic Jvoaoa Tubatic is a trade name of Mitsubishi Kasei, (v)
A modified polyethylene was produced in the same manner as in Example t-(2) using a polyethylene resin having a density of 00 and A7 #/ca). The amount of grafted maleic anhydride was 0.1% by weight. [Calyx] A mica-filled composition was prepared using the same procedure except that 1.2 dVFl polyethylene was used, and its physical properties were measured.

The results are shown in Table 1.

Example 3 (1) Production of block copolymer A copolymer was produced in the method of Example 1 by omitting the third step of ethylene homopolymerization.

The resulting nine-but-four-block copolymer had a VIP coating of 3. To parts by weight of the above block copolymer were mixed with to parts by weight of the modified polyolefin of Example-/, and the same mica was mixed in the ratio as in Example-7 to produce a mica-filled composition. In the same manner as in Example-/, molding was performed and physical properties were measured.

The results are shown in Table-7.

Comparative Example-Example 1-(1) block copolymer Example-/-(
Example 9: The polyethylene of 2) was mixed without any modification, and the same evaluation as in Example 1 was performed. The results are shown in Table 7.

Comparative Example - The block copolymer of Example 1 and the base polyethylene for producing modified polyethylene were mixed in advance at a weight ratio of 100:21, and 0.3 parts by weight of maleic anhydride was added to 10 parts by weight of this mixture. When 0.02 parts by weight of α, e1' bistarchybutylperoxyP diisopropylbenzene was added and the graft reaction was carried out at 230°C, 0.
A modified polymer grafted with 13% by weight of maleic anhydride was obtained. The same evaluation as in Example 7 was performed using this modified polymer. The results are shown in Table-7.

Example-μ [η) = 0. polyethylene of de/9 (Tsubachik'JT200.M engineering=ko09/10 minutes, ρ=0.
Modified polyethylene was produced by carrying out the same operation as in Example -/-(2) using (2≦79/CQ'). [η]=O
In step 19, modified polyethylene grafted with 0.2% by weight of maleic anhydride was obtained. [ri] was O9ri19. The same evaluation as in Example No. was performed using this modified polyethylene. The results are shown in Table-/&C.

Comparative Example 3 Evaluation was carried out in exactly the same manner as in Example 1 except that the values used for the block copolymer and modified polyethylene were changed. The results are shown in Table-7.

Comparative Example - Parts by weight of the modified polyethylene λj of Example -/-(2) were mixed with parts by weight of propylene homopolymer of μ(y) = /, A dl/g, and the same evaluation as in Example 7 was obtained. I did it. The results are shown in Table-7.

Procedural amendment (LI1) 2. Name of launch Polyp fog pyrene composition 3 Person making the amendment: Applicant (jya) Mitsubishi Chemical Industries, Ltd. 4 agents〒100 2-5-2 Marunouchi, Chiyoda-ku, Tokyo (1 other person) 6. Contents of amendment +11% The range of permission request is corrected as shown in the attached sheet.

% by weight.”

(31 Specification, page 7, line D, Krj~λj heavy weight%'' is corrected to read ``3~3!wt%'').

(4 specifications @pg/-page 2, line 2 K "Density θ, RI/J da l/匡j" is corrected to "Density Q, RI 1/a:, butene-/unit content 4 mo1%".

(5) Add the following example after Table 7 on page it of the specification.

[Example! , 6 Repeat the same operation as in Example- except that the amount of modified Borie≠syn used was changed, and! A squid filling composition was prepared and its physical properties were measured.

Table 1 shows the amounts of each component used and the physical properties of the resulting squid filling composition.

Table 1) CML; maleic anhydride” and above Appendix Claims (11 (A) polypropylene g content, (B) rubbery random copolymer component of ethylene and glopylene, and (0)
iK limiting viscosity f) Z O6! (fj / f more than 4'
, less than 3 dl/t, consisting of three components of a modified polyethylene component grafted with an unsaturated carboxylic acid or its rust conductor, or each component (M), (B), (C) and K (D) A polypropylene composition comprising a polyethylene component having an intrinsic viscosity of i, rd17'y or higher, wherein (A) a polypropylene component is present in an amount of % by weight of the composition.
Polypropylene composition (2) obtained by a stepwise polymerization reaction using a single catalyst system, obtained by dividing (A) and (A) To)
Claim 1, characterized in that it is a composition obtained by mixing a block copolymer consisting of the three components (C) and (C), and a modified polyethylene component (C), which is separately produced.
Range of the composition described in paragraph 7. The composition described in paragraph 1.

Claims (2)

[Claims] (1) (A) polypropylene component, (to) rubbery random copolymer component of ethylene and propylene, and (C
) The intrinsic viscosity is o, z dl/1! That's it, Jd&'l
consisting of three modified polyethylene components grafted with unsaturated carboxylic acids or derivatives thereof, or (
, A), (b), and 0, as well as ■ having an intrinsic viscosity of 1.
A polypropylene composition comprising a polypropylene component to which a polyethylene component of s dl/E1 or more is added, characterized in that (A) the polypropylene component is present in an amount of j0 weight or more of the total amount of the composition. (2) Two components of (A) and ■ or u (A), ■, and (g) obtained by stepwise polymerization reaction using a single catalyst system
The composition according to claim 1, characterized in that the composition is obtained by completely mixing a block copolymer consisting of three components, and a separately produced modified polyethylene component.