JPH06287367A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having good compatibility among the respective components and being excellent in a balance among mechanical properties such as impact strength and tensile strength. CONSTITUTION:The composition comprises polypropylene (A), polyphenylene ether (B) and 0.1-50 pts.wt., per 100 pts.wt. total weight of components A and B, block copolymer obtained by reacting polypropylene (i) prepared by introducing a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group and a sulfonic group into a terminal olefinic unsaturation with polyphenylene ether (ii) terminated with a functional group reactive with the functional group of component (i).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, mechanical strength and dimensional accuracy, which are excellent features of polyphenylene ether (hereinafter referred to as "PPE"), and moldability and organic solvent resistance, which are excellent features of polypropylene. TECHNICAL FIELD The present invention relates to a high-performance thermoplastic resin composition having both properties. The present thermoplastic resin composition is an engineering plastic useful as an industrial material for automobile parts such as ignition coils, gears, ignition manifolds, switch sealing materials, electrical parts, mechanical parts and the like.

[0002]

2. Description of the Related Art PPE has excellent heat resistance, dimensional stability,
It is known as an engineering plastic that has non-hygroscopicity and electrical properties, but its melt flowability is poor,
Molding processing such as injection molding or extrusion molding is difficult, and the molded product has the drawbacks of poor solvent resistance and impact resistance.

On the other hand, polypropylene is widely used in the production of molded articles such as bolts, sheets and plates because it has excellent moldability, resistance to organic solvents, low specific gravity and is inexpensive. However, the heat resistance is not as good as that of engineering plastics, which hinders the use of engineering plastics in the field of application. If a resin composition having both the heat resistance and toughness of PPE and the good organic solvent resistance of polypropylene can be obtained, and the drawbacks of both are complemented, the field of application as engineering plastic will be expanded.

Therefore, for the purpose of improving the molding processability and solvent resistance of PPE, Japanese Patent Publication No. 17504/1990 discloses that
A composition using a graft copolymer having polypropylene and PPE as components as a compatibilizer has been proposed.

However, this graft copolymer is
When multiple maleic anhydrides are added to one molecule of polypropylene and the amount of addition between each molecule is not uniform, when reacted with PPE having an epoxy group at the end of the molecular chain,
The gel is considered to be due to the crosslinking reaction, and the yield of the graft copolymer cannot be said to be sufficiently high.

[0006] Although the above composition has a temporary effect of improving the compatibility, the mechanical strength such as Izod impact strength and tensile elongation has not reached a practically satisfactory level.

[0007]

Therefore, if a resin having both the good properties of PPE and polypropylene and complementing the unfavorable properties can be obtained, the field of application will be broadened as an engineering plastic, and its industrial significance will be very great. . In order to provide a molding material that complements the drawbacks while maintaining the advantages of both resins, the affinity of the two-phase structural interface of both components, which are essentially poor in compatibilizer, is increased, and the adhesiveness is improved. An excellent affinity improving technique that suppresses delamination, which is likely to occur when subjected to shear stress during molding such as injection molding, is desired in the form of a uniform and fine mixed form of these two phases.

The present invention solves the above problems and provides a PPE
Another object of the present invention is to provide a thermoplastic resin composition composed of polypropylene and a specific block copolymer, which has improved affinity and is excellent in rigidity and impact strength, and which is in a state of being uniformly finely dispersed and mixed.

[0009]

The present invention is a thermoplastic resin composition comprising the following components (A), (B) and (C). (A) Polypropylene (B) PPE (C) (i) A functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group and a sulfonic acid group is added to the end of the molecular chain. Polypropylene introduced into the olefinic unsaturated bond, (i
i) A block copolymer obtained by reacting a polyphenylene ether having a functional group that reacts with the functional group of component (i) at the molecular chain end is added to 100 parts by weight of the total amount of components (A) and (B). 0.1 to 50 parts by weight

In particular, the above-mentioned heat wherein the raw material component (ii) of the component (C) is a PPE having a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group and an alkoxysilyl group. It is a plastic resin composition. Hereinafter, the present invention will be described in detail.

<Polypropylene (A)> The polypropylene of the component (A) used in the present invention has a crystallinity of 10% or more at room temperature by the X-ray diffraction method and a melting point of 120 by the DSC method from the viewpoint of heat resistance and strength. It is a crystalline polypropylene having a temperature of not less than 0 ° C. and is a propylene homopolymer or a block or random copolymer of propylene and an α-olefin other than propylene (excluding chain non-conjugated dienes).

Specific examples of α-olefins other than propylene constituting the propylene copolymer include ethylene and 1
-Butene, 1-hexene, 3-methyl-1-butene, 3
-Methyl-1-pentene, 4-methyl-1-pentene,
3,3-dimethyl-1-butene, 4,4-dimethyl-1
-Pentene, 3-methyl-1-hexene, 4-methyl-
1-hexene, 4,4-dimethyl-1-hexene, 5-
Methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.1] -heptane, divinylbenzene, isopropenyl. Styrene, 4-
Methyl-1,4-hexadiene, 5-methyl-1,4-
Hexadiene, 7-methyl-1,6-octadiene,
Examples include 1,9-decadiene and 1,13-tetradecadiene.

Of these, preferred are ethylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1. -Hexene, 4-methyl-1,
4-hexadiene, 5-methyl-1,4-hexadiene, divinylbenzene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like can be mentioned, and particularly ethylene, 1-butene, 3-methyl. -1-butene or 4-methyl-1-pentene, divinylbenzene, 7-
Methyl-1,6-octadiene or 1,9-decadiene is preferred. These α-olefins may be one kind,
Further, it is acceptable to use two or more kinds. Particularly, when the α-olefin is 1-hexene, it is preferably used in combination with at least one of ethylene, 1-butene, 4-methyl-1-pentene and 3-methyl-1-butene. When two or more α-olefins are used, the α-olefins may be randomly distributed in the propylene copolymer resin, or may be distributed in blocks.

<< PPE (B) >> The PPE of the component (B) used in the present invention has the general formula (I)

[0015]

[Chemical 1]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents a hydrogen atom. , A halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and m represents a number of 10 or more). It is a polymer or a copolymer. Preferable examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl and n-.
Butyl, n-amyl, isoamyl, 2-methylbutyl,
It is n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

Suitable PPE homopolymers are those composed of, for example, 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patents and literature. Also suitable are PPE containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength.

The molecular weight of PPE is such that the intrinsic viscosity at 30 ° C. usually measured in chloroform is about 0.2 to 0.8 dl / g. PPE is usually produced by oxidative coupling of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, or cobalt, usually in combination with various other substances, and the like.

<< Block Copolymer (C) >><Polypropylene (i) Having Functional Group Introduced into Olefinic Unsaturated Bond at End of Molecular Chain> (1) Polypropylene Component Having Olefinic Unsaturated Bond at End of Molecular Chain ( The polypropylene used as the raw material for C) has an olefinic unsaturated bond at the molecular chain terminal on one side of the polymer, and the terminal on one side is substantially entirely vinylidene bonded. The molecular weight of this polypropylene is arbitrary, but in general, the number average molecular weight measured by gel permeation chromatography is 1,000 to 1,000.
50,000 is preferable, and more preferably 2,000 to 5
0,000, particularly preferably 5,000 to 200,0
00.

Such polypropylene can be produced by bringing propylene into contact with a catalyst comprising a specific component (a) and a specific component (b) to polymerize it, as described later.

The polypropylene used in the present invention preferably has a triad [mm] fraction or [rr] fraction of 0.5 or more, more preferably 0.6 or more, as measured by ¹³ C-NMR. Particularly preferably, it is 0.75 or more.

Here, the [mm] fraction of the triad, [r
r] fraction is a “triad”, which is a monomer unit in polypropylene and is a minimum unit of a three-dimensional structure, that is, “3”.
[Mm] (isotactic), [mr] (heterotactic) and [rr] (syndiotactic) in the total number x of three possible stereoisomeric structures. ] The ratio of the number y of triads having a structure (y / x) and the ratio of the number z of triads having a [rr] structure (z / x).

The measurement of ¹³ C-NMR was carried out by JEOL. Using FX-200 (trade name), measurement temperature 130 ° C., measurement frequency 50.1 MHz, spectrum width 8
000Hz, pulse repetition time 2.0 seconds, pulse width 7μ
Second, the number of times of integration is 10,000 to 50,000. Moreover, the analysis of the spectrum is performed by A. Zambelli.
Macromolecules 21 617 (1988) and Tetsuro Asakura Proceedings of the Polymer Society of Japan 36 (8) 2408 (1987).

The above-mentioned polypropylene may contain other copolymerizable α-olefin within a range not exceeding 50 mol%. Examples of the α-olefin include ethylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 3,3-dimethyl-1. -Butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane , Allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.1]
-Heptane etc. may be mentioned. Among these, preferable examples include ethylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene and the like. Of these, ethylene, 1-butene, 3-methyl-1-butene and 4-methyl-1-pentene are particularly preferable. These α-olefins may be used alone or in combination of two or more. When two or more α-olefins are used, the α-olefins may be randomly distributed in the unsaturated polymer or may be distributed in blocks.

I) Catalyst The above polypropylene can be produced by bringing propylene into contact with a catalyst containing the following components (a) and (b) to polymerize the catalyst.

Ii) Component (a) Component (a) is a transition metal compound represented by the following general formula (II). Q _a (Cp (R ¹ ) _u ) (Cp (R ² ) _v ) MeUV (II)

[In the formula, Q represents a bonding group bridging a cyclopentadienyl group, a represents an integer of 0 or 1, Cp represents a cyclopentadienyl group or a derivative containing a conjugated 5-membered ring, R ¹ and R ² are each a hydrocarbon group, a halogen atom, or an oxygen-, silicon-, phosphorus- or nitrogen-containing hydrocarbon group (R ¹ or R ² may be bonded to the cyclopentadienyl group at multiple positions, , A plurality of R ¹ or R ² may be the same or different), Me represents a transition metal of Group IVB to VIB of the Periodic Table, U and V each represent a hydrogen atom, a halogen atom, a hydrocarbon group, It represents an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group (U and V may be the same or different). u is an integer of 0 ≦ u ≦ 5, and v is an integer of 0 ≦ v ≦ 5]

Q, Cp, R ¹ , R ² and M of the general formula (II)
Details of e, U and V are as follows.

Q is a bonding group which bridges a cyclopentadienyl group, and specifically, (i) methylene, ethylene, isopropylene, diphenylmethylene, and other alkylene groups, (b) silylene, dimethylsilylene. , A silylene group such as disilylene and tetramethyldisilylene, and a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms including (c) germanium, phosphorus, nitrogen, boron and aluminum. Of these, Q is preferably an alkylene group or a silylene group.

Cp is cyclopentadiene, indene,
A conjugated 5-membered ring such as fluorene, or a derivative of such a conjugated 5-membered ring, that is, for example, one or more hydrogen atoms of these conjugated 5-membered rings are hydrocarbons, for example, having 1 carbon atom.
To those containing 20 to 20 are substituted.

R ¹ and R ² each have 1 to 2 carbon atoms.
0, preferably 1 to 12 hydrocarbon groups, halogen, oxygen, silicon, phosphorus or nitrogen containing hydrocarbon groups. R ¹
Alternatively, R ² may be bonded to the cyclopentadienyl group at multiple positions. When a plurality of R ¹ or R ² are present, they may be the same or different.

Me is a group IVB to VIB transition metal of the periodic table, preferably a group IVB transition metal such as titanium, zirconium and hafnium.

U and V are (a) a hydrogen atom,
(B) a halogen atom, (c) a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, (d) a hydrocarbon group containing silicon, (e) an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 alkoxy groups. A group, (f) amino group, (to) carbon-containing amino group having 1 to 10 carbon atoms (U and V may be the same or different) or (thi) phosphorus-containing hydrocarbon group. u is 0 ≦ u ≦ 5
And v is an integer of 0 ≦ v ≦ 5.

Specific examples of the component (a) when Me is zirconium are as follows. (1) bis (cyclopentadienyl) zirconium dichloride, (2) bis (methylcyclopentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadiene (Enyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6) bis (pentamethylcyclopentadienyl) zirconium dichloride,
(7) Bis (indenyl) zirconium dichloride,
(8) Bis (fluorenyl) zirconium dichloride,
(9) Bis (cyclopentadienyl) zirconium monochloride monohydride, (10) Bis (cyclopentadienyl) methylzirconium monochloride, (1)
1) Bis (cyclopentadienyl) ethyl zirconium monochloride, (12) Bis (cyclopentadienyl)
Phenyl zirconium monochloride, (13) bis (cyclopentadienyl) zirconium dimethyl, (14)
Bis (cyclopentadienyl) zirconium diphenyl, (15) bis (cyclopentadienyl) zirconium dineopentyl, (16) bis (cyclopentadienyl) zirconium dihydride, (17) (cyclopentadienyl) (indenyl) ) Zirconium dichloride, (18) (cyclopentadienyl) (fluorenyl) zirconium dichloride,

(19) Methylenebis (indenyl) zirconium dichloride, (20) Ethylenebis (indenyl) zirconium dichloride, (21) Ethylenebis (indenyl) zirconium monohydride monochloride, (22) Ethylenebis (indenyl) methylzirconium monochloride , (23) ethylenebis (indenyl) zirconium monomethoxymonochloride, (2
4) ethylene bis (indenyl) zirconium diethoxide, (25) ethylene bis (indenyl) zirconium dimethyl, (26) ethylene bis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride,
(27) Ethylene (2,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl)
Zirconium dichloride, (28) isopropylidene bis (indenyl) zirconium dichloride, (29) isopropylidene bis (2,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (30) ) Dimethylsilylenebis (indenyl) zirconium dichloride, (3
1) tetramethyldisilylene bis (indenyl) zirconium dichloride, (32) dimethylsilylene (4,
5,6,7-Tetrahydrinindenyl) zirconium dichloride, (33) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (34)
Dimethylgermane bis (indenyl) zirconium dichloride, (35) methylaluminum bis (indenyl) zirconium dichloride, (36) ethylaluminum bis (indenyl) zirconium dichloride, (3)
7) phenylaluminum bis (indenyl) zirconium dichloride, (38) phenylphosphinobis (indenyl) zirconium dichloride, (39) ethylboranobis (indenyl) zirconium dichloride,

(40) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (41) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride Hydride, (42) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (43) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (44) Methylene (cyclopentadienyl) (trityl cyclopentadienyl) zirconium dichloride, (45) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (46) isopropylidene (cyclopenta Enyl) (3,4-dimethyl cyclopentadienyl) zirconium dichloride, (47)
Isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (48) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (49) isopropylidene (2-methylcyclopentadienyl) ( Fluorenyl) zirconium dichloride, (50) isopropylidene (2,5-dimethylcyclopentadienyl) (3 ′,
-4 ′ dimethylcyclopentadienyl) zirconium dichloride, (51) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride,

(52) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (53) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(54) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (5
5) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (5
6) Diphenylmethylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium dichloride, (57) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (58) cyclohexylidene (cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, (59) cyclohexylidene (2,
5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride,

(60) Dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (61) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (62) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (63) dimethyl Silylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (64) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (65) dimethylsilylene (cyclopenta) (Dienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (66) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (67) dimethyi Silylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride, (68) dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,

(69) Dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (70) Dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (71) Dimethylsilylene (2-Ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (72) Dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (73) Dimethylsilylene (2-methylcyclopentadienyl) ) (2,7-Di-t-butylfluorenyl) zirconium dichloride, (74) dimethylsilylene (2,5-dimethylcyclopentadienyl)
(2,7-di-t-butylfluorenyl) zirconium dichloride, (75) dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (76 ) Dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
(77) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (78) dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (79) dimethylsilylene ( Ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (80) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,

(81) Dimethylgermane (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(82) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride, (83) Phenylalumino (cyclopentadienyl) (fluorenyl)
Examples include zirconium dichloride and the like.

In the present invention, a compound in which the chlorine atom of the above compound is replaced with a bromine atom or an iodine atom can also be used.

When Me is titanium, hafnium, niobium, molybdenum, or tungsten, compounds in which the central metal of the zirconium compound as described above is replaced with a corresponding metal can be exemplified.

Of these compounds, the zirconium compound or the hafnium compound is preferable as the component (a). More preferred are zirconium compounds or hafnium compounds having a structure crosslinked with an alkylene group.

Iii) Component (b) Component (b) is an alumoxane. Alumoxane is 1
It is a product obtained by reacting one or more trialkylaluminums with water. The trialkylaluminum preferably has an alkyl group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms.

Specific examples of the component (b) include (a) those obtained from one kind of trialkylaluminum and water, for example, methylalumoxane, ethylalumoxane,
Butyl alumoxane, isobutyl alumoxane, etc.
(B) There are those obtained from two types of trialkylaluminum and water, such as methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane.

Of these, methylalumoxane is particularly preferable. A plurality of these alumoxanes can be used in combination. Further, in the present invention, it is also possible to use alumoxane and alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum or dimethylaluminum chloride in combination.

Alumoxanes are generally represented by the general formula (II
I)

[0048]

[Chemical 2]

The cyclic alumoxane represented by the general formula (I
V)

[0050]

[Chemical 3]

It is a linear alumoxane represented by or a mixture thereof. However, in the formula, R ³ , R ⁴ , R ^5, and R ⁶ are each a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, and most preferably a methyl group,
p and q each represent a number of 2 to 100.

Iv) Preparation of component (b) The alumoxane described above can be produced by various known methods. Specifically, the following methods can be exemplified.

(A) A method in which a trialkylaluminum is directly reacted with water by using an appropriate organic solvent such as toluene, benzene or ether. (B) A method of reacting a trialkylaluminum with a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. (C) A method of reacting trialkylaluminum with water impregnated in silica gel or the like.

V) Production of polypropylene As a method of polymerizing propylene by using a catalyst containing the catalyst component (a) and the component (b), it goes without saying that a usual slurry polymerization method can be adopted, but a substantial solvent is used. A liquid phase solventless polymerization method, a solution polymerization method, or a gas phase polymerization method can be employed. It is also possible to carry out by a system of carrying out continuous polymerization, batchwise polymerization or preliminary polymerization. As a polymerization solvent in the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture. The polymerization temperature is about −78 to 200 ° C., preferably 0 to
The temperature is 150 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time.

The amounts of component (a) and component (b) used are
The atomic ratio of [aluminum atom in component (b)] / [transition metal of component (a)] is 0.01 to 100,000, preferably 0.1 to 30,000. Regarding the contact between the component (a) and the component (b), they can be contacted separately during the polymerization, or they can be contacted in advance outside the polymerization tank.

The polymerization pressure is not particularly limited, but is usually 1
It is about 1000 kg / cm ² G.

(2) Introduction of Functional Group into Polypropylene Having Olefinic Unsaturated Bond at End of Molecular Chain In the present invention, the above-mentioned polypropylene is modified so that olefinic unsaturated bond at end of molecular chain has carboxyl group and acid anhydride. Introduce a physical group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group or a sulfonic acid group.

In the present invention, the introduction of a functional group into an olefinic unsaturated bond means that the functional group is derived by utilizing the olefinic unsaturated bond, and the functional group is directly attached to the olefinic unsaturated bond. The functional group can be introduced by a method such as generation or binding of the functional group-containing compound to the olefinically unsaturated bond. The method of introducing the functional group is not particularly limited, but is generally performed by the method shown below.

I) Carboxyl group and acid anhydride A polypropylene having an olefinically unsaturated bond at the terminal of the molecular chain and an unsaturated carboxylic acid or acid anhydride are thermally reacted under heating conditions. This reaction is carried out in the presence or the absence of a solvent.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclododecane; benzene. Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene; chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane, tetrachloroethylene, etc. Halogenated hydrocarbon etc. can be illustrated. These can also be used as a mixed solvent of two or more kinds.

The temperature of the above modification reaction is usually 50 to 25.
It is 0 ° C., preferably 60 to 200 ° C., and the reaction time is usually 0.5 to 20 hours, preferably about 1 to 10 hours. The modification reaction can be carried out under either normal pressure or increased pressure.

The proportion of unsaturated carboxylic acid or acid anhydride supplied to the reaction is usually 0.2 to 300 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of polypropylene.
It is in the range of 0 parts by weight.

As the unsaturated carboxylic acid or acid anhydride,
For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, picicyclo [2.2.1] hept-2-ene-5,6
-Unsaturated carboxylic acids such as dicarboxylic acids; maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, picocyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, etc. And unsaturated carboxylic acid anhydrides thereof.

Ii) Hydroxyl group The method of introducing a hydroxyl group into the unsaturated group of polypropylene having an olefinic unsaturated bond at the terminal of the molecular chain is a method of oxidizing the olefinic unsaturated bond, or a method of containing one or more hydroxyl groups in the molecule. The method is roughly classified into a method by an addition reaction of the compound to an olefinic unsaturated bond and other methods.

Examples of the method of oxidizing the olefinic unsaturated bond include (a) oxidation via hydrogen peroxide solution and an organic acid such as formic acid through a peracid, and (b) phase transfer of a quaternary ammonium salt or the like. Oxidation with permanganate or the like in the presence or absence of a catalyst, (C) Oxidation with hydrogen peroxide solution, permanganate, etc., using an oxide such as (osmium, ruthenium, tungsten, selenium) as a catalyst,
(D) Hydrolysis of an adduct with a halogen such as bromine or hydrogen halide or an adduct of sulfuric acid, (e) hydrolysis of an epoxy group introduced by various reactions, (f) diborane or 9-borabicyclo [3. 3.1] Nonan (abbreviation 9
-BBN) and the like, followed by a hydroboration reaction and then oxidizing the boron binding site.

On the other hand, a group of compounds containing one or more hydroxyl groups in the molecule has active hydrogens (2 or more groups) which should undergo an addition reaction to an olefinic unsaturated bond, particularly a Michael type addition reaction. Having a hydroxyl group of
(Including the case where one of them is used in an addition reaction), and specific examples thereof include thiol compounds such as thioglycerol and thioglycol. In addition, the hydroxyl group can be introduced by addition reaction of aldehyde known as Prince reaction, oxidation reaction subsequent to hydroboration, demercuration reaction subsequent to oxymercuration with mercuric acetate, or the like.

The reaction is carried out in a state where the polymer is swollen or dissolved in a solvent or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent to be used should be appropriately selected depending on the type of reaction, but it is an aliphatic, alicyclic or aromatic hydrocarbon and its halide, an ester having 6 or more carbon atoms, a ketone, an ether, and carbon disulfide. It is often selected from the above, and these can also be used as a mixed solvent of two or more kinds. The reaction in the molten state is
For example, an ordinary granulator, twin-screw kneader, plastomill, etc. can be used.

Iii) Epoxy group The method of introducing an epoxy group into the unsaturated group of polypropylene having an olefinic unsaturated bond at the end of the molecular chain is a method of oxidizing an olefinic unsaturated bond, or one or more epoxies in the molecule. It is roughly classified into a method by an addition reaction of a compound containing a group to an olefinically unsaturated bond and other methods.

Examples of the method by the oxidation of the olefinic unsaturated bond include (a) oxidation with peracids such as performic acid, peracetic acid and perbenzoic acid, and (b) the presence of a metalloporphyrin complex such as a manganese porphyrin complex. Or, oxidation in the absence of sodium hypochlorite, etc., (c) vanadium,
Oxidation with hydrogen peroxide or hydroperoxide in the presence or absence of a catalyst such as tungsten or molybdenum compound, (d) oxidation with alkaline hydrogen peroxide, (e)
There is a method such as neutralization of an adduct with an acetic acid / t-butyl hypochlorite system with an alkali.

On the other hand, a group of compounds having one or more epoxy groups in the molecule has active hydrogen which should undergo an addition reaction to an olefinic unsaturated bond, particularly a Michael type addition reaction. And thiol compounds such as thioglycidol and glycidyl thioglycolate.

The reaction is carried out in a state where the polymer is swollen or dissolved in a solvent or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent to be used should be appropriately selected depending on the type of reaction, but it is an aliphatic, alicyclic or aromatic hydrocarbon and its halide, an ester having 6 or more carbon atoms, a ketone, an ether, and carbon disulfide. It is often selected from the above, and these can also be used as a mixed solvent of two or more kinds. The reaction in the molten state is
For example, an ordinary granulator, twin-screw kneader, plastomill, etc. can be used.

Iv) Amino group The method of introducing an amino group into the unsaturated group of polypropylene having an olefinic unsaturated bond at the terminal of the molecular chain is as follows.
After reacting with borane, a method of reacting with an aminating reagent such as hydroxylamine-O-sulfonic acid, a method of radically adding (b) allylamine or the like, (c) a carboxylic acid, a carboxylic acid derivative or an acid at the terminal After introducing an anhydride, a method of reacting with a polyvalent amine, a method of introducing an amide group at the (d) terminal and then reducing, a method of introducing an epoxy group at the (e) terminal, and then adding ammonia, polyvalent amine, etc. Examples thereof include a reaction method and a method of introducing a halogen at the (e) terminal and then reacting with a polyvalent amine.

The reaction is carried out in a state where the polymer is swollen or dissolved in a solvent or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent to be used should be appropriately selected according to the type of reaction, but it is not limited to aliphatic, alicyclic, aromatic hydrocarbons and their halides, esters having 6 or more carbon atoms, ketones, ethers and carbon disulfide. Often selected from the above, these can also be used as a mixed solvent of two or more kinds. For the reaction in the molten state, for example, an ordinary granulator, twin-screw kneader, plastomill and the like can be used.

V) Alkoxysilyl Group The method of introducing an alkoxysilyl group into the unsaturated group of polypropylene having an olefinic unsaturated bond at the end of the molecular chain is based on an alkoxysilane compound having a functional group that reacts with the olefinic unsaturated bond. The method is adopted. Specifically, for example, a method of adding a thiol compound having an alkoxysilyl group such as (3-mercaptopropyl) trimethoxysilane; a method of utilizing hydrosilylation of trimethoxysilane, triethoxysilane, etc .;
There is a method of addition-polymerizing a compound having an ethylenically unsaturated bond and an alkoxysilyl group such as vinyltrimethoxysilane and vinyltriethoxysilane.

The reaction is carried out in a state where the polymer is swollen or dissolved in a solvent or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent to be used should be appropriately selected depending on the type of reaction, but it is an aliphatic, alicyclic or aromatic hydrocarbon and its halide, an ester having 6 or more carbon atoms, a ketone, an ether, and carbon disulfide. It is often selected from the above, and these can also be used as a mixed solvent of two or more kinds. The reaction in the molten state is
For example, an ordinary granulator, twin-screw kneader, plastomill, etc. can be used.

Vi) Sulfonic Acid Group The method of introducing a sulfonic acid group into the unsaturated group of polypropylene having an olefinic unsaturated bond at the terminal of the molecular chain is as follows: sulfuric acid such as concentrated sulfuric acid, fuming sulfuric acid, sulfuric anhydride, or sulfur trioxide. And a Lewis base such as acetic anhydride, acetic acid, dioxane, tetrahydrofuran, pyridine, dimethylaniline, dimethylformamide, N-methylpyrrolidone, triethyl phosphate, and triethylamine.

The reaction is carried out in a state where the unsaturated polymer is swollen or dissolved in a solvent or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent to be used should be appropriately selected depending on the type of reaction, but aliphatic, alicyclic, aromatic hydrocarbons and their halides,
Often selected from esters, ketones, ethers and carbon disulfide having 6 or more carbon atoms, these can also be used as a mixed solvent of two or more kinds. For the reaction in the molten state, for example, an ordinary granulator, twin-screw kneader, plastomill and the like can be used.

In introducing each of the above functional groups, the selectivity of the reaction does not necessarily have to be 100%, and a product of a side reaction may be mixed if the functional group is substantially introduced.

The introduction amount of the functional group is 5% or more, preferably 20% or more, more preferably 30% or more, most preferably 50% or more of the olefinic unsaturated bond of unsaturated polypropylene. If the amount introduced is less than 5%, the production rate of the block copolymer decreases.

<PPE having a functional group at the end of the molecular chain (i
i)> (1) PPE The raw material PPE used for the component (C) is represented by the general formula (I).

[0081]

[Chemical 4]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents a hydrogen atom. Represents a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and m represents an integer of 10 or more).

The PPE represented by the general formula (I) has the formula (V)

[0084]

[Chemical 5]

It is a homopolymer or a copolymer composed of the structural unit of. Here, Q ¹ and Q ² are the same as above. Examples of suitable primary alkyl groups are methyl, ethyl,
n-propyl, n-butyl, n-amyl, isoamyl,
It is a 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl group. Suitable examples of secondary lower alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, each Q ¹ is an alkyl group or a phenyl group,
Particularly, it is an alkyl group having 1 to 4 carbon atoms, and each Q ² is a hydrogen atom.

Suitable homopolymers of PPE are those composed of, for example, 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers and random copolymers are
It is described in patents and literature. Also suitable are PPE containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength. For example, it is a resin obtained by graft-copolymerizing a vinyl monomer such as acrylonitrile or a vinyl aromatic compound such as styrene, or a polymer such as polystyrene or an elastomer onto PPE.

The molecular weight of PPE is such that the intrinsic viscosity at 30 ° C. usually measured in chloroform is about 0.2 to 0.8 dl / g.

PPE is usually produced by oxidative coupling of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, or cobalt, usually in combination with various other substances, and the like.

(2) Introduction of functional group into PPE In the present invention, the above PPE (I) is modified to introduce a functional group into the terminal of the molecular chain. The introduction method is not particularly limited. The introduced functional group is also not particularly limited as long as it reacts with the functional group of the component (i), but is not limited to carboxyl group, acid anhydride group, hydroxyl group,
Epoxy groups, amino groups or alkoxysilyl groups are preferred.

The introduction method will be exemplified below. i) Carboxyl group and acid anhydride group The terminal phenolic hydroxyl group of PPE (I) has the general formula (V
I)

[0091]

[Chemical 6]

(In the formula, R ⁷ and R ⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁹ represents a direct bond or a divalent hydrocarbon group having 1 to 32 carbon atoms. Y is -OR
^When they represent ¹⁰ or —OH, or when these substituents are adjacent to each other, they may be combined together to form an acid anhydride. R ¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms or an alkali metal atom. X represents a halogen atom. n is 1
Represented by the general formula (VII)

[0093]

[Chemical 7]

(Wherein Q ¹ , Q ² , R ⁷ , R ⁸ , R ⁹ ,
Y, m and n are the same as above) to obtain the end group-modified PPE. Specifically, the terminal carboxylic acid-modified PPE represented by the general formula (VII) can be easily prepared by reacting PPE (I) with a benzyl halide compound (VI) in the presence of a basic compound in an organic solvent. Can be manufactured. Further, in a mixed solvent of an organic solvent capable of dissolving PPE and an aqueous solution of a water-soluble inorganic basic compound, PPE (I) and a halogenated benzyl compound (VI) in the presence of a phase transfer catalyst.
It can be easily produced by reacting

The organic solvent used here is P as the raw material.
It is desirable that PE can be dissolved. Specific examples thereof include aromatic solvents such as benzene, toluene and xylene; halogenated aromatic solvents such as chlorobenzene and dichlorobenzene; halogenated hydrocarbon solvents such as chloroform, trichloroethylene and carbon tetrachloride.

Specific examples of the above-mentioned basic catalyst include alcoholates such as sodium methoxide and sodium ethoxide; benzyldimethylamine, triethylamine, tributylamine, 1,8-diazabicyclo [5.4.
0] -7-undecene (DBU) and the like tertiary amines. Specific examples of the water-soluble basic catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate.

Examples of the phase transfer catalyst include quaternary ammonium salt compounds, quaternary phosphonium salt compounds and tertiary sulfonium salt compounds. Preferred are quaternary ammonium salt compounds, and specific examples thereof include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate and trioctylmethylammonium chloride. Etc.

In this reaction, 1 to 30 mol, preferably 2 to 20 mol of the modifier represented by the general formula (VI) is used per 1 mol of the terminal phenolic hydroxyl group of PPE (I). The organic solvent is 300 to 100 relative to 100 parts by weight of PPE.
Use 0 parts by weight. The basic catalyst is used in an amount of 1 to 10 equivalents, preferably 1 to 3 equivalents per equivalent of the modifier used.
The phase transfer catalyst is used in an amount of 1 to 10 parts by weight per 100 parts by weight of PPE.

The production conditions of the terminal carboxylic acid-modified PPE represented by the general formula (VII) will be explained in detail. PPE is dissolved in an organic solvent by heating, and a basic catalyst is added thereto.
It is produced by adding a benzyl halide compound as a modifier at a temperature from room temperature to a temperature not exceeding the boiling point of the organic solvent to be used for reaction, and further stirring with heating until the reaction is completed.
Alternatively, after heating PPE in an organic solvent to dissolve it and adding an aqueous solution of a basic catalyst and a phase transfer catalyst thereto,
It is produced by adding a benzyl halide compound as a modifier at a temperature from room temperature to a temperature not exceeding the boiling point of the organic solvent to be used for reaction, and further stirring with heating until the reaction is completed.

Ii) Hydroxyl group The terminal hydroxyl group-modified PPE can be produced by the following methods (a) to (e).

(A) PPE (I) is added with the formula (VIII)

[0102]

[Chemical 8]

The glycidol represented by the formula is reacted to give a compound of the general formula (IX)

[0104]

[Chemical 9]

(In the formula, Q ¹ , Q ² and m are the same as above.
r represents an integer of 1 to 10).

(B) PPE (I) is added to the general formula (X)

[0107]

[Chemical 10]

An epihalohydrin represented by the formula (wherein X represents a halogen atom), for example, epichlorohydrin is reacted, and then the obtained terminal glycidyl-modified PPE is hydrolyzed to give a compound represented by the general formula (XI).

[0109]

[Chemical 11]

(Wherein Q ¹ , Q ² and m are the same as above)
A method for producing a hydroxyalkylated PPE represented by:

(C) PPE (I) was prepared by adding the compound of the general formula (XII) X—R ¹⁰ —OH (XII)

(In the formula, R ¹⁰ represents an alkylene group having 1 to ¹⁰ carbon atoms, X is the same as above), for example, 2-chloroethanol or 3
-Chlor-1-propanol or the like is reacted to give a compound of the general formula (XI
II)

[0113]

[Chemical 12]

A method for producing a hydroxyalkylated PPE represented by the formula (wherein Q ¹ , Q ² , m and R ¹⁰ are the same as above).

(D) PPE (I) is added with the compound of the general formula (XIV)

[0116]

[Chemical 13]

(In the formula, R ¹¹ represents a hydrogen atom or a carbon number of 1 to 8)
(Representing an alkyl group of) is reacted with an alkylene carbonate, such as ethylene carbonate or propylene carbonate, to give a compound of the general formula (XV)

[0118]

[Chemical 14]

A method for producing a hydroxyalkylated PPE represented by the formula (wherein Q ¹ , Q ² , m and R ¹¹ are the same as above).

(E) PPE (I) is added with general formula (XVI)

[0121]

[Chemical 15]

(Wherein R ¹¹ is as defined above) is reacted with an alkylene oxide such as ethylene oxide or propylene oxide to give a compound of the general formula (XV)

[0123]

[Chemical 16]

A method for producing a hydroxyalkylated PPE represented by the formula (wherein Q ¹ , Q ² , m and R ¹¹ are the same as above).

The organic solvent used here is an aromatic hydrocarbon such as benzene, toluene or xylene; a halogenated hydrocarbon such as chloroform or carbon tetrachloride; a halogenated aromatic such as chlorobenzene or dichlorobenzene. Hydrocarbon; N-methyl-2-pyrrolidone, 1,3-dimethyl-
Heterocyclic compounds such as 2-imidazolidinone.

Examples of the basic catalyst include alcoholates such as sodium methoxide and sodium ethoxide; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. Can be mentioned.

The reaction amount ratio of PPE and the modifier used in these reactions is 1 to 50 mol of the modifier with respect to 1 mol of the terminal phenolic hydroxyl group of PPE, and the amount of the basic catalyst used is 100 parts by weight of PPE. On the other hand, it is 0.5 to 50 parts by weight.

Iii) Epoxy group The method of introducing an epoxy group into PPE (I) is a reaction utilizing a terminal phenolic hydroxyl group of PPE, specifically, an addition reaction of epichlorohydrin, 2,2-bis (4-glycidylphenylene ether). ) Addition reaction of propane or epoxy resin can be used (JP-A-63-1255).
25 publication).

Iv) Amino Group The terminal amino group-modified PPE can be produced by the methods shown in (a) to (d) below.

[0130] (a) the PPE (I), the general formula ^{(XVII) R 12 - (N} = C = O) s (XVII) ( wherein, R ¹² is a divalent or more aliphatic 1 to 32 carbon atoms in the Which represents a hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, and s is an integer of 2 or more), and hydrolyzes the isocyanato group of the terminal isocyanate-modified PPE obtained by reacting a polyfunctional isocyanate represented by Then, the general formula (X
VIII)

[0131]

[Chemical 17]

A method for producing a terminal amino group-modified PPE represented by the formula (wherein Q ¹ , Q ² , R ¹² , m and s are the same as above).

(B) PPE (I) is represented by the general formula (XIX) X—R ¹³ —NH ₂ (XIX) (wherein R ¹³ is an aliphatic hydrocarbon group having 1 to 32 carbon atoms or an aromatic hydrocarbon group). Group or an araliphatic hydrocarbon group, and X represents a halogen atom) is reacted with a halogenated primary amine represented by the general formula (XX)

[0134]

[Chemical 18]

A method for producing a terminal amino group-modified PPE represented by the formula (wherein Q ¹ , Q ² , R ¹³ and n are the same as above).

(C) The terminal epoxidized PPE is reacted with a polyamine compound to give a compound of the general formula (XXI)

[0137]

[Chemical 19]

(In the formula, Q ¹ , Q ² and m are the same as above.
And D represents a polyamine residue).

(D) PPE (I) is reacted with a compound having both a carbon-carbon double bond or a carbon-carbon triple bond and an amino group in the molecule to introduce an amino group by a method for producing an amino group-modified PPE. can do.

V) Alkoxysilyl group PPE is represented by the general formula (XXII)

[0141]

[Chemical 20]

(In the formula, Z represents an oxygen atom or a nitrogen atom, R ¹⁴ represents an alkylene group having 1 to 12 carbon atoms, and R ¹⁵
And R ¹⁶ each represent a hydrocarbon group having 1 to 6 carbon atoms. y is 1 when Z is an oxygen atom, 2 when Z is a nitrogen atom, and t is an integer of 1 to 3) modified with a compound having a glycidyl group and an alkoxysilyl group in the same molecule. It can be manufactured. Specific examples of the compound (XXII) having a glycidyl group and an alkoxysilyl group in the same molecule are N-glycidyl-N, N-bis [3-
(Methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (trimethoxysilyl)
Propyl] amine, 3-glycidyloxypropyl (methyl) dimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl (methyl) diethoxysilane and the like can be mentioned. Particularly preferred is 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyl (methyl) diethoxysilane.

The method for modifying PPE is as follows.
General formula (XXIII)

[0144]

[Chemical 21]

(Wherein Z, R ¹⁴ , R ¹⁵ , R ¹⁶ , t and y
Is the same as above), and the modified PPE represented by
It can be easily produced by reacting (I) with a modifier represented by the general formula (XXII) in the presence of a basic catalyst in an organic solvent.

The organic solvent used here is preferably capable of dissolving PPE. Specifically, aromatic solvents such as benzene, toluene and xylene; halogenated aromatic solvents such as chlorobenzene and dichlorobenzene; carbon halide hydration solvents such as chloroform, trichloroethylene and carbon tetrachloride; N-methyl-2-pyrrolidone, 1,3-
An aprotic polar solvent such as dimethyl-2-imidazolidinone may be used. Examples of the basic catalyst include alcoholates such as sodium methoxide and sodium ethoxide; tertiary amines such as benzyldimethylamine and tributylamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

This reaction is carried out in a proportion of 2 moles of the modifying agent represented by the general formula (XXII) to 1 mol of the terminal phenolic hydroxyl group of PPE.
50 mol, preferably 5 to 20 mol is used. The organic solvent is used in an amount of 500 to 1,000 parts by weight based on 100 parts by weight of PPE. The basic catalyst is used in an amount of 1 to 3 parts by weight per 100 parts by weight of PPE used.

The general procedure for making modified PPE is:
(I) is dissolved in an organic solvent by heating, then a basic catalyst dissolved in a small amount of ethanol or methanol is added, a modifier is added at a temperature of 50 to 200 ° C., and the mixture is heated until the reaction is completed. To do.

In introducing each of the above functional groups, the selectivity of the reaction does not necessarily have to be 100%, and a product of a side reaction may be mixed if the functional group is substantially introduced.

The amount of functional group introduced is 5 at the end of PPE.
% Or more, preferably 20% or more, more preferably 30%
As described above, it is most preferably 50% or more. 5% introduction amount
If it is less than 100%, the production rate of the block copolymer decreases.

<Block Copolymer (C)> The block copolymer (C) used in the present invention is obtained by reacting the functional group at the molecular chain end of polypropylene with the functional group at the molecular chain end of PPE. -B type block copolymer.

The method for producing the block copolymer (C) is not particularly limited, but under the condition that each functional group is suitable for the reaction,
Each polymer is carried out in a swollen or dissolved state with a solvent or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent used is appropriately selected.

A catalyst or the like which promotes the reaction may be used in the reaction of each functional group. As a specific example of the reaction, for example, when a polymer having an epoxy group and an acid anhydride group is reacted, toluene, xylene, trichlorobenzene or the like is used as a solvent, and basic N, N-dimethylaminopyridine or the like is used as a catalyst. Can be used to react.

When a polymer having a hydroxyl group and an acid anhydride group is reacted, it can be reacted using toluene, xylene, trichlorobenzene or the like as a solvent and p-toluenesulfonic acid or the like as a catalyst. The block copolymer (C) is the unreacted component (i) and / or component (ii).
May be contained.

<< Composition Ratio of Constituent Components >> In the thermoplastic resin composition of the present invention, the compounding ratio of the polypropylene of the component (A) and the PPE of the component (B) is such that mechanical strength, moldability and solvent resistance are harmonized. From the viewpoint, the content of the component (A) is 10 to 90% by weight, preferably 20% with respect to the total of the components (A) and (B).
-80% by weight, more preferably 30-70% by weight.

When the content of the component (A) is less than 10% by weight, the effect of improving the moldability and solvent resistance of the composition is smaller than that of PPE, and when it exceeds 90% by weight, the effect of improving the heat resistance and the rigidity is better than that of polypropylene. small.

The block copolymer of the component (C) is 0.10 parts by weight based on 100 parts by weight of the total amount of the above components (A) and (B).
It is 1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, and more preferably 0.2 to 30 parts by weight. If it is less than 0.1 part by weight, the effect of improving the physical properties of the resin composition is small, and if it exceeds 50 parts by weight, the practical meaning of the resin composition is small in terms of cost and the like.

<< Additional Components >> The thermoplastic resin composition of the present invention may contain components other than the above-mentioned components (A), (B) and (C). For example, a part of the component (A) may be replaced with another olefin resin in the resin composition up to 80% by weight. Further, an antioxidant, a weather resistance improver, a nucleating agent, a twist resistance, a plasticity, a fluidity improver and the like may be contained in the resin composition in an amount of 20% by weight or less. Further, organic and inorganic fillers such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate and silica may be contained in an amount of 50% by weight or less, and a colorant dispersant may be included in an amount of 5% by weight or less. it can. Further, addition of impact strength improver, for example, styrene-butadiene copolymer rubber or hydride thereof, ethylene-propylene- (diene) copolymer rubber, and modification thereof with α, β-unsaturated carboxylic acid anhydride. Or a modified product of unsaturated glycidyl ester or unsaturated glycidyl ether, a copolymer composed of an unsaturated epoxy compound and ethylene, or an unsaturated epoxy compound, a copolymer composed of ethylene and an ethylenically unsaturated compound, etc. You may contain 30weight%. These additional components may be used alone or in combination of two or more.

<< Preparation of Thermoplastic Resin Composition >> As a melt-kneading method for obtaining the thermoplastic resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, powdery or granular components, if necessary, together with the additives and the like described in the section of additional components,
After uniform mixing with a Henschel mixer, ribbon blender, V-type blender, etc., kneading with a uniaxial or multiaxial kneading extruder, roll, Banbury mixer, etc. can be carried out. At the time of kneading, a solvent or the like may coexist.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, sheet molding are used. Various molding methods such as thermoforming, rotational molding, laminated molding and press molding can be applied.

[0161]

【Example】

Reference Example 1 (1) Synthesis of polypropylene having olefinic unsaturated bond at molecular chain end i) Production of catalyst component (a) Ethylenebis (indenyl) zirconium dichloride [hereinafter referred to as (a-1)] was prepared according to J. Orgmet. Chem. 342 21
~ 29 (1988) and J. Orgmet. Chem. 369 359-370 (198
Synthesized according to 9).

Ii) Preparation of catalyst component (b) In 565 ml of a toluene solution containing 48.2 g of trimethylaluminum, while stirring, 50 g of copper sulfate pentahydrate was added at 0 ° C. to 5 g.
It was put in every 5 minutes. Then slowly add the solution to 2
The temperature was raised to 5 ° C., the reaction was carried out at 25 ° C. for 2 hours, and the temperature was further raised to 35 ° C. to carry out the reaction for 2 days. The remaining copper sulfate solid was separated and the concentration of methylalumoxane was 27.3 mg / ml (2.
A toluene solution of 7 w / v%) was obtained.

Iii) Preparation of Resin A-0 A stainless steel autoclave with an internal volume of 1.0 liter equipped with a stirrer and a temperature controller was added with 400 ml of fully dehydrated and deoxygenated toluene and methylalumoxane (b).
580 mg and component (a-1) 0.418 mg (0.00
1 mmol) was introduced, and propylene pressure was 7 kg / cm ² G and polymerization was performed at 40 ° C. for 4 hours. After completion of the polymerization, the polymerization solution was extracted into 3 liters of methanol, the polymer was filtered off and dried, and 180 g of resin (hereinafter referred to as "resin A-0")
Was recovered. As a result of gel permeation chromatography (hereinafter referred to as “GPC”) measurement, this product had a number average molecular weight (M _n ) of 18.7 × 10 ³ and a molecular weight distribution (M _w).
/ _Mn ) was 1.99.

¹³ C-NMR (manufactured by JEOL Ltd., trade name: J
EOL. FX-200) analysis showed that triad [m
The [m] fraction was 0.888, and vinylidene bonds were all at one end (0.79 per 1000 carbon atoms).

(2) Synthesis of polypropylene having maleic anhydride added to the terminal A stainless steel autoclave having an internal volume of 1 liter was sufficiently replaced with nitrogen to obtain the resin A-0: 10 obtained in (1) above.
g, decane 500 ml, maleic anhydride 5 g,
It heated up at 200 degreeC and heated for 8 hours. Then, after cooling to 50 ° C., the content was poured into 3 liters of acetone to precipitate a polymer. The precipitated polymer is filtered,
After washing with acetone and filtration were repeated 3 times, the product was dried under reduced pressure.
The obtained polymer (hereinafter referred to as "resin A-1") was 9.
Infrared spectroscopic analysis and ¹ H-NMR analysis showed that maleic anhydride was added to the terminal 90.5% olefinically unsaturated bond. As a result of GPC measurement, M _n
Was 1.83 × 10 ³ and M _w / M _n was 2.01, which means that the raw material polymer was not changed.

Reference Example 2: Synthesis of PPE Having Epoxy Group at Terminal End 10 liters of epichlorohydrin was placed in a stainless steel autoclave having an internal volume of 30 liters, and then poly (2,6-dimethyl-1,4-phenylene ether) was added.
300 g (manufactured by Nippon Polyether Co., intrinsic viscosity 0.47 dl / g measured in chloroform at 30 ° C.) was added. Next, this solution is heated and heated by an external jacket and kept at 100 ° C for about 30 minutes while stirring to completely dissolve the polymer, and then 50 ml of 10% aqueous sodium hydroxide solution is added thereto, and the mixture is kept under a nitrogen atmosphere at 100 ° C for 3 hours. It was made to react. After completion of the reaction, epichlorohydrin was distilled off under reduced pressure, and the obtained polymer was dissolved in 5 liters of chloroform. After removing solids (NaCl formed and excess NaOH) which were liberated in the polymer solution by filtration, methanol / water (50
/ 50) mixed solvent is added to reprecipitate the polymer, and the polymer is washed 3 times with 10 liters of the same solvent and then dried at 100 ° C. for about 10 hours to give glycidylated PPE (hereinafter referred to as “resin B”).
-1 ”). The polymer obtained by this operation was titrated using toluene as a solvent according to the method specified in ISO-3001. As a result, the amount of glycidyl groups contained in 100 g of the polymer was 5.6 × 10 ⁻³ mol. Was

Reference Example 3: Synthesis of PPE Having Amino Group at Terminal End In a dry separable flask having an internal volume of 10 liters,
To 500 g of poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., intrinsic viscosity measured in chloroform at 30 ° C .: 0.30 dl / g) was added 5 liters of toluene under a nitrogen atmosphere. The PPE was dissolved by heating and stirring at 70 ° C. Subsequently, 175 g of a 50% aqueous sodium hydroxide solution was added as a basic catalyst, and 50 g of trioctylmethylammonium chloride was added as a phase transfer catalyst, and then the temperature of the mixture was raised to 90 ° C.
Stirring was continued for 0 minutes. Then 3-chloropropylamine 7
5 g was dissolved in 250 ml water and added over 15 minutes. Furthermore, after heating and stirring for 7 hours, the reaction mixture was poured into 25 liters of methanol to precipitate the modified resin produced. After this was filtered off, it was washed with 25 liters of water and further with 25 liters of methanol. It was dried by heating under reduced pressure at 80 ° C. to obtain aminated PPE (hereinafter referred to as “resin B-2”). The recovery rate was 99%.

Confirmation of amino groups and reaction rate of terminal phenolic hydroxyl groups of PPE were 1.5% by weight of aminated PPE.
Was carried out by measuring the infrared absorption spectrum of the above carbon tetrachloride solution using a quartz cell having an optical path length of 10 mm. Absorption by an amino group was observed at a position of 3380 cm ^-1 . The reaction rate was 100% as calculated from the value of the absorbance (3622 cm ^-1 ) of the terminal phenolic hydroxyl group of PPE before and after the reaction. Furthermore, ¹ H-NMR analysis revealed that the number of primary amine halides added was 1 molecule.

Reference Example (Comparative) 4: Production of Maleic Anhydride-Modified Polypropylene 0.8 parts by weight of benzoyl peroxide and 1 part by weight of maleic anhydride were added to 100 parts by weight of a homopolymer powder of polypropylene, and then added in a Henschel mixer. The mixture was mixed, extruded by an extruder at 220 ° C., cooled with water and pelletized. The modified polypropylene (hereinafter referred to as "resin A-2") had a maleic anhydride content of 0.25 mol% and a melt flow rate (MFR) of 13 g / 10 minutes.

Reference Example 5 Production of Block Copolymer A well-dried round bottom flask having an internal volume of 500 ml was replaced with nitrogen, and 10 g of Resin A-1 obtained in Reference Example 1, Reference Example 2
Resin B-1 (10 g) obtained in Step 1, trichlorobenzene 200
ml and N, N-dimethylaminopyridine 0.1 g were charged, the temperature was raised to 150 ° C., and the reaction was carried out with stirring for 15 hours. After the reaction was completed, the reaction solution was poured into a large excess of methanol, and the polymer was separated by filtration and dried. The resulting polymer (hereinafter "resin C-
1 ") was 19.6 g.

The polymer was subjected to Soxhlet extraction for 8 hours using xylene as a solvent using a wire mesh of 80 mesh, and no xylene insoluble matter was found.

The polymer obtained was subjected to Soxhlet extraction with chloroform for 8 hours to recover the chloroform-insoluble matter. Infrared spectroscopic analysis of the polymer gave a PPE content of 35.1% by weight.

Reference Example 6 Production of Block Copolymer A well-dried round bottom flask having an internal volume of 500 ml was replaced with nitrogen, 110 g of Resin A-, 10 g of Resin B-2 and 200 ml of xylene were charged, and the temperature was raised to 100 ° C. The mixture was warmed and reacted with stirring for 15 hours. After the reaction was completed, the reaction solution was poured into a large excess of methanol, and the polymer was separated by filtration and dried. The obtained polymer (hereinafter referred to as "resin C-2") was 19.8 g. When Soxhlet extraction was carried out in the same manner as in Example 1, there was no xylene insoluble matter. Similarly, the content of PPE insoluble in chloroform was 25.5% by weight.

Reference Example (Comparative) 7: Production of Copolymer Composition The same procedure as in Reference Example 5 was carried out except that the resin A-2 obtained in Reference Example 4 was used in place of the resin A-1.

The xylene insoluble content of the obtained polymer (hereinafter referred to as "resin C-3") was 20.1% by weight. The PPE content of the insoluble matter in chloroform was 25.7% by weight.

Examples 1 to 4 and Comparative Examples 1 to 4 The block and graft copolymers obtained in Reference Examples 5, 6 and 7, the resin A-0 obtained in Reference Example 1 and a homopolymer of polypropylene (Mitsubishi Petrochemical Co., Ltd. Company name, MA8) and poly (2,6-dimethyl-1,4-phenylene ether)
(Nippon polyether Co., Ltd., intrinsic viscosity measured in chloroform at 30 ° C .: 0.30 dl / g) was used to prepare each component according to the composition ratio shown in Table 1 using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho). Used, 230 ℃, 180rpm
The mixture was kneaded for 5 minutes and then pulverized to obtain a granular resin composition.

[0177]

[Table 1]

The properties of the obtained resin composition were measured by using an injection molding machine [Custom Scientific (Custom Scientifi
c) CS183MMX minimax manufactured by SMC] was used to measure and evaluate a test piece having a thickness of 2 mm, which was injection-molded at a temperature of 280 ° C., by the following method. The evaluation results are shown in Table 1.

(1) Izod impact strength: length 31.5
mm, width 6.2mm, thickness 3.2mm, injection molded,
Using an Izod impact tester (Minimax CS-138TI type manufactured by Custom Scientific), 2
The Izod impact strength without notch at 3 ° C. was measured.

(2) Strength at break and elongation at break: Tensile test pieces having a parallel part length of 7 mm and a parallel part diameter of 1.5 mm were injection-molded, and a tensile tester (manufactured by Custom Scientific, model CS-183TE) was used. ) Was used to conduct a tensile test under the conditions of a tensile speed of 1 cm / min to measure the strength at break and the elongation at break.

[0181]

INDUSTRIAL APPLICABILITY As described above, the thermoplastic resin composition of the present invention has a very good affinity between components, impact strength,
Since it has an excellent balance of mechanical strength such as tensile strength, it has a wide range of uses and can be an industrially useful material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Haruo Omura 1 Tohocho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (2)

[Claims] 1. A thermoplastic resin composition comprising the following components (A), (B) and (C). (A) Polypropylene (B) Polyphenylene ether (C) (i) A functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group and a sulfonic acid group is attached to the molecular chain end. Polypropylene introduced into the olefinically unsaturated bond of (i
i) A block copolymer obtained by reacting a polyphenylene ether having a functional group that reacts with the functional group of component (i) at the molecular chain end is added to 100 parts by weight of the total amount of components (A) and (B). 0.1 to 50 parts by weight 2. The raw material component (ii) of the component (C) is a polyphenylene ether having a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group and an alkoxysilyl group. The thermoplastic resin composition according to claim 1.