JP5430117B2 - Method for producing heat-resistant cloth copolymer, heat-resistant cloth copolymer obtained, and use thereof - Google Patents

Description

  The present invention relates to a specific cross-copolymer excellent in heat resistance and excellent in softness and transparency, and a production method and use thereof.

  Using a copolymer (macromer, main chain) containing a small amount of divinylbenzene, obtained with a specific single-site coordination polymerization catalyst, a heterogeneous polymer chain (cross) by anionic polymerization or radical polymerization via the vinyl group of this divinylbenzene unit. A method for introducing and bonding a chain), that is, a method for producing a so-called cross copolymer has been proposed (Patent Document 1). According to this document, the styrene monomer and divinylbenzene monomer in the polymerization solution are highly active and are incorporated into the olefin polymer at a high conversion rate, thereby providing a very efficient polymerization method. In particular, since the vinyl group of the divinylbenzene unit in the polymer does not polymerize and remains with high efficiency, a cross copolymer can be produced using the resulting macromer (main chain). The obtained polymer (cross copolymer) also has improved various physical properties as compared with the main chain (macromer), and also has improved heat resistance. However, when the disclosed cross chain is polystyrene, the heat resistance is about 100 ° C. of the glass transition temperature, and further improvement in heat resistance is required.

On the other hand, heat-resistant copolymers obtained by copolymerization of aromatic vinyl compounds and unsaturated dicarboxylic acid anhydrides or imidized unsaturated dicarboxylic acid anhydrides by radical polymerization are known. This includes a copolymer obtained by copolymerizing an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride and then imidizing the acid anhydride by reaction with a primary amine. These copolymer resins are excellent in heat resistance but lack in impact resistance, so they are mixed with fibers or radically copolymerized in the presence of rubber components such as butadiene in advance to improve impact resistance. It has been proposed.
No. 00/037517

The present invention improves a heat resistance of a conventional cross copolymer, and at the same time, improves a new physical property of the other heat-resistant cross copolymer (in the following specification, it may be simply referred to as a cross copolymer). Is to provide.

  A method for producing a cross-copolymer comprising a coordination polymerization step and a radical polymerization step subsequent thereto, wherein in the coordination polymerization step, an aromatic polyene copolymerized macromer is synthesized using a single-site coordination polymerization catalyst. In the radical polymerization step, a cross-copolymer characterized by radical polymerization in the presence of an aromatic polyene copolymer macromer, an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride, or an imidized unsaturated dicarboxylic acid anhydride It is a manufacturing method. Further, as a radical polymerization step, the copolymer obtained by radical polymerization in the presence of an aromatic polyene copolymer macromer, an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride is further imidized. It is a manufacturing method of a cross copolymer.

  The heat-resistant cloth copolymer obtained by the production method of the present invention has characteristics that are superior in heat resistance and oil resistance as compared with conventional cloth copolymers.

The production method of the present invention is a method for producing a cross-copolymer comprising a coordination polymerization step and a radical polymerization step subsequent thereto, and in the coordination polymerization step, an aromatic polyene copolymer is prepared using a single site coordination polymerization catalyst. A production method characterized by synthesizing a polymerized macromer, followed by radical polymerization in the presence of an aromatic polyene copolymerized macromer, an aromatic vinyl compound and an imidized unsaturated dicarboxylic acid anhydride as a radical polymerization step, Moreover, it is a heat resistant cross copolymer obtained by this manufacturing method.
The production method of the present invention is a method for producing a cross-copolymer comprising a coordination polymerization step and a radical polymerization step that follows the coordination polymerization step. The coordination polymerization step uses an aromatic polyene using a single-site coordination polymerization catalyst. A synthesis method comprising synthesizing a copolymerized macromer, and then performing radical polymerization in the presence of the aromatic polyene copolymerized macromer, an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride as a radical polymerization step, Further, it is a production method for imidizing the obtained copolymer, and is a heat-resistant cloth copolymer obtained by these production methods.
In the present production method, the aromatic polyene copolymerized macromer used includes 0.01 to 1 mol% of aromatic polyene units, preferably 0.01 to 0.5 mol%, In addition, it is composed of one or more kinds of monomer units capable of coordination polymerization, and has a weight average molecular weight of 1,000 to 500,000, preferably 10,000 to 300,000, molecular weight distribution (weight average molecular weight / number average molecular weight ) Is a copolymer of 1.1 to 6 and preferably 1.5 to 3.

Preferably, in this production method, the aromatic polyene copolymer macromer used is an ethylene-aromatic vinyl compound-aromatic polyene copolymer, ethylene-olefin-aromatic polyene copolymer, ethylene-olefin-aromatic. It is a manufacturing method characterized by being an aromatic polyene copolymer macromer which is at least one selected from a vinyl compound-aromatic polyene copolymer.
In the cross-copolymer main chain derived from the aromatic polyene copolymer macromer of the present invention, a cross-copolymer finally obtained when a crystal structure derived from an olefin chain structure, for example, a crystal structure based on an ethylene chain exists more than a certain amount. The softness of the coalescence may be impaired, and the dimensional stability of the molded body, such as shrinkage due to crystallization, may be impaired during the molding process. Therefore, in order to obtain a cross-copolymer having excellent softness and molding stability, it is preferable that the total crystal melting heat including olefin crystallinity and other crystallinity is DSC in a temperature range of 50 ° C to 200 ° C. The total crystal heat of fusion measured in (1) is 100 J / g or less, more preferably 50 J / g or less, particularly preferably 30 J / g or less.

Here, when the aromatic polyene copolymerized macromer used is an ethylene-aromatic vinyl compound-aromatic polyene copolymer, a preferable composition satisfying this condition is an aromatic vinyl unit content of 5 mol% or more and 50 mol%. In the following, it is preferably 10 mol% or more and 50 mol% or less, the aromatic polyene unit content is 0.01 mol% or more and 1 mol% or less, and the balance is the ethylene unit content.
When the aromatic polyene copolymerized macromer used is an ethylene-olefin-aromatic polyene copolymer, the olefin unit content is 5 mol% to 50 mol%, preferably 10 mol% to 50 mol%, aromatic. The polyene unit content is 0.01 mol% or more and 1 mol% or less, and the balance is the ethylene unit content.

When the aromatic polyene copolymerized macromer used is an ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer, the total of the aromatic vinyl unit content (mol%) and the olefin unit content (mol%) is 5 mol% or more and 50 mol% or less, preferably 10 mol% or more and 50 mol% or less, aromatic polyene unit content 0.01 mol% or more and 1 mol% or less, and the balance is ethylene unit content.
When the aromatic vinyl unit or olefin unit content shown above, or the total thereof, is lower than 5 mol%, crystallization occurs based on the ethylene chain structure, and the softness and dimensional stability during molding are lost. In addition, when the aromatic vinyl unit content, olefin unit content, or the total thereof is higher than 50 mol%, the glass transition temperature of the finally obtained cross-copolymer becomes high, the low-temperature characteristics deteriorate, This is not preferable because the softness of the resin may be impaired and brittleness may develop.

  The heat-resistant cross-copolymer obtained by this method includes an aromatic polyene copolymer macromer that is a main chain, an aromatic vinyl compound that is a cross-chain and an unsaturated dicarboxylic acid anhydride, or an imidized unsaturated dicarboxylic acid anhydride. The copolymer polymer chain is considered to contain a structure (cross-copolymer structure or segregated star polymer structure) in which the polymer chain is bonded via a main chain aromatic polyene unit. However, the structure and the ratio of the present cross-copolymer are arbitrary, and the heat-resistant cross-copolymer of the present invention is defined as a copolymer (polymer) obtained by the production method of the present invention.

Examples of the coordination polymerizable monomer used in the present invention include ethylene, an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 5 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms.
Examples of the olefin used in the present invention include α-olefins having 3 to 20 carbon atoms, that is, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and vinylcyclohexane. 5-20 cyclic olefins, namely cyclopentene, benzocyclobutane, norbornene. Preferably, propylene, 1-butene, 1-hexene or 1-octene is used alone or as a mixture, and most preferably propylene and 1-butene are used. The aromatic vinyl compound used in the present invention is an aromatic vinyl compound having 8 to 20 carbon atoms, such as styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot. -Butyl styrene, mt-butyl styrene, pt-butyl styrene, p-chlorostyrene, o-chlorostyrene and the like. Industrially, styrene, p-methylstyrene, p-chlorostyrene, particularly preferably styrene is used.

  The aromatic polyene used in the present invention is an aromatic polyene having 10 to 30 carbon atoms and having a plurality of double bonds (vinyl group) and one or more aromatic groups and capable of coordination polymerization. There is an aromatic polyene in which one of the double bonds (vinyl group) is used for coordination polymerization and the remaining double bond in the polymerized state can be radically polymerized. Preferably, any one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene is preferably used.

Examples of the ethylene-aromatic vinyl compound-aromatic polyene copolymer used in the aromatic polyene copolymer macromer of the present invention include ethylene-styrene-divinylbenzene copolymer as the most preferred example, and ethylene-olefin. Examples of the aromatic polyene copolymer include ethylene-propylene-divinylbenzene copolymer and ethylene-1-butene-divinylbenzene copolymer, and ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer. Examples of the polymer include an ethylene-propylene-styrene-divinylbenzene copolymer and an ethylene-1-butene-styrene-divinylbenzene copolymer.
In the case of the preferred composition ranges shown below, the finally obtained cross-copolymer is rich in heat resistance and softness and can exhibit good mechanical properties.
The composition of the aromatic polyene copolymerized macromer shown above can be controlled within the above range by a known general method, but the simplest is to change the charged composition ratio of the aromatic vinyl compound or olefin monomer. Alternatively, it can be achieved by changing the ethylene partial pressure.

  Furthermore, in this production method, the mass ratio of the aromatic polyene copolymer macromer obtained in the coordination polymerization step to the cross copolymer finally obtained through the radical polymerization step is arbitrary, but it is 10% by mass or more and 95%. It is preferable that it is below mass%. If the mass ratio is less than 10% by mass, physical properties (softness and impact resistance) derived from the main chain of the finally obtained cross-copolymer are insufficient, and if it is 95% by mass or more, physical properties derived from the cross chain. For example, heat resistance etc. will fall. Furthermore, when the purpose is a heat-resistant resin or heat-resistant thermoplastic elastomer rich in softness and impact resistance, this mass ratio is 20% by mass or more and 80% by mass or less. The cross-copolymer obtained by this production method preferably has an A hardness of 40 or more and a D hardness of 70 or less (A hardness of 99 or less). The tensile modulus is preferably 1 MPa or more and 200 MPa or less. Furthermore, in the case of aiming at a heat-resistant thermoplastic elastomer rich in softness, the present mass ratio is 40% by mass or more and 80% by mass or less. In this case, the A hardness is in the range of 50 to 90. The tensile modulus is 3 MPa or more and 100 MPa or less.

The mass ratio of the aromatic polyene copolymerized macromer obtained in the present coordination polymerization step is, for example, the amount of ethylene consumed or the polymer in the case where the coordination polymerization step and the subsequent radical polymerization step are continuously performed using the same polymerization solution. It can be controlled by monitoring the concentration and composition and calculating the mass of the copolymer produced in the main polymerization step. In order to reduce the mass ratio, for example, the above monitoring may be performed, the time of the coordination polymerization process may be shortened while calculating the mass of the copolymer to be produced, and the polymerization process may be started early. In order to increase the polymerization time, the polymerization time may be lengthened to delay the start of the radical polymerization process. Further, a monomer used in the radical polymerization step may be additionally added at the start of the radical polymerization step or during the step. The mass ratio of the aromatic polyene copolymerized macromer obtained in the present coordination polymerization step can be arbitrarily changed by the additional amount of monomer added.
Moreover, in the manufacturing method of this invention, a coordination polymerization process and a radical polymerization process can be implemented separately. That is, the aromatic polyene copolymerized macromer obtained in the coordination polymerization step is separated and recovered from the polymerization solution, and an appropriate amount thereof can be dissolved in a new polymerization solvent and monomer solution to perform radical polymerization. In this case, the composition can be controlled by the amount of aromatic polyene copolymerized macromer used and the amount of monomer used / polymerization conversion rate.

When an ethylene-aromatic vinyl compound-aromatic polyene copolymer is used as the aromatic polyene copolymer macromer, a cross-copolymer excellent in mechanical properties, texture and oil resistance can be obtained. When an ethylene-olefin-aromatic polyene copolymer is used as the aromatic polyene copolymer macromer, a cross-copolymer having excellent low temperature characteristics and a low embrittlement temperature can be obtained. Furthermore, a cross copolymer having improved compatibility with polyolefin can be obtained. Further, when an ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer is used as the aromatic polyene copolymer macromer, a cross-copolymer having both of the above characteristics in a balanced manner can be obtained depending on the composition. .

In particular, when an ethylene-olefin-aromatic polyene copolymer is used as an aromatic polyene copolymer macromer, an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride or an imidized unsaturated dicarboxylic acid anhydride are used as the main chain polyolefin. A polymer in which the product copolymer polymer chain is bonded via an aromatic polyene unit is obtained. Such a polymer is considered useful as a modification of polyolefin (improvement of colorability), a compatibilizer, an adhesive, and a heat seal material.
The aromatic polyene copolymer macromer obtained in the coordination polymerization step of the production method has an aromatic polyene unit content of 0.01 mol% or more and 1 mol% or less. When the aromatic polyene unit content is lower than the above range, the cross-linking efficiency decreases, and the non-cross-linked component contained in the resulting cross-copolymer, that is, the aromatic polyene copolymer macromer or the aromatic vinyl compound-imidized unsaturated dicarboxylic acid. The ratio of the acid anhydride copolymer is increased, the physical properties as a cross-copolymer are lowered, and the properties as a simple mixture are manifested, which is not preferable. If the aromatic polyene unit content is higher than the above, the physical properties derived from the main chain of the finally obtained cross-copolymer will be difficult to develop, and the fluidity, molding processability, gel generation, etc. will occur. The possibility increases.
Considering the mechanical properties and molding processability (evaluable by fluidity and MFR (Melt Flow Rate)) of the finally obtained cross-copolymer, the preferable aromatic polyene unit content is 0.01 mol% or more and 0.5. It is less than mol%.
A preferable MFR value of the finally obtained cross-copolymer is 0.01 g / 10 min or more and 200 g / 10 min or less, particularly preferably 0.1 g / 10 min or more and 50 g / min under the measurement conditions of 260 ° C. and a load of 10 kg. 10 minutes or less.

Below, the manufacturing method of this invention is demonstrated in detail.
<Coordination polymerization process>
In the coordination polymerization step of this production method, a single site coordination polymerization catalyst is used. Preferably, a single site coordination polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a cocatalyst is used.

In the formula, A and B may be the same or different and are a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. Here, the substituted benzoindenyl group is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, It is a benzoindenyl group substituted by OSiR ₃ group, SiR ₃ group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). Adjacent substituents may be combined to form a 5- to 8-membered aromatic ring or alicyclic ring.
Here, the substituted indenyl group, the substituted cyclopentadienyl group, or the substituted fluorenyl group is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number of 7 An indenyl group or a cyclopentadienyl group substituted with a ~ 20 alkylaryl group, halogen atom, OSiR ₃ group, SiR ₃ group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms) Or a fluorenyl group.

Y has a bond with A and B, and in addition, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (in addition to 1 to 3 nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus A methylene group or a boron group having an atom or a silicon atom. The substituents may be different or the same. Y may have a cyclic structure. X is hydrogen, a hydroxyl group, halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium.

In the coordination polymerization step of this production method, more preferably, a single site coordination polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a cocatalyst is used.
In the coordination polymerization step, more preferably, in the transition metal compound represented by the general formula (1), A and B may be the same or different, and are unsubstituted or substituted benzoindenyl groups, unsubstituted Or, it is a group selected from substituted indenyl groups. Here, the unsubstituted or substituted benzoindenyl group is an unsubstituted or substituted benzoindenyl group represented by the general formulas (2), (3), and (4). The unsubstituted and substituted indenyl group is an unsubstituted and substituted indenyl group represented by the following general formula (5).

In general formulas (2), (3), and (4), R1 to R3 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and a halogen. An atom, OSiR ₃ group, SiR ₃ group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R1s, R2s, and R3s may be the same as or different from each other, and adjacent R1 and R2 groups may be combined to form a 5- to 8-membered aromatic or alicyclic ring.

In the general formula (5), R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, an SiR ₃ group, or It is a PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R4 may be the same or different from each other.
Examples of the unsubstituted benzoindenyl group include a 4,5-benzo-1-indenyl group, a 5,6-benzo-1-indenyl group, and a 6,7-benzo-1-indenyl group. Can be exemplified by a 1-indenyl group. Examples of the substituted benzoindenyl group include α-acenaphtho-1-indenyl group, 3-cyclopenta [c] phenanthryl group, and 1-cyclopenta [l] phenanthryl group.
Y has a bond with A and B, and in addition, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (in addition to 1 to 3 nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus A methylene group or a boron group having an atom or a silicon atom. The substituents may be different or the same. Y may have a cyclic structure. X is hydrogen, a hydroxyl group, halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium.

Further, the transition metal compound is preferably a racemate. Suitable examples of such transition metal compounds include transition metal compounds having a substituted methylene bridge structure specifically exemplified in EP-087492A2, JP-A-11-130808, and JP-A-9-309925, and WO01 / This is a transition metal compound having a boron cross-linking structure specifically exemplified in Japanese Patent No. 068719.
Furthermore, the transition metal compound of the single site coordination polymerization catalyst that is most preferably used has a structure represented by the general formula (1), and A and B may be the same or different. Y is a group selected from the unsubstituted or substituted benzoindenyl group represented by the formula (2), (3), (4) and the unsubstituted or substituted indenyl group represented by the general formula (5), and Y is It has a bond with A and B, and in addition, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (may contain 1 to 3 nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, silicon atoms) And the transition metal compound is a racemate. When this condition is satisfied, the present invention exhibits an industrially highly advantageous high activity in producing an ethylene-aromatic vinyl compound-aromatic polyene copolymer and an ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer. Furthermore, the obtained ethylene-aromatic vinyl compound-aromatic polyene copolymer in this composition range can have isotactic stereoregularity in the alternating structure of the ethylene-aromatic vinyl compound. Therefore, the cross copolymer of the present invention can have microcrystallinity derived from this alternate structure. In addition, the present ethylene-aromatic vinyl compound-aromatic polyene copolymer can give good mechanical properties and oil resistance based on the microcrystallinity of the alternating structure compared to the case without stereoregularity. Can finally be inherited by the cross-copolymer of the present invention.

The crystalline melting point due to the microcrystalline nature of the alternating structure of ethylene-aromatic vinyl compound-aromatic polyene copolymer is generally in the range of 50 ° C. to 200 ° C., and the heat of crystal melting by DSC is 100 J / g or less, preferably 50 J / g or less, most preferably 30 J / g or less. The finally obtained cross-copolymer of the present invention can have a heat of crystal fusion of 50 J / g or less, preferably 30 J / g or less as a whole. Crystallinity that gives heat of crystal melting within this range does not adversely affect the softness and molding processability of the present cross-copolymer, but rather is advantageous in terms of excellent mechanical properties and oil resistance.
Moreover, the transition metal compound shown by following General formula (6) can also be used suitably.

In the formula, Cp represents an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. The group to be selected. Here, a substituted cyclopentaphenanthryl group, a substituted benzoindenyl group, a substituted cyclopentadienyl group, a substituted indenyl group, or a substituted fluorenyl group is an alkyl in which one or more substitutable hydrogen atoms are 1 to 20 carbon atoms. Group, aryl group having 6 to 10 carbon atoms, alkylaryl group having 7 to 20 carbon atoms, halogen atom, OSiR ₃ group, SiR ₃ group or PR ₂ group (R is a hydrocarbon group having 1 to 10 carbon atoms. A cyclopentaphenanthryl group, a benzoindenyl group, a cyclopentadienyl group, an indenyl group, or a fluorenyl group.

Y ′ is a methylene group, a silylene group, an ethylene group, a germylene group, or a boron group that has a bond with Cp and Z, and also has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. The substituents may be different or the same. Y ′ may have a cyclic structure.
Z is a ligand containing a nitrogen atom, an oxygen atom or a sulfur atom, coordinated to M ′ by a nitrogen atom, an oxygen atom or a sulfur atom, having a bond with Y ′, and also having hydrogen or a carbon number of 1 to 15 It is a group having a substituent.
M ′ is zirconium, hafnium, or titanium.
X ′ is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms.
n is an integer of 1 or 2.
Transition metal compounds represented by the general formula (6) are described in WO99 / 14221 , EP416815, and US6255496.

  In the coordination polymerization step of this production method, a single site coordination polymerization catalyst composed of a transition metal compound represented by the general formula (1) and a cocatalyst is preferably used. By using this transition metal compound, the present copolymer can be obtained with very high activity and productivity. Furthermore, since the copolymerizability with respect to aromatic polyene (divinylbenzene) is remarkably high, the conversion rate can be increased. For this reason, the aromatic polyene (divinylbenzene) remaining in the polymerization liquid obtained in the coordination polymerization process. ) Concentration / amount can be significantly reduced. Therefore, it is possible to use the polymerization liquid obtained in the coordination polymerization step, the aromatic polyene copolymerized macromer therein and the remaining unreacted aromatic vinyl compound (styrene) as they are in the next radical polymerization step. Highly useful. In contrast, when a single-site coordination polymerization catalyst that is not sufficiently copolymerizable with aromatic polyene (divinylbenzene) is used, the concentration / amount of aromatic polyene (divinylbenzene) remaining in the polymerization solution increases, When this polymerization solution is used in the radical polymerization step of the next step, the polymerization solution viscosity may be increased, the molding processability of the resulting cross-copolymer may be reduced, or gelation may be caused. In such a case, it is necessary to separate and recover the aromatic polyene copolymerized macromer from the polymerization solution obtained in the coordination polymerization step, dissolve it in a new solvent and use it in the radical polymerization step, which is disadvantageous industrially. It becomes.

When producing an ethylene-olefin-aromatic polyene copolymer or an ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer as an aromatic polyene copolymer macromer in the coordination polymerization step of this production method. The single site coordination polymerization catalyst composed of the transition metal compound represented by the above general formula (6) and a cocatalyst can also be suitably used. When this catalyst is used, an ethylene-olefin-aromatic polyene copolymer or an ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer having a sufficiently high molecular weight can be obtained. Preferred for polymer production.

As the co-catalyst used in the coordination polymerization step of this production method, a known co-catalyst conventionally used in combination with a transition metal compound can be used. As such a cocatalyst, an alumoxane or boron compound such as methylaluminoxane (or methylalumoxane or MAO) is preferably used. If necessary, alkylaluminum such as triisobutylaluminum and triethylaluminum may be used together with these alumoxanes and boron compounds. Examples of such promoters are described in EP-0874922A2, JP-A-11-130808, JP-A-9-309925, WO00 / 20426, EP0985689A2, and JP-A-6-184179. Cocatalysts and alkylaluminum compounds.
A co-catalyst such as alumoxane is used in an aluminum atom / transition metal atom ratio of 0.1 to 100,000, preferably 10 to 10,000, relative to the metal of the transition metal compound. If it is less than 0.1, the transition metal compound cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous.

  When a boron compound is used as the cocatalyst, it is used at a boron atom / transition metal atom ratio of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the transition metal compound cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The transition metal compound and the cocatalyst may be mixed and prepared outside the polymerization facility, or may be mixed in the facility during polymerization.

In producing the aromatic polyene copolymerized macromer in the coordination polymerization step of the present invention, the monomers, transition metal compounds, and promoters exemplified above are brought into contact with each other. Can be used.
As the above copolymerization method, polymerization is performed in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform. And the like, using a saturated aliphatic or aromatic hydrocarbon or halogenated hydrocarbon alone or in a mixed solvent. Preferably, a mixed alkane solvent, cyclohexane, methylcyclohexane, toluene, ethylbenzene or the like is used. The polymerization form may be either solution polymerization or slurry polymerization. Moreover, well-known methods, such as batch polymerization, continuous polymerization, prepolymerization, and multistage polymerization, can be used as needed.
It is also possible to use a single tank or a plurality of connected tank-type polymerization cans or a single linear or loop polymerization apparatus. Pipe-shaped polymerization cans include various known mixers such as dynamic or static mixers and static mixers that also remove heat, and various known mixers such as coolers equipped with heat removal thin tubes. You may have a cooler. Moreover, you may have a batch type prepolymerization can. Furthermore, methods such as gas phase polymerization can be used.

The polymerization temperature is suitably -78 ° C to 200 ° C. A polymerization temperature lower than −78 ° C. is industrially disadvantageous, and if it exceeds 200 ° C., the transition metal compound is decomposed, which is not suitable. Furthermore, industrially preferable, it is 0 degreeC-160 degreeC, Most preferably, it is 30 degreeC-160 degreeC.
The pressure at the time of polymerization is suitably from 0.1 to 100 atm, preferably from 1 to 30 atm, particularly industrially particularly preferably from 1 to 10 atm.

<Radical polymerization process>
In the radical polymerization step of the production method of the present invention, a radical polymerization initiator is used in the presence of the aromatic polyene copolymerized macromer obtained in the coordination polymerization step, the aromatic vinyl compound and the imidized unsaturated dicarboxylic acid anhydride. To conduct polymerization.
In the radical polymerization step of the production method of the present invention, a radical polymerization initiator is used in the presence of the aromatic polyene copolymerized macromer obtained in the coordination polymerization step, the aromatic vinyl compound and the unsaturated dicarboxylic acid anhydride. Polymerization.
The aromatic vinyl compound used here is the same as the aromatic vinyl compound used in the coordination polymerization step. The unsaturated dicarboxylic acid anhydride, maleic acid (maleic anhydride) anhydride, itaconic acid, citraconic acid or include anhydrides such as A co knit acid, preferably maleic anhydride is used. The imidized unsaturated dicarboxylic acid anhydride is an imidized unsaturated dicarboxylic acid anhydride obtained by a reaction with ammonia or amines having a substituent having 1 to 20 carbon atoms. The amines may contain one or more other OH groups, COOH groups, NH groups, SH groups, SiR ₃ groups, and Si (OR) ₃ groups in the structure. Examples of such amines include aniline (phenylamine), cyclohexylamine, methylamine, ethylamine, glycine, and ethanolamine.

Examples of most suitable imidized unsaturated dicarboxylic acid anhydrides include N-phenylmaleimide (available as Imirex-P from Nippon Shokubai Co., Ltd.), N-methylmaleimide, N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd. -C)), N-glycine maleimide and the like.
If the copolymer of aromatic vinyl compound (styrene) and unsaturated dicarboxylic acid anhydride is a cross chain, imidation treatment is usually performed to stabilize the unsaturated dicarboxylic acid anhydride unit and increase the heat resistance. Do. This imidization treatment is performed by reacting with the corresponding ammonia or primary amine by a known method. In this case, examples of the primary amine used include aniline (phenylamine), methylamine, ethylamine, glycine, cyclohexylamine, benzylamine, and ethanolamine. When the imidation treatment is performed in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, such as an autoclave, and when it is performed in a bulk melt state, an extruder equipped with a devolatilizer may be used. . The temperature of the imidization treatment is about 80 to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 80 ° C., the reaction rate is slow, and the reaction takes a long time and is not practical. On the other hand, when it exceeds 350 ° C., physical properties are deteriorated due to thermal decomposition of the polymer. A catalyst may be used during the imidation treatment. In that case, a tertiary amine such as triethylamine is preferably used.

Moreover, you may copolymerize the vinyl monomer copolymerizable with these. The copolymerization amount is from 0 to 50 mol% based on the total number of moles of the aromatic vinyl compound and unsaturated dicarboxylic anhydride or imidized unsaturated dicarboxylic anhydride used in the radical polymerization step. It is. Examples of vinyl monomers that can be copolymerized include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylate and ethyl acrylate, methyl methacrylate, and ethyl methacrylate. There are methacrylic acid ester monomers such as acrylic acid, methacrylic acid vinyl carboxylic acid monomers, acrylic acid amides, methacrylic acid amides, etc., among these monomers such as acrylonitrile, methacrylic acid esters, acrylic acid, methacrylic acid, etc. preferable.
Examples of crosslinkable monomers having two or more vinyl groups include diacrylate compounds such as divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylol. Triacrylate compounds such as methane triacrylate, dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diaryl compounds such as diaryl phthalate and diaryl maleate, aryl acrylate, aryl methacrylate, etc. There are unsaturated carboxylic acid aryls, and these may be used alone or in combination of two or more. . The amount of the crosslinkable monomer having 2 or more vinyl groups used is the total mole of the aromatic vinyl compound and unsaturated dicarboxylic anhydride or imidized unsaturated dicarboxylic anhydride used in the radical polymerization step. Preferably it is 0-1 mol% with respect to a number. If it is 1 mol% or more, a gel is likely to be formed.

In the radical polymerization step of the present invention, a known radical polymerization method can be used, but a known method that can be used for copolymerization of an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride or an imidized unsaturated dicarboxylic acid anhydride. It is preferable to use a radical polymerization polymerization initiator. As such examples, a peroxide-based (peroxide), an azo-based polymerization initiator, etc. can be freely selected by those skilled in the art as required.
Examples of these are the Japanese peroxide catalog organic peroxides 10th edition (downloadable from http://www.nof.co.jp/business/chemical/pdf/product01/Catalog_all.pdf), Wako Pure Chemical. It is described in catalogs and can be obtained from these companies.
Although there is no restriction | limiting in particular in the usage-amount of a polymerization initiator, Generally 0.001-5 mass parts is used with respect to 100 mass parts of monomers. In the case of using an initiator such as a peroxide (peroxide) or an azo polymerization initiator, or a curing agent, the curing treatment is performed at an appropriate temperature and time in consideration of its half-life. The conditions in this case are arbitrary according to the initiator and the curing agent, but generally a temperature range of about 50 ° C. to 150 ° C. is appropriate.
In the radical polymerization step of the present invention, a known chain transfer agent can be used mainly for the purpose of controlling the molecular weight of the cross chain. Examples of such chain transfer agents include mercaptan derivatives such as t-dodecyl mercaptan, α-styrene dimer and the like.

  The radical polymerization step of the present invention is performed after the above coordination polymerization step. At this time, the copolymer obtained in the coordination polymerization step uses any polymer recovery method such as a crumb forming method, a steam stripping method, a devolatilization tank, a direct devolatilization method using a devolatilization extruder, etc. Then, it may be separated and recovered from the polymerization solution and used in the radical polymerization step. However, it is economically preferable to use the residual olefin in the subsequent radical polymerization step after releasing or without releasing the residual olefin from the polymerization solution after the coordination polymerization. It is one of the features of the present invention that a polymer solution containing a polymer can be used in the radical polymerization step without separating the polymer from the polymerization solution. There is also an advantage that unreacted aromatic vinyl monomer (styrene) remaining in the polymerization solution in the coordination polymerization step can be used as a monomer for the next step. Use of the residual styrene monomer in the coordination polymerization step as an aromatic vinyl monomer in the radical polymerization step is very preferable from the viewpoint of simplification of the process.

As the solvent for the radical polymerization step, the same solvent as that for the coordination polymerization step can be used. However, when the polymer is separated and recovered from the coordination polymerization step polymerization solution and used in the radical polymerization step, a solvent different from the above coordination polymerization step can be used. Examples of such a solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
As the polymerization form, any known method used for radical polymerization can be used. The polymerization temperature is suitably from 30 ° C to 200 ° C. A polymerization temperature lower than 30 ° C is industrially disadvantageous in terms of stirring and mixing or high heat removal from the high viscosity of the polymer solution at a low temperature. If it exceeds 200 ° C, undesirable side reactions such as chain transfer occur. It is possible and not appropriate. Furthermore, industrially preferable, it is 50 to 150 degreeC. The pressure at the time of polymerization is suitably from 0.1 atm to 10 atm.

The composition of the copolymer comprising the aromatic vinyl compound and unsaturated dicarboxylic acid anhydride obtained in the radical polymerization step or imidized unsaturated dicarboxylic acid anhydride is determined by a known method, for example, ¹ H-NMR or ¹³ C-NMR. Can be sought. It can also be obtained by chemical analysis. A preferred composition (molar ratio of monomer units) is an aromatic vinyl compound: unsaturated dicarboxylic acid anhydride or imidized unsaturated dicarboxylic acid anhydride in the range of 40:60 to 99: 1, more preferably 50. : 50 to 70:30.
Further, the composition is preferably a composition range in which a glass transition temperature by DSC measurement is 130 ° C. or higher and 260 ° C. or lower, more preferably 160 ° C. or higher and 240 ° C. or lower. This composition can be controlled by the feed ratio of raw material macromers and monomers and the addition of these raw materials and / or radical polymerization initiators.

  In the radical polymerization step, the length of the cross chain and the molecular weight of the homopolymer that has not been crossed can be arbitrarily changed by appropriately adjusting the amount of the chain transfer agent added. The length (molecular weight) of the cross chain portion can be estimated from the molecular weight of the homopolymer that has not been cross-linked, but the length is preferably 3,000 to 150,000, more preferably 5,000 to 100,000, as a weight average molecular weight. Hereinafter, it is particularly preferably from 10,000 to 50,000. The molecular weight distribution (Mw / Mn) is preferably 5 or less, particularly preferably 3 or less.

<Resin composition>
The cross-copolymer of the present invention can be used as a composition with an aromatic vinyl compound polymer or olefin polymer described below. In this case, the present cross-copolymer can be used in the range of 1 to 99% by mass relative to the total mass of the composition. The cross-copolymer of the present invention exhibits relatively good compatibility with aromatic vinyl compound polymers and olefin polymers. Therefore, when this cross copolymer is used in the range of 1 to 50% by mass relative to the total mass of the composition, for example, impact resistance improvement and softening of the counterpart aromatic vinyl compound polymer (polystyrene etc.) and polyolefin When it is used in the range of 50 to 99% by mass relative to the total mass of the composition, it is effective for adjusting the physical properties (for example, elastic modulus) of the present cross copolymer and improving heat resistance and oil resistance. There is.

  The cross-copolymer of the present invention can be used as a compatibilizer for olefin polymers and polar polymers. In this case, the composition ratio of the olefin polymer and the polar polymer is arbitrary, and the present cross-copolymer can be used in the range of 1 to 50% by mass relative to the total mass of the composition.

  Furthermore, the cross-copolymer of the present invention can be used as a composition with a block copolymer-based polymer, and can be used in the range of 1 to 99% by mass with respect to the total mass of the composition. Since the cross-copolymer of the present invention has good softness and oil resistance, oil resistance can be imparted without impairing its softness and mechanical properties in a composition with a block copolymer-based polymer.

"Aromatic vinyl compound polymer"
A polymer of an aromatic vinyl compound alone or a statistical copolymer containing at least one monomer component copolymerizable with an aromatic vinyl compound and having an aromatic vinyl unit content of 10% by mass or more, preferably 30% by mass or more. Examples of the aromatic vinyl monomer used in the aromatic vinyl compound polymer include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt- Examples include butyl styrene, pt-butyl styrene, and α-methyl styrene. Moreover, the compound etc. which have a some vinyl group in one molecule, such as divinylbenzene, are also mentioned. In addition, a statistical copolymer between these plural aromatic vinyl compounds is also used. Note that the stereoregularity between the aromatic groups of the aromatic vinyl compound may be any of atactic, isotactic, and syndiotactic.

  Examples of the monomer copolymerizable with the aromatic vinyl compound include butadiene, isoprene and other conjugated dienes; acrylic acid, methacrylic acid, and amide derivatives and ester derivatives thereof; acrylonitrile, maleic anhydride and derivatives thereof. The type of copolymerization is statistical copolymerization. The above aromatic vinyl compound-based polymer has a polystyrene-equivalent weight average molecular weight of 30,000 or more, preferably 50,000 or more and 500,000 or less, preferably 300,000, in order to develop physical properties and molding processability as a practical resin. Must be: Further, a rubber component may be blended or grafted to impart impact resistance. Examples of the aromatic vinyl compound polymer used include isotactic polystyrene (i-PS), syndiotactic polystyrene (s-PS), atactic polystyrene (a-PS), rubber-reinforced polystyrene (HIPS), and acrylonitrile-butadiene. -Styrene copolymer (ABS resin), styrene-acrylonitrile copolymer (AS resin), styrene-methacrylic acid ester copolymer such as styrene-methyl methacrylate copolymer; styrene-diene copolymer (SBR, etc.) And hydrogenated products thereof; styrene-maleic acid copolymers; styrene-imidated maleic acid copolymers and the like.

"Olefin polymer"
An olefin homopolymer or copolymer composed of olefin monomers having 2 to 20 carbon atoms, such as high density polyethylene (LDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polyolefin elastomer ( POE), isotactic polypropylene (including i-PP, homo PP, random PP, block PP), syndiotactic polypropylene (s-PP), atactic polypropylene (a-PP), propylene-ethylene block copolymer , Propylene-ethylene random copolymer, propylene-butene copolymer, ethylene-norbornene copolymer, and ethylene-vinylcyclohexane copolymer. If necessary, a copolymer obtained by copolymerizing dienes such as butadiene and α-ω diene may be used. Examples thereof include an ethylene-propylene-diene copolymer (EPDM) and an ethylene-propylene-ethylidene norbornene copolymer. The above olefinic polymers require a polystyrene equivalent weight average molecular weight of 10,000 or more, preferably 30,000 or more and 500,000 or less, preferably 300,000 or less, in order to develop physical properties and molding processability as practical resins. It is.

"Block copolymer polymer"
It is a block copolymer having a diblock, triblock, multiblock, starblock or tapered block structure obtained by living polymerization by anionic polymerization or other polymerization methods. Examples thereof include styrene-butadiene block copolymer (SBS), styrene-isoprene copolymer (SIS), and hydrogenated products thereof (SEBS and SIPS). The above block copolymer-based polymer has a polystyrene-reduced weight average molecular weight of 5,000 or more, preferably 10,000 or more and 300,000 or less, preferably 200,000 or less, in order to develop physical properties and molding processability as practical resins. is necessary.

  The cross copolymer of the present invention can also be used as a composition with the following “other resins, elastomers, and rubbers”.

"Other resins, elastomers, rubber"
Examples include petroleum resins and hydrogenated products thereof, polyamides such as nylon; polyimides; polyesters such as polyethylene terephthalate; polyvinyl alcohol, natural rubber, silicone resin, and silicone rubber.

<Plasticizer>
The cross-copolymer of the present invention can be blended with any known plasticizer conventionally used for vinyl chloride and other resins. The plasticizer preferably used is an oxygen-containing or nitrogen-containing plasticizer, and is a plasticizer selected from an ester plasticizer, an epoxy plasticizer, an ether plasticizer, or an amide plasticizer.

These plasticizers have a relatively good compatibility with the ethylene-aromatic vinyl compound-aromatic polyene copolymer used in the cross-copolymer of the present invention and are difficult to bleed, and the glass transition temperature is lowered. The plasticizing effect that can be evaluated by the degree is large and can be suitably used. When these plasticizers are used, the ethylene-aromatic vinyl compound-aromatic polyene copolymer, particularly the ethylene-aromatic vinyl compound-divinylbenzene copolymer used in the cross-copolymer of the present invention has a specific effect. It has the effect of promoting the crystallization of the isotactic alternating structure of ethylene and aromatic vinyl units in the polymer to increase the degree of crystallinity, and also exhibits the effect of improving heat resistance and oil resistance in addition to the usual plasticizing effect I can do it.
On the other hand, for example, aromatic, aliphatic and alicyclic mineral oils tend to bleed due to low compatibility with the ethylene-aromatic vinyl compound-aromatic polyene copolymer of this composition, and the glass transition temperature is lowered. Since there are few plasticizing effects that can be evaluated by the degree to which it does, it may not be appropriate.

  Examples of ester plasticizers that can be suitably used in the present invention include phthalic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelate esters, citrate esters, acetyl citrate esters, and glutamate esters. Mono fatty acid esters such as succinic acid esters and acetic acid esters, phosphoric acid esters and polyesters thereof.

  Examples of the epoxy plasticizer that can be suitably used in the present invention include epoxidized soybean oil and epoxidized linseed oil.

Examples of ether plasticizers that can be suitably used in the present invention include polyethylene glycol, polypropylene glycol, copolymers and mixtures thereof.
Examples of the amide plasticizer that can be suitably used in the present invention include sulfonic acid amides. These plasticizers may be used alone or in combination.

  An ester plasticizer is particularly preferably used in the present invention. These plasticizers are excellent in compatibility with the ethylene-aromatic vinyl compound-aromatic polyene copolymer in this composition range, excellent in plasticizing effect (high glass transition temperature reduction degree), and advantageous in that there is little bleeding. There is. In addition, it has an excellent effect of promoting crystallization of an alternating structure of ethylene and aromatic vinyl units, which is suitable because it gives a high melting point. Furthermore, a plasticizer of adipic acid ester or acetylcitrate ester is most preferably used in the present invention. When these plasticizers are used, there is an advantage that the crystallization speed is remarkably high, crystals grow in a short time from melt molding, and various physical properties are stabilized.

  The compounding amount of the plasticizer is 1 part by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the cross copolymer of the present invention or the resin composition thereof. If the amount is less than 1 part by mass, the above effect is insufficient. If the amount is more than 30 parts by mass, bleeding, excessive softening, and excessive stickiness may be caused.

<Inorganic filler (filler)>
Hereinafter, the inorganic filler that can be used in the present invention will be described.
The inorganic filler is also used to impart flame retardancy to the present cross copolymer. The volume average particle diameter of the inorganic filler is preferably 50 μm or less, more preferably 10 μm or less. If the volume average particle diameter is less than 0.5 μm or exceeds 50 μm, the mechanical properties (tensile strength, elongation at break, etc.) will decrease when the film is formed, and this will cause a decrease in flexibility and pinholes. May end up. The volume average particle diameter is a volume average particle diameter measured by a laser diffraction method.

  Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenyl phosphite, ammonium polyphosphate, polyphosphate amide, zirconium oxide and magnesium oxide. , Zinc oxide, titanium oxide, molybdenum oxide, guanidine phosphate, hydrotalcite, snakerite, zinc borate, anhydrous zinc borate, zinc metaborate, barium metaborate, antimony oxide, antimony trioxide, antimony pentoxide, red phosphorus, Talc, alumina, silica, boehmite, bentonite, sodium silicate, calcium silicate, calcium sulfate, calcium carbonate, and magnesium carbonate, and one or more compounds selected from these are used. In particular, the use of at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, hydrotalcite, and magnesium carbonate is excellent in flame retardancy and is economically advantageous.

The compounding quantity of an inorganic filler is 1-300 mass parts with respect to 100 mass parts of this cross copolymer or its resin composition, Preferably it is the range of 5-200 mass parts. If the inorganic filler is less than 1 part by mass, flame retardancy may be inferior. On the other hand, when the inorganic filler exceeds 300 parts by mass, mechanical properties such as moldability and strength of the resin composition may be inferior.
When an inorganic filler is blended as a non-halogen flame retardant, char (carbonized layer) can be formed and the flame retardancy of a film or the like can be improved.

  The method for producing the resin composition, plasticizer composition, and filler composition of the present invention is not particularly limited, and a known appropriate blending method can be used. For example, melt mixing can be performed with a single-screw or twin-screw extruder, a Banbury mixer, a plast mill, a kneader, a heating roll, or the like. Prior to melt mixing, the raw materials may be mixed uniformly with a Henschel mixer, ribbon blender, super mixer, tumbler, or the like. The melt mixing temperature is not particularly limited, but is generally 150 to 300 ° C, preferably 200 to 250 ° C.

As a molding method for obtaining a molded body of the cross copolymer of the present invention or various compositions thereof, known methods such as vacuum molding, injection molding, blow molding, inflation molding, extrusion molding, profile extrusion molding, roll molding, calendar molding, etc. Can be used to form various sheets, films, bags, tubes, containers, foamed materials, foamed sheets, wire covering materials, and the like.
Furthermore, since the resin and the resin composition described in the present invention basically do not contain halogen, they have a basic feature that environmental adaptability and safety are high.

<Film, sheet>
When the cross copolymer of the present invention or the resin composition thereof is used as a film, the thickness is not particularly limited, but is generally 3 μm to 1 mm, preferably 10 μm to 0.5 mm. In order to produce a film or sheet comprising the resin composition of the present invention, a molding method such as inflation molding, T-die molding, calender molding, roll molding or the like can be employed. For the purpose of improving physical properties, the film of the present invention may be other suitable films such as isotactic or syndiotactic polypropylene, high density polyethylene, low density polyethylene (LDPE or LLDPE), polystyrene, polyethylene terephthalate, It can be multilayered with a film such as ethylene-vinyl acetate copolymer (EVA). Furthermore, the film of this invention can have self-adhesiveness and adhesiveness by selecting a composition suitably. However, when stronger self-adhesiveness is required, a multilayer film with another film having self-adhesiveness can be formed.

Although the specific use of the film of this invention is not specifically limited, It is useful as a general packaging material and a container, and can be used for a packaging film, a stretch film, a shrink film, various masking films, a protective film, a bag, and a pouch. it can.
<Tape base material>
Moreover, the film which consists of the resin composition which mainly contains the cross copolymer of this invention or a cross copolymer can be used as various tape base materials. Here, the resin composition mainly containing the cross-copolymer is contained in an amount of 50% by mass or more based on the tape base material mass (mainly the resin mass) excluding the above <inorganic filler>. Show. Other resins that may be blended as the resin composition are arbitrary, but are preferably the above “aromatic vinyl compound-based polymer”, “olefin-based polymer”, and / or “block copolymer-based polymer”. These are appropriately blended for adjusting the elastic modulus and modulus of the tape substrate.
The <inorganic filler> is suitably added to impart flame retardancy to the tape base material, and its blending amount is arbitrary within a known range, but is generally 1% by mass with respect to the total mass of the tape base material. It is 70 mass% or less.
When used as a tape substrate, the softness, oil resistance, and characteristic tensile properties of the present cross copolymer are advantageous. In order to form a pressure-sensitive adhesive tape using the composition containing the present cross-copolymer as a tape base material, known pressure-sensitive adhesives, additives, and known molding methods are used. Such pressure-sensitive adhesives, additives, and molding methods are described in, for example, Japanese Patent Publication No. 2000-111646. Adhesive tapes made of this tape base material include various binding tapes, sealing tapes, protective tapes, fixing tapes, various tapes for electronic materials, such as dicing tapes, back grinding tapes, masking tapes, etc. It can be suitably used as a tape base material. It is also useful as various labels.

  If necessary, the film of the present invention can be subjected to surface treatment such as corona, ozone, and plasma, application of an antifogging agent, application of a lubricant, printing, and the like. The film of the present invention can be produced as a stretched film subjected to stretching orientation such as uniaxial or biaxial as required. If necessary, the films of the present invention can be bonded to each other or to other materials such as thermoplastic resins by a technique such as fusion using a technique such as heat, ultrasonic waves or high frequency, adhesion using a solvent or the like.

  Furthermore, when the film of the present invention has a thickness of, for example, 100 μm or more, it can be formed as a tray for packaging foods, electrical products and the like by a technique such as vacuum forming, compression molding, and pressure forming.

  A known colorant, antioxidant, ultraviolet absorber, lubricant, stabilizer, and other additives can be blended with the tape base material as necessary, as long as the effects of the present invention are not impaired.

  In the present invention, the tape substrate is usually a cross-copolymer, and if necessary, an aromatic vinyl compound-based resin and an olefin-based resin and an inorganic filler (and a material blended as necessary, such as a filler). By dry blending, kneading the mixture using a Banbury mixer, roll, extruder, etc., and molding the kneaded product into a film by a known molding method such as compression molding, calendar molding, injection molding, extrusion molding, etc. can get.

Although the thickness of a tape base material changes also with uses of an adhesive tape, it does not restrict | limit in particular, For example, 40-500 micrometers, Preferably it is 70-200 micrometers, More preferably, it is 80-160 micrometers. In addition, the tape base material may have a single layer form or may have a multiple layer form.
<Dynamic vulcanizate>
The cross copolymer of the present invention can be made into a thermoplastic elastomer composition by dynamic vulcanization treatment together with other polymers. Specifically, the cross-copolymer of the present invention is 50% by mass to 95% by mass, preferably 60% by mass to 95% by mass, and the other polymer is 5% by mass to 50% by mass, preferably 5% by mass. It is a thermoplastic elastomer containing 40% by mass or less and obtained by dynamic vulcanization treatment. Here, the other polymer is the “aromatic vinyl compound polymer”, “olefin polymer”, “block copolymer polymer”, or “other resin, elastomer, rubber”.
More preferably, the thermoplastic elastomer composition obtained by dynamic vulcanization treatment containing 50 to 95% by mass of the cross-copolymer of the present invention and 5 to 50% by mass of a crystalline propylene polymer. It is a thing. Here, the crystalline propylene-based polymer has isotactic or syndiotactic stereoregularity among the above propylene-based polymers, and the crystalline melting point is 100 ° C. or higher and 170 ° C. or lower, preferably 120 ° C. or higher and 170 ° C. or lower. Is a polymer. The crystalline propylene-based polymer can be used alone or in combination.
The thermoplastic elastomer composition of the present invention is a blend of (A) the cross-copolymer of the present invention and (B) other polymer (such as a crystalline propylene-based polymer), an organic peroxide or a phenol resin crosslinking agent. It can be obtained by dynamic vulcanization treatment (dynamic heat treatment) in the presence. The dynamic vulcanization treatment is a technique in which dispersion and crosslinking are simultaneously caused by strongly kneading various compounds in a molten state under conditions where the crosslinking agent reacts. Y. It is described in detail in Coran et al. (Rub. Chem. And Technol. Vol. 53, 141 (1980)) and is widely known. The dynamic vulcanization is performed using a Banbury mixer, a closed kneader such as a pressure kneader, a single or twin screw extruder, and the like. The kneading temperature is usually 130 to 300 ° C, preferably 150 to 250 ° C. The kneading time is usually 1 to 30 minutes.

Specific examples of the organic peroxide used in the dynamic vulcanization treatment include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) -hexane, and 2,5-dimethyl. -2,5-di (tert-butylperoxy) -hexyne-3, di-tert-butyl peroxide and the like. In the present invention, the organic peroxide is preferably used in a proportion of 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the (A) cross-copolymer of the present invention. In addition, during the dynamic vulcanization treatment with organic peroxides, it is possible to add a peroxide crosslinking aid such as a maleimide compound and a polyfunctional vinyl monomer such as divinylbenzene or trimethylolpropane trimethacrylate. .
In addition to the polymer component, the “plasticizer” and “inorganic filler” can be added during the dynamic vulcanization treatment. “Plasticizer” is preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polymer component, and “inorganic filler” is preferably used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the polymer component.
The thermoplastic elastomer composition thus obtained can have both the high heat resistance of the crystalline propylene-based polymer and the characteristics such as the softness, oil resistance, and mechanical properties of the cross-copolymer of the present invention. In particular, the softness of the cross-copolymer of the present invention contributes to the expression of this feature. Moreover, it is considered that the fact that the cross-copolymer of the present invention has substantially no polyethylene crystallinity contributes to the improvement of the compatibility with the crystalline propylene polymer.

<Composition with petroleum resin / hydrogenated petroleum resin>
A petroleum resin and / or hydrogenated petroleum resin can be added to the cross copolymer of the present invention to obtain a resin composition. The blending is as described above, but preferably, the cross-copolymer of the present invention is in the range of 70 to 99% by mass, the petroleum resin and / or the hydrogenated petroleum resin in the range of 1 to 30% by mass, Particularly preferably, the cross copolymer of the present invention is in the range of 80% by mass to 99% by mass and the hydrogenated petroleum resin is in the range of 1% by mass to 20% by mass.
In the case of the above blending range, the moldability (specified by the MFR value) can be widely controlled without impairing the original mechanical properties of the cross copolymer, and can be adjusted to the MFR suitable for the molding method. The MFR of the resin composition increases as the blending amount of the petroleum resin and / or hydrogenated petroleum resin having a sufficiently lower molecular weight than the cross-copolymer increases. The MFR can be easily adjusted by those skilled in the art by adjusting the blending amount within the above range.
Furthermore, blending petroleum resin and / or hydrogenated petroleum resin within this range has the effect of significantly improving the transparency of the cross-copolymer. In consideration of coloring and transparency of the resin composition, a hydrogenated petroleum resin having high colorless transparency is preferable for this purpose. When the amount of petroleum resin and / or hydrogenated petroleum resin is less than the above range, the above effect is not sufficient. Some are not preferred. Of course, in the case where the adhesiveness is required, for example, an adhesive, a heat seal film or the like, it can be blended more than the above range.

<Wire covering material>
The cross-copolymer and resin composition described in the present invention can be suitably used as various electric wires and cable coating materials. In particular, a composition with a filler and / or a known flame retardant is excellent in softness, mechanical properties, abrasion resistance, and oil resistance, and is suitable for such applications. Moreover, in order to improve heat resistance, it is also possible to perform various well-known crosslinking methods, for example, the chemical crosslinking by a crosslinking agent, the crosslinking method by an electron beam, etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is limited to a following example and is not interpreted.

  The analysis of the copolymer obtained in the examples was carried out by the following means.

Determination of the styrene unit content in the copolymer was performed by ¹ H-NMR, and α-500 manufactured by JEOL Ltd. and AC-250 manufactured by BRUCKER were used as the equipment. It was dissolved in deuterated 1,1,2,2-tetrachloroethane, and the measurement was performed at 130 ° C. The area intensity of the peak derived from the phenyl group proton (6.5 to 7.5 ppm) and the proton peak derived from the alkyl group (0.8 to 3 ppm) was compared based on TMS.
The α-olefin (octene, hexene, propylene) unit content in the copolymer is similarly determined by ¹ H-NMR, and a peak derived from a methyl group proton derived from an α-olefin unit and a proton peak derived from an alkyl group. The area strength comparison was performed. In this method, with respect to the methyl group at the polymer terminal, the abundance ratio was obtained from the number average molecular weight obtained separately, the contribution was corrected, and the α-olefin unit content was obtained.

As for the molecular weight, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined using GPC (gel permeation chromatography). The measurement was performed under the following conditions.
Column: Two TSK-GEL MultiporeHXL-M φ7.8 × 300 mm (manufactured by Tosoh Corporation) were connected in series.
Column temperature: 40 ° C
Solvent: THF
Liquid feed flow rate: 1.0 ml / min.
Alternatively, the molecular weight was calculated under the following conditions using high temperature GPC (HLC-8121GPC / HT manufactured by Tosoh Corporation).
Column: Two TSK-GEL GMHHR-H HT (manufactured by Tosoh Corporation) were connected in series.
Column temperature: 145 ° C
Solvent: orthodichlorobenzene liquid flow rate: 1.0 ml / min.

  DSC measurement was performed under a nitrogen stream using an EXSTAR6000 manufactured by Seiko Instruments Inc. That is, using 10 mg of the resin composition, DSC measurement was performed from −100 ° C. to 260 ° C. at a temperature rising rate of 10 ° C./min, and the melting point, heat of crystal melting, and glass transition point were determined.

<Tensile test>
As a sample, a 1.0 mm thick sheet formed by a hot press method (temperature 260 ° C., 5 minutes, pressure 100 kg / cm 2) was used. In accordance with JIS K-6251, the sheet was cut into a No. 2 1/2 type test piece shape and measured at a tensile speed of 300 mm / min using an Orientec UCT-1T type tensile tester.

<A hardness>
The hardness A was determined according to the durometer hardness test method of JIS K-7215 plastic. This hardness is an instantaneous value.

<Total light transmittance, haze>
Transparency is Nippon Denshoku according to the method for testing the optical properties of JIS K-7375 plastic by forming a sheet to a thickness of 1.0 mm by the hot press method (temperature 260 ° C., time 5 minutes, pressure 100 kg / cm ² G). Total light transmittance and haze were measured using a turbidimeter NDH2000 manufactured by Kogyo Co., Ltd.
<Measurement of viscoelastic spectrum>
Using a dynamic viscoelasticity measuring apparatus (Rheometrics RSA-III), the frequency was 1 Hz and the temperature range was −60 ° C. to + 250 ° C. A sample for measurement (4 mm × 60 mm) was cut out from a film having a thickness of about 0.3 to 0.5 mm obtained by a hot press method (temperature 260 ° C., time 5 minutes, pressure 100 kg / cm ² G).
<Heat deformation test>
JIS No. 2 small 1/2 dumbbell is hung in a predetermined oven, heat-treated at a predetermined temperature for 1 hour, length measured before and after dumbbell longitudinal and width directions, and stretch / shrink deformation by the following formula The rate was determined. The maximum temperature at which the main elongation / shrinkage deformation rate falls within 5% in all the longitudinal and width directions was defined as the heat resistant deformation temperature.
Elongation deformation rate = 100 × (length after test−length before test) / length before test Shrinkage deformation rate = 100 × (length before test−length after test) / length before test This test was conducted up to 180 ° C.
<Room temperature oil resistance test>
JIS No. 2 small ½ dumbbells were immersed in engine oil and olive oil, and the breaking strength retention before and after immersion was determined by a tensile test 14 days later.
Breaking strength retention rate (%) = 100 × (breaking strength after immersion / breaking strength before immersion)

<Divinylbenzene>
The metadivinylbenzene used in the following examples is divinylbenzene manufactured by Nippon Steel Chemical Co., Ltd. (purity of 80% or more as a meta-para mixed product divinylbenzene).

<Catalyst (transition metal compound)>
In Examples A, B, C and E below, rac (racemic) -dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride (Formula 8) was used as a catalyst (transition metal compound). .

In Examples D, F, H, and I, tetramethylcyclopentadienyldimethylsilane tertiary butylamido titanium dichloride (Formula 9) was used as a catalyst (transition metal compound).

In Example G, diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride (Formula 10) was used as a catalyst (transition metal compound).

Example A (Synthesis of Macromer A)
<Coordination polymerization process>
Using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst, the reaction was carried out as follows.
Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a heating / cooling jacket.
4200 ml of cyclohexane, 600 ml of styrene and divinylbenzene (20.8 mmol as meta, paradivinylbenzene) manufactured by Nippon Steel Chemical Co., Ltd. were charged, and about 100 L of nitrogen was bubbled at an internal temperature of 60 ° C. to purge the system and the reaction solution. 25.2 mmol (described as MAO in the table) of triisobutylaluminum 8.4 mmol and methylalumoxane (manufactured by Tosoh Finechem Co., Ltd., MMAO-3A) were added on the basis of Al, and the mixture was heated and stirred at an internal temperature of 85 ° C. Immediately after introduction of ethylene and stabilization at a pressure of 0.45 MPa (3.5 kg / cm ² G), rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium was removed from a catalyst tank placed on the autoclave. About 30 ml of a toluene solution in which 17 μmol of dichloride and 0.98 mmol of triisobutylaluminum were dissolved was added to the reaction solution. While maintaining the internal temperature at 85 ° C. and supplying ethylene, the pressure was maintained at 0.45 MPa, and polymerization was carried out for 1 hour (coordination polymerization step). After completion of the reaction, the obtained polymer solution was put into a large amount of methanol solution and stirred vigorously to recover the polymer.
The polymer was air-dried at room temperature for 1 day and then dried at 50 ° C. in a vacuum until no mass change was observed. 680 g of polymer (macromer) was obtained, and the composition, molecular weight and the like were determined.

Example B (Synthesis of Macromer B)
Using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst, the reaction was carried out as follows.
Polymerization was carried out using an autoclave with a capacity of 50 L, a stirrer and a heating / cooling jacket.
Cyclohexane 26.5 L, styrene 3.5 L and divinylbenzene (meta, para-mixed product, 122 mmol as divinylbenzene) were charged, adjusted to an internal temperature of 60 ° C., and stirred (220 rpm). Dry nitrogen gas was bubbled into the liquid for several tens of minutes at a flow rate of 30 L / min to purge the water in the system and the polymerization liquid. Next, 20 mmol of triisobutylaluminum and methylalumoxane (manufactured by Tosoh Fachem Corp., MMAO-3A) were added based on Al (40 mmol (described as MAO in the table)), and immediately the system was purged with ethylene. After sufficiently purging, the internal temperature was raised to 90 ° C., ethylene was introduced, and after stabilizing at a pressure of 0.50 MPa (4.0 kg / cm ² G), from the catalyst tank installed on the autoclave, rac− About 50 ml of a toluene solution in which 80 μmol of dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were dissolved was added to the autoclave. Further, polymerization was carried out for about 90 minutes while maintaining the internal temperature at 90 ° C. and maintaining the pressure at 0.50 MPa while supplying ethylene.
After the polymerization is completed, the ethylene is immediately purged, and the resulting polymer solution is gradually poured into a vigorously stirred heated water containing a dispersing agent (pluronic) and potassium alum with a gear pump, the solvent is removed, and the polymer is dispersed in the heated water. A crumb (size about 1 cm) was obtained. This polymer crumb was centrifuged and dehydrated, air-dried at room temperature for one day and night, and then dried in a vacuum at 60 ° C. until no mass change was observed. As a result, about 2.8 kg of polymer (macromer) was obtained.

Example C (Synthesis of Macromer C)
The same polymerization apparatus and the same catalyst as in Example B were used and the same procedure was carried out except that the polymerization conditions were changed to those shown in Table 1.

Example D (Synthesis of Macromer D, ethylene-octene-divinylbenzene copolymer)
Tetramethylcyclopentadienyldimethylsilane tertiary butylamido titanium dichloride was used as a catalyst, and the reaction was carried out as follows.
Polymerization was carried out using the same 10 L autoclave as in Example A. 4200 ml of cyclohexane, 600 ml of 1-octene and divinylbenzene (42.4 mmol as meta, paradivinylbenzene) manufactured by Nippon Steel Chemical Co., Ltd. were charged, and the system and the reaction solution were purged by bubbling about 100 L of nitrogen at an internal temperature of 60 ° C. . 8.4 mmol of triisobutylaluminum and 25.2 mmol of methylalumoxane (manufactured by Tosoh Finechem Co., Ltd., MMAO-3A) were added based on Al, and the mixture was heated and stirred at an internal temperature of 100 ° C. Immediately after introduction of ethylene and stabilization at a pressure of 0.55 MPa (4.5 kg / cm ² G), 29 μmol of tetramethylcyclopentadienyldimethylsilane tertiary butylamido titanium dichloride was obtained from a catalyst tank placed on the autoclave. About 30 ml of a toluene solution in which 0.98 mmol of triisobutylaluminum was dissolved was added to the reaction solution. While maintaining the internal temperature at 100 ° C. and supplying ethylene, the pressure was maintained at 0.55 MPa, and polymerization was carried out for 30 minutes (coordination polymerization step). After completion of the reaction, the obtained polymer solution was put into a large amount of methanol solution and stirred vigorously to recover the polymer.
The polymer was air-dried at room temperature for 1 day and then dried at 50 ° C. in a vacuum until no mass change was observed. 530 g of polymer (macromer) was obtained, and the composition, molecular weight and the like were determined.

Example E (Synthesis of Macromer E)
The same polymerization apparatus and the same catalyst as in Example B were used and the same procedure was carried out except that the polymerization conditions were changed to those shown in Table 1.

Example F (Synthesis of macromer F, ethylene-hexene-divinylbenzene copolymer)
<Coordination polymerization process>
Tetramethylcyclopentadienyldimethylsilane tertiary butylamido titanium dichloride was used as a catalyst, and the reaction was carried out as follows.
Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a heating / cooling jacket. 4400 ml of toluene, 400 ml of 1-hexene and divinylbenzene (36 mmol as meta, paradivinylbenzene) were charged, and about 100 L of nitrogen was bubbled at an internal temperature of 50 ° C. to purge the system and the reaction solution. 28.4 mmol of triisobutylaluminum 8.4 mmol and methylalumoxane (manufactured by Tosoh Finechem Co., Ltd., MMAO-3A) were added based on Al, and the mixture was heated and stirred at an internal temperature of 95 ° C. Immediately after introduction of ethylene and stabilization at a pressure of 0.6 MPa (5.1 kg / cm 2 G), 33 μmol of tetramethylcyclopentadienyldimethylsilane tertiary butylamido titanium titanium chloride, triisobutyl was obtained from a catalyst tank placed on the autoclave. About 30 ml of a toluene solution in which 0.98 mmol of aluminum was dissolved was added to the reaction solution. While maintaining the internal temperature at 100 ° C. and supplying ethylene, the pressure was maintained at 0.6 MPa, and polymerization was carried out for 24 minutes (coordination polymerization step). After completion of the reaction, the obtained polymer solution was put into a large amount of methanol solution and stirred vigorously to recover the polymer.
The polymer was air-dried at room temperature for 1 day and then dried at 50 ° C. in a vacuum until no mass change was observed. 480 g of polymer (macromer) was obtained, and the composition, molecular weight and the like were determined.
Example I was also carried out under the conditions described in Table 1 using the same catalyst as F.

Example G (Synthesis of Macromer G, ethylene-hexene-divinylbenzene copolymer)
Diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride was used as a catalyst, and the reaction was carried out under the conditions shown in Table 1.

Example H (Synthesis of macromer H, ethylene-propylene-divinylbenzene copolymer)
The same catalyst as in Example D was used in the same procedure, except that the polymerization conditions were changed to those described in Table 1.
Polymerization was carried out using the same 10 L autoclave as in Example A. 4800 ml of cyclohexane and divinylbenzene (25 mmol as meta and paradivinylbenzene) were charged, and about 100 L of nitrogen was bubbled at an internal temperature of 60 ° C. to purge the system and the reaction solution. 8.4 mmol of triisobutylaluminum and 38 mmol of methylalumoxane (manufactured by Tosoh Finechem Co., Ltd., MMAO-3A) were added on the basis of Al, and the mixture was heated and stirred at an internal temperature of 95 ° C. Immediately after introducing propylene in 100 NL (normal liter) and then in ethylene and stabilizing at a pressure of 0.9 MPa (8.1 kg / cm 2 G), tetramethylcyclopentadienyl dimethylsilane tertiary from a catalyst tank installed on the autoclave. About 30 ml of a toluene solution in which 38 μmol of butyramide titanium dichloride and 0.98 mmol of triisobutylaluminum were dissolved was added to the reaction solution. While the internal temperature was 100 ° C. and ethylene was supplied, the pressure was maintained at 0.8 MPa, and polymerization was carried out for 3.5 hours (coordination polymerization step). After completion of the reaction, the obtained polymer solution was put into a large amount of methanol solution and stirred vigorously to recover the polymer.
The polymer was air-dried at room temperature for 1 day and then dried at 50 ° C. in a vacuum until no mass change was observed. 260 g of polymer (macromer) was obtained, and the composition, molecular weight and the like were determined.

The analysis results of the obtained macromer are shown in Table 2.

Example 1
<Radical polymerization process>
A 1 L autoclave was charged with 50 g of the macromer obtained in Example A of the coordination polymerization step, 21 g of styrene monomer, 229 g of toluene, and 1.6 g of a chain transfer agent n-DDM: 1-dodecanethiol (inside the autoclave). Was heated to 90 ° C. after nitrogen substitution. After completion of the temperature increase, a liquid mixture in which 400 g of toluene, 35 g of N-phenylmaleimide and 0.08 g of perbutyl O were dissolved was fed for 2 hours. After completion of the feed, the reaction was continued for another 30 minutes while maintaining 90 ° C. After completion of the reaction, the obtained polymer solution was put into a large amount of isopropyl alcohol solution, and stirred vigorously to recover the polymer.
The polymer was air-dried at room temperature for 1 day and then dried at 50 ° C. in a vacuum until no mass change was observed. 86 g of polymer (cross copolymer) was obtained.

Examples 2-14
Polymerization was carried out under the conditions described in Table 3 in the same procedure as in Example 1.

Example 15
Polymerization was carried out under the same conditions as in Example 1. However, the addition liquid using maleic anhydride as an unsaturated dicarboxylic anhydride instead of N-phenylmaleimide was fed. After completion of the reaction, the polymer was recovered by pouring into a large amount of isopropyl alcohol solution. Next, the polymer and aniline recovered as an imidization step were added, and imidization using triethylamine as a catalyst was performed in an autoclave, to obtain a cross copolymer having the same composition as in Example 1.

Comparative Example 1
Instead of the macromer obtained in the examples, divinylbenzene-free styrene-ethylene copolymer (styrene unit content 23 mol%, molecular weight Mw 120,000, Mw / Mn = 2.2, catalyst was rac-dimethylmethylenebis ( Polymerization was carried out under the conditions described in Table 3 in the same procedure as in Example 1, using 4,5-benzo-1-indenyl) zirconium dichloride and producing by the method described in JP-A-11-130808.

  Table 4 shows the measurement results of hardness, transparency, mechanical properties, and MFR of the polymers obtained in Examples 1 to 14 and Comparative Example 1. MFR was measured under a load condition of 260 ° C. and 10 kg.

The yield, composition, molecular weight and the like of the polymer obtained in the coordination polymerization step were determined. The divinylbenzene unit content of the polymer obtained in the coordination polymerization step was determined from the difference between the amount of unreacted divinylbenzene in the polymerization solution determined by gas chromatography analysis and the amount of divinylbenzene used for the polymerization.
The mass ratio of the aromatic polyene copolymer macromer obtained in the coordination polymerization process to the cross copolymer finally obtained through the radical polymerization process is the mass of the macromer used and the mass of the obtained cross copolymer. It was calculated from the ratio.

The composition of the cross-linked styrene-maleimide (N-phenylmaleimide) copolymer was determined from ¹³ C-NMR spectrum, but the styrene unit content was in the range of 50 to 55 mol%. Furthermore, the Tg derived from the cross chain obtained from the DSC measurement of the cross copolymer obtained this time was in the range of 210 ° C. to 230 ° C., so that the composition was almost in the vicinity of 50 mol% styrene unit content. I know that there is.
Table 2 shows the TUS / DOU values of the main chain ethylene-styrene-divinylbenzene copolymer obtained in this example coordination polymerization step according to US6096849. Here, TUS is the total content of vinyl groups contained in the copolymer, and is the sum of the content of vinyl groups derived from aromatic polyene (divinylbenzene) units and vinyl groups at the end of the polymer. Asked. The DOU value is the divinylbenzene unit content contained in the main chain ethylene-styrene-divinylbenzene copolymer.
In the aromatic polyene copolymerized macromer (ethylene-styrene-divinylbenzene copolymer, ethylene-olefin-divinylbenzene copolymer) obtained in the coordination polymerization process of the present invention, the TUS / DOU value is higher than 1.1. The value is approximately 1.2 or more and 10 or less, preferably 1.2 or more and 3 or less. When the TUS / DOU value is larger, the aromatic polyene unit content is too small, and the function as the cross copolymer of the present invention may be lost. In addition, when the TUS / DOU value is 1.1 or less, the aromatic polyene unit content is too much and the function derived from the main chain is easily lost, and the molding processability of the cross copolymer may be deteriorated. There is a risk that a gel component is generated in the cross-copolymer.

  The cross-copolymer of the present invention has a value of A hardness of 40 or more, D hardness of 70 or less, and a tensile elastic modulus of 1 MPa or more and 400 MPa or less. A dot spread of 30% or more is indicated. Furthermore, when the mass ratio with respect to the cross-copolymer finally obtained through the radical polymerization step of the aromatic polyene copolymer macromer obtained in the coordination polymerization step is 40% by mass or more and 80% by mass or less, the A hardness is 50 90 or less and a tensile modulus of 3 MPa or more and 100 MPa or less, and even better mechanical properties as a thermoplastic elastomer, that is, a breaking strength of 5 MPa or more and an elongation at break of 100% or more.

Furthermore, the cross-copolymers of the present invention all have a heat distortion temperature of 180 ° C. or higher, a remarkably high heat distortion temperature, and good mechanical properties. On the other hand, the copolymer (Comparative Example 1) synthesized using a styrene-ethylene copolymer gave a low heat distortion temperature in the heat distortion test (Table 5).

When the room temperature oil resistance of the cross-copolymer obtained in the present invention was evaluated, it was found that a high breaking strength retention was exhibited even in engine oil and olive oil. On the other hand, the copolymer synthesized using styrene-ethylene copolymer (Comparative Example 1) gave a result that the strength was significantly reduced and the oil resistance was poor (Table 6).

It can be seen that the cross-copolymer of the present invention has tensile properties closer to that of soft vinyl chloride compared to conventional ethylene-styrene copolymers and other soft resins. This characteristic can be shown by the ratio Rm value of stress (MPa) at the time of 100% elongation to the tensile elastic modulus (MPa) (= stress at the time of 100% elongation / tensile elastic modulus).
In the case of general soft vinyl chloride, the Rm value is in the range of about 0.15 to 0.5. It is understood that the Rm value of the cross-copolymer obtained in this example is approximately 0.2 to 0.6, which is a value in the same range as that of soft PVC, and has a tensile property similar to that of soft PVC, that is, texture. I understand that.
When the aromatic polyene copolymer macromer used is selected from α-olefins such as ethylene-octene-divinylbenzene copolymer, ethylene-hexene-divinylbenzene copolymer, and ethylene-propylene-divinylbenzene copolymer as the comonomer Although the mechanical properties are slightly inferior, a glass copolymer having a low glass transition temperature and excellent cold resistance can be obtained.

In FIG. 1, the viscoelasticity measurement result obtained by each Example and the comparative example is shown. In the drawing, the vertical axis notation E ′ (Pa), for example, 1.0E + 06 indicates 1 MPa.

The cross copolymer of the present invention has a storage elastic modulus of 1 × 10 ⁵ Pa or more up to 200 ° C. and has heat resistance characteristics as compared with the conventional ethylene-styrene copolymer and other soft resins. I understand. Further, a cross copolymer using an ethylene-octene-divinylbenzene copolymer as a macromer (Example 9), an ethylene-hexene-divinylbenzene copolymer (Example 11), an ethylene-propylene-divinylbenzene copolymer ( It can be seen that Example 13) is excellent in softness under low temperature conditions.
On the other hand, the polymer obtained in Comparative Example 1 softened and melted around 80 ° C. Further, the commercially available PP elastomer 1 softened and melted at around 120 ° C. Furthermore, the sample of the commercially available PP elastomer 2 was broken at around 120 ° C.

2 and 3 show TEM photographs of the polymers obtained in Example 4 and Comparative Example 1. FIG. In the case of Example 4, a very highly dispersed fine structure is observed (FIG. 2), whereas in Comparative Example 1, a phase separation structure having a size of several hundred nm is observed (FIG. 3).

It is a viscoelasticity measurement result obtained by each Example and the comparative example. 4 is a TEM photograph of the polymer obtained in Example 4. 2 is a TEM photograph of the polymer obtained in Comparative Example 1.

Claims (16)

A method for producing a cross copolymer comprising a coordination polymerization step and a radical polymerization step subsequent thereto , wherein in the coordination polymerization step, an ethylene-aromatic vinyl compound-aromatic polyene is used using a single site coordination polymerization catalyst. One or more aromatic polyene copolymer macromers selected from copolymers, ethylene-aromatic vinyl compounds-olefin-aromatic polyene copolymers, ethylene-olefin-aromatic polyene copolymers , and then radical polymerization A process for producing a cross-copolymer, characterized in that, in the step, an aromatic polyene copolymerized macromer, an aromatic vinyl compound, and an imidized unsaturated dicarboxylic acid anhydride are copolymerized. In the method for producing a cross-copolymer comprising a coordination polymerization step, a radical polymerization step and an imidization step, (1) in the coordination polymerization step, a single site coordination polymerization catalyst is used, and an ethylene-aromatic vinyl compound-aromatic One or more aromatic polyene copolymer macromers selected from aromatic polyene copolymers, ethylene-aromatic vinyl compounds-olefin-aromatic polyene copolymers, and ethylene-olefin-aromatic polyene copolymers , (2 ) Next, in the radical polymerization step, aromatic polyene copolymerized macromer, aromatic vinyl compound and unsaturated dicarboxylic acid anhydride are copolymerized, and (3) the resulting copolymer is imidized. A method for producing a cross-copolymer. The cross copolymer of claim 1 or 2 , wherein an aromatic polyene copolymer macromer having a sum of heats of crystal melting measured by DSC in a temperature range of 50 ° C to 200 ° C is 70 J / g or less. Manufacturing method of coalescence. The aromatic polyene copolymer macromer is an ethylene-aromatic vinyl compound-aromatic polyene copolymer, wherein the aromatic vinyl unit content is 5 mol% or more and 50 mol% or less, and the aromatic polyene unit content is 0.01 mol% or more. The method for producing a cross-copolymer according to any one of claims 1 to 3 , wherein the content is 1 mol% or less and the balance is an ethylene unit content. The aromatic polyene copolymer macromer is an ethylene-olefin-aromatic polyene copolymer having an olefin unit content of 5 mol% to 50 mol%, an aromatic polyene unit content of 0.01 mol% to 1 mol%, The method for producing a cross copolymer according to any one of claims 1 to 4 , wherein the balance is an ethylene unit content. The aromatic polyene copolymer macromer is an ethylene-olefin-aromatic vinyl compound-aromatic polyene copolymer, and the total content of the aromatic vinyl unit and the olefin unit is 5 mol% to 50 mol%. unit content 0.01 mol% 1 mol% or less, the manufacturing method of the cross-copolymer of any one of claims 1 to 5 in which the balance being an ethylene unit content. In the coordination polymerization step, either one of claims 1-6, characterized by using a single site coordination polymerization catalyst composed of a transition metal compound and a cocatalyst represented by the following general formula (1) Single A process for producing the cross copolymer according to item.


In the formula, A and B may be the same or different and are a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. Here, the substituted benzoindenyl group is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, It is a benzoindenyl group substituted by OSiR ₃ group, SiR ₃ group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). Adjacent substituents may be combined to form a 5- to 8-membered aromatic ring or alicyclic ring.
Here, the substituted indenyl group, the substituted cyclopentadienyl group, or the substituted fluorenyl group is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number of 7 20 alkylaryl group, a halogen atom, OSiR3 group, SiR ₃ group or a PR ₂ group (R is either a hydrocarbon group having 1 to 10 carbon atoms) indenyl group substituted with cyclopentadienyl groups, or Fluorenyl group.
Y has a bond with A and B, and in addition, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (in addition to 1 to 3 nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus A methylene group or a boron group having an atom or a silicon atom. The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium. In the coordination polymerization step, either one of claims 1-6, characterized by using a single site coordination polymerization catalyst composed of a transition metal compound and a cocatalyst represented by the following general formula (1) Single A process for producing the cross copolymer according to item.


In the formula, A and B may be the same or different and are groups selected from an unsubstituted or substituted benzoindenyl group and an unsubstituted or substituted indenyl group. Here, the unsubstituted or substituted benzoindenyl group is an unsubstituted or substituted benzoindenyl group represented by the general formulas (2), (3), and (4). The unsubstituted and substituted indenyl group is an unsubstituted and substituted indenyl group represented by the following general formula (5).






In general formulas (2), (3), and (4), R1 to R3 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and a halogen. An atom, OSiR ₃ group, SiR ₃ group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R1s, R2s, and R3s may be the same as or different from each other, and adjacent R1 and R2 groups may be combined to form a 5- to 8-membered aromatic or alicyclic ring.


In the general formula (5), R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, an SiR ₃ group, or It is a PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R4 may be the same or different from each other.
Y has a bond with A and B, and in addition, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (in addition to 1 to 3 nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus A methylene group or a boron group having an atom or a silicon atom. The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium. In the coordination polymerization step, either one of claims 1-6, characterized by using a single site coordination polymerization catalyst composed of a transition metal compound and a cocatalyst represented by the following general formula (6) Single A process for producing the cross copolymer according to item.


In the formula, Cp represents an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. The group to be selected. Here, a substituted cyclopentaphenanthryl group, a substituted benzoindenyl group, a substituted cyclopentadienyl group, a substituted indenyl group, or a substituted fluorenyl group is an alkyl in which one or more substitutable hydrogen atoms are 1 to 20 carbon atoms. Group, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, an SiR ₃ group or a PR2 group (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms) ) Substituted with a cyclopentaphenanthryl group, a benzoindenyl group, a cyclopentadienyl group, an indenyl group, or a fluorenyl group.
Y ′ is a methylene group, a silylene group, an ethylene group, a germylene group, or a boron group that has a bond with Cp and Z, and also has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. The substituents may be different or the same. Y ′ may have a cyclic structure. Z is a ligand containing nitrogen, oxygen or sulfur, coordinated to M ′ with nitrogen, oxygen or sulfur, having a bond with Y ′, and having hydrogen or a substituent having 1 to 15 carbon atoms. is there.
M ′ is zirconium, hafnium, or titanium.
X ′ is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms.
n is an integer of 1 or 2. The method for producing a cross-copolymer according to any one of claims 1 to 9 , wherein the aromatic polyene compound is divinylbenzene. The method for producing a cross-copolymer according to any one of claims 1 to 10 , wherein the aromatic vinyl monomer used in the radical polymerization step is styrene. The imidized unsaturated dicarboxylic acid anhydride monomer used in the radical polymerization step is one or more selected from N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide, and N-glycylmaleimide The method for producing a cross copolymer according to any one of claims 1 and 3 to 11 . Unsaturated dicarboxylic acid anhydride monomer to be used in the radical polymerization process, to maleic acid, itaconic acid, characterized in that one or at two or more selected from citraconic acid or anhydride of the respective acid A co knit acid, method for producing a cross-copolymer of claim 2 Symbol placement. Coordination polymerization are aromatic vinyl monomer is styrene in the step, the residual styrene monomer after the polymerization, any one of claims 1 to 13, characterized in that used as the aromatic vinyl monomer in the radical polymerization process A process for producing a cross-copolymer. Glass transition temperature, 130 cross-copolymer obtained by the production method of any one of claims 1-14, characterized in that ° C. or more and 260 ° C. or less. Molded body comprising a cross-copolymer obtained by the process of any one of claims 1-14.