JPS5946531B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition, more specifically a resin composition selected from synchropentadiene ring-opening polymers and copolymers containing synchropentadiene as a main component with norbornene derivatives or monocycloolefins. The present invention relates to a resin composition comprising at least one polymer selected from styrene homopolymers and copolymers of styrene.

The present inventors have discovered that synchropentadiene is (2) a soluble catalyst component of a reaction product obtained by reacting tungsten oxide or its salt with a Lewis acid and molecular oxygen in a mono-logenated hydrocarbon solvent; ) Polymerization with high activity and high yield using a catalyst system consisting of a combination of at least one or more organic metal compounds from Groups 1 to 2 of the periodic table, resulting in 100% ring-opened polymerization. We have already discovered and proposed a method for providing coalescence (Japanese Patent Application No. 51-99312).

Furthermore, the present inventors carried out ring-opening copolymerization of synchropentadiene and norbornene using the above catalyst system, and obtained a ring-opening copolymer of synchropentadiene and norbornene derivatives that is amorphous and easy to process. 51-92645).
Furthermore, as a result of investigating the polymerization catalyst system, we succeeded in obtaining a ring-opening polymer of synchropentadiene, which is amorphous and easy to process.

Many of these synchropentadiene monopolymers and copolymers have excellent heat resistance and transparency, and unlike conventionally obtained synchropentadiene polymers, they are easy to mold and process, making them suitable for a wide range of applications. You can expect it.

However, it has drawbacks such as slightly low fluidity during processing and deterioration when exposed to high temperatures during processing. On the other hand, styrene resins such as polystyrene have advantages such as good fluidity during processing and low prices, but they have poor heat resistance and, with the exception of two types, have poor impact resistance. It has the disadvantage of being low.

In order to solve these drawbacks, the present inventors conducted extensive research and found that by mixing both resins, the drawbacks of both can be compensated for and a resin composition having excellent properties can be obtained. invention has been achieved. That is, the resin composition of the present invention has properties that combine the high fluidity of a styrene resin and the heat resistance of a synchropentadiene ring-opening (co)polymer, and has high industrial value. The synchropentadiene ring-opening polymer used in the present invention is a linear polymer having the structure of the following formula [1]. For example, synchropentadiene is combined with a compound containing molybdenum or tungsten and the formula RnSnX4-n (where R is 1-1
Alkyl or aryl group having 8 carbon atoms, n-1 to
4.x is F,. Cl,. Br,. It can be synthesized by bringing it into contact with a catalyst system containing at least an organotin compound aridized with a halogen such as I.

Although either crystalline or amorphous synchropentadiene ring-opening polymers may be used in the present invention, it is preferable to use an amorphous polymer that is easy to knead. In the ring-opened copolymer of synchropentadiene and norbornene derivative used in the present invention, the norbornene derivative used as a comonomer has a general formula represented by the following formula [] [] or []. It is something that can be done.

Here, AlB of the formula []. C. D is hydrogen, carbon number 1-18
is an alkyl group, aromatic group, ester group, ether group, cyano group, amide group, halogen group, or other polar group, and Z in the formula [] is an oxygen atom, an alkyl group having 1 to 18 carbon atoms, or an aromatic substituted group. It is a nitrogen atom, and a structure containing an imide group or an acid anhydride group belongs to this category, and x and Y in the formula [] represent a structure in which hydrocarbons are bonded in a cyclic manner.

Examples of the aromatic group include phenyl group, pyridyl group, quinolyl group, naphthyl group, and others.

X in the above [] formula. The cyclic structure of Y hydrocarbons is, for example, -CH2- and -CH-CH/
Examples of the bond with \ include the CH2CH2 structure and \CH-CH/.

The above norbornene derivatives are produced by combining cyclopentadiene with a compound having a double bond such as an ethylenic olefin, a vinyl compound, or a cycloolefin.
Diels-Alder) reaction.

[0rganicReact10nsv01.4.60
-173 (1948)] Examples of compounds belonging to this category are as follows, but the present invention is not limited thereto.

As norbornene or alkyl-substituted norbornene, bicyclo[2,2,1]-heptene-2,5-methyl-bicyclo[2,2,1]-heptene 2,5,5-dimethyl-bicyclo[2,2,1] Heptene-2,5,6-dimethylbicyclo[2.2.1]-Heptene-2,5-ethylbicyclo[2.2.1]-Heptene-2,5-ethylidene-bicyclo[2.2. 1] - Hebten 1 2, 5
-Methyl-6-ethylbicyclo[2,2,1]-heptene-2,5,6-diethylbicyclo[2,2,1]-
Heptene-2,5-propylubicyclo[2.2.1]
-Heptene-2,5-butylbicyclo[2.2.1]-
Heptene-2,5-bentirubicyclo [2.2.1]
-Heptene-2,5-hexyrubicyclo[2.2.1
]-heptene-2,5-octylubicyclo[2-2.
1] 1-heptene-2,5-decylubicyclo[2.2.
1]-heptene-2,5-cyclohexyl-bicyclo[
2.2.1]-heptene-2 and the like.

As the aromatic group-substituted norbornene, 5-phenylubicyclo[2.2.1]-heptene-2,5-methyl~5
- phenylubicyclo[2.2.1]-heptene-2,
5-Ethyl-5-phenylbicyclo[2,2-1]-heptene-2,5,6-diphenylbicyclo[2,2,1]
]-heptene-2,5-(P-tolyl)-bicyclo[2
・2.1]-heptene-2,5-(P-tert-monobutylphenyl)-bicyclo[2.2.1]-heptene-2,
5-(P-chlorophenyl)-bicyclo[2.2.1]
-Heptene-2,5-α-naphthylbicyclo[2.2
・1]-heptene-2,5-α-antonyrubicyclo[2.2.1]-heptene-2,2-phenyl-1.4
;5,8-dimethano-1,2,3,4,4a,5,8.
8a-octahydronaphthalene, 2methyl-2-phenyl-1,4; 5,8-dimethano-1,2,3,4,4a
・5.8.8a.-Octahydronaphthalene 2-ethyl-2-phenyl 1.4; 5.8-dimethano-1.2.3
・4,4a,5,8,8a-octahydronaphthalene,
2-(P-tolyl)-1.4; 5.8-dimethano-1.
2,3,4,4a,5,8,8a-octahydronaphthalene 2(P-tert-butyruphenyl)-1,4;
5,8-dimethano-1,2,3,4,4a,5,8,8
a-octahydronaphthalene 2-α-naphthyl 1.4:
5,8-dimethano-1,2,3,4,4a,5,8,8
a-octahydronaphthalene and 2-α-antonyl-1,4;5,8-dimethano-1,2,3,4,4a.
Examples include 5.8.8a-octahydronaphthalene, 5-pyridylubicyclo[2.2.1]heptene-2, and 5-quinolylbicyclo[2.2.1]-heptene-2. As polar group-substituted norbornene derivatives, mono-logen group, ester group, cyano group, ether group, imide group,
Norbornene derivatives having a substituent such as an acid anhydride group, an amide group, or a polar group thereof can be mentioned. For example, as a norbornene derivative having a substituent containing a rogen atom or a rogen atom, 5-chloroubicyclo[2
・2.1]-heptene-2,5.5-dichlororubicyclo[2.2.1]-heptene-2,5.6-dichlororubicyclo[2.2.1]-heptene-2,5. 5,6 trichlororubicyclo[2,2,1]-heptene-2,5
・5.6.6-tetrachlorubicyclo [2.2.1
]-heptene-2,5-chloromethyl-bicyclo[2.
2.1]-heptene-2.5.6-dichloromethyl-bicyclo[2.2.1]-heptene-2.5-chloro-5
-Methyl-bicyclo[2.2.1]-heptene-2,5
-chloro6-methyl-bicyclo[2,2,1]-heptene-2,5-chloromethyl-6-methyl-bicyclo[2
・2.1]-heptene-2,5-(β-chloroethyl)
-Bicyclo[2.2.1]-heptene-2,5-(α-
chloroethyl)-bicyclo[2.2.1]-heptene-
2,5-(β-chloropropyl)-bicyclo[2.2.
1]-Heptene-2,5-(γ-chloropropyl)-bicyclo[2.2.1]-heptene-2,5-(β-chloroethyl)-6-methyl-bicyclo[2.2.1]heptene -2, and 5-chloromethyl-6-ethylbicyclo[2.2.1]-heptene-2, and .--rogen-based norbornene derivatives in which chlorine in the above norbornene derivatives is replaced with bromine.

Examples of norbornene derivatives having an ester group or a substituent containing an ester group include 5-methoxycarbonylbicyclo[2.2.1]-heptene-2, 5-ethoxycarbonylbicyclo[2.2.1]-heptene-2 , 5-butoxycarbonyl-bicyclo[2.2.1]-heptene-2:5-allyloxycarbonyl-bicyclo[2.2.
1]-Heptene-2,5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]Heptene-2,5-hexoxycarbonyl-6-methyl-bicyclo[2.2.1]
-Heptene-2,5-ethoxycarbonyl-6-phenylbicyclo[2,2,1] -Heptene-2,5-heptyl-6-octoxycarbonylbicyclo[2,2,1]
]-Heptene-2,5-methoxycarbonyl-6-methoxycarbonylmethyl-bicyclo[2,2,1]-Heptene-2,5,6-dimethoxycarbonyl-bicyclo[
2.2.1]-heptene ~ 2,5.6-diethoxycarbonylrubicyclo[2.2.1]-heptene-2,5.
5-dibutoxycarbonylbicyclo[2.2.1]heptene-2,5-methyl-6.6-dimethoxycarbonylbicyclo[2.2.1]-heptene2,5-ω-methoxycarbonylheptyl-6 Octylubicyclo [2
・2.1]-heptene-2,5-ω-methoxycarbonyl-2-decenyl-6-pentylbicyclo[2.2.
1]-heptene-2,5-ω-methoxycarbonylheptyl-6-2-octenyl-bicyclo[2.2.1]-heptene-2,5-acetoxymethyl-bicyclo[2.2
・1]-Heptene-2,5-acetoxymethyl-bicyclo[2.2.1]-heptene-2,5-propionoxymethyl-bicyclo[2.2.1]-heptene-2, and 5-stearoxy Methyl-bicyclo[2.2.1]-
Examples include heptene 2 and the like.

Examples of norbornene derivatives having a cyano group or a substituent containing a cyano group include 5-cyanobicyclo[2.2
・1]-Heptene-2,5,5-dicyanobicyclo[
2,2,1]-heptene-2,5,6-dicyanobicyclo[2,2,1]-heptene-2,5-cyano-5-
Methyl-bicyclo[2.2.1]-heptene-2,5-
Cyano-6-methyl-bicyclo[2.2.1]-hebutene-2,5-cyano-5-ethyl-bicyclo[2.2.
1]-heptene-2,5-cyano-6-isopropylubicyclo[2.2.1]-heptene-2,5-cyano-5
-n-octylbicyclo[2.2.1]-heptene-
2,5-cyano-6-phenylrubicyclo [2.2.1
]-heptene-2,5-ω-cyano-n-2-octenylrubicyclo[2.2.1]-heptene2,6-ω-cyano-n-hebutylrubicyclo[2.2.1]-heptene -2 and 5-n-pentyl-6-ω-cyano-2-
Examples include decenylrubicyclo[2.2.1]-heptene-2.

Examples of norbornene derivatives having an ether group or a substituent containing an ether group include 5-methoxybicyclo[
2.2.1]-heptene 2,5-ethoxybicyclo[
2.2.1] Heptene-2,5-n-propoxybicyclo[2.2.1]-Heptene-2,5-isopropoxybicyclo[2.2.1]-Hebutene-2,5- n-
Butoxybicyclo[2.2.1]-heptene-2,5
-cyclohexoxybicyclo[2.2.1]-heptene-2,5-methoxymethyl-bicyclo[2.2.1]
-Heptene-2,5-butoxymethyl-bicyclo[2.
2.1]-heptene-2.5-methoxy-6-methoxymethyl-bicyclo[2.2.1]-heptene-2 and 5-phenoxybicyclo[2.2.1]-hebutene-2. It will be done.

As a norbornene derivative having an imido group or a substituent containing an imido group, N-substituted-3,6-methylene-1.
2,3,6-tetrahydrosis-phthalimide K-Sat
]N-R, examples of which include the following.

N-methyl-3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-ethyl-3,6-
Methylene-1,2,3,6-tetrahydrosis-phthalimide, N-n-propyl-3,6-methylene-1,
2,3,6-tetrahydrosis-phthalimide, N-
Isopropyl-3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-n-butyl-3
・6-methylene-1,2,3,6-tetrahydrocysulfthalimide, N-tertiary-1-butyl-3,6-methylene-1,2,3,6-tetrahydrocysophthalimide, N-amyl-3. 6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-hexyl-3.
6-methylene 1,2,3,6-tetrahydrosis-phthalimide, N-octyl-3,6-methylene-1,2
・3,6-tetrahydrosis-phthalimide, N-decyl-3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-dodecyl-3,6-methylene-1,2,3,6-tetrahydro cis-phthalimide, N-cyclohexyl-3,6-methylene-1,2.
3,6-tetrahydrosis-phthalimide, N-(4
-methylcyclohexyl)-3,6-methylene-1,2
・3,6-tetrahydrosis-phthalimide, N-phenyl-3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-(4-methylphenyl)-
3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-(3-methylphenyl)-3.
6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-(4-ethylphenyl)-3,6-
Methylene-1,2,3,6-tetrahydrosis-phthalimide, N-methoxycarbonylmethyl-3,6-methylene-1,2,3,6-tetrahydrocysulfthalimide, N-ethoxycarbonylmethyl-3,6 -Methylene-1,2,3,6-tetrahydrosis-phthalimide, N-butoxycarbonylmethyl-3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide and N-acetoxy-3,6-methylene- 1, 2, 3
-6-tetrahydrosis-phthalimide.

As a norbornene derivative having an acid anhydride group, 2-
Norbornene-5,6-dicarboxylic anhydride is a typical example thereof. As a norbornene derivative having an amide group or a substituent containing an amide group, N-N-
Dimethyl-bicyclo[2.2.1]heptene-2-carboxylic acid amide-5, N-methyl-N-ethylbicyclo[2.2.1]-heptene-2-carboxylic acid amide-5
, N-N-di-n-propyl-bicyclo[2.2.1]-
Heptene-2-carboxylic acid amide-5, N-N-dicyclohexyrubicyclo[2.2.1]-heptene-2-
Carboxylic acid amide-5, N-N-diphenylubicyclo[2.2.1]-heptene-2-carboxylic acid amide-5
, N-N-dibenzylubicyclo[2.2.1]-heptene-2-carboxylic acid amide-5, N-N-dimethyl-
5-methyl-bicyclo[2.2.1]-heptene-2-
Carboxylic acid amide-5, N-N-diethyl-6-methyl-bicyclo[2.2.1]-heptene-2-carboxylic acid amide and N-N-N'.N'-tetramethyl-bicyclo[2. 2.1]-heptene-2-dicarboxylic acid amide-5.6.

Norbornene derivatives represented by the structural formula [] include tricyclo[6.2.1.05゛10]undecadiene-2.7, tricyclo[6.2.1.05゜10]
-undecadiene-2.6, tricyclo[7.2.1.
05゛11] Dodecadiene-2, 6, or -2, 7, -
2.8, tricyclo[8.2.1.05゛12]-tridecadiene 2.6, or 2.7, -2.8, tricyclo[5.2.1.05゛0]-decene-2, tricyclo [
6.2.1.05゜10〕-undecene-12, tricyclo[7.2.1.05゜11]-dodecene-12, tricyclo[8.2.1.05''12]-tridecene-12, etc. can be mentioned.

These ring-opening copolymers of norporene derivatives and synchropentadiene are synthesized using the same method as for the synchropentadiene ring-opening polymer described above.
-92645, 99312, (A soluble catalyst component of the reaction product obtained by reacting tungsten oxide or a salt thereof with a Lewis acid and molecular oxygen in a logenated hydrocarbon solvent, and (8) at least one or more compounds of organometallic compounds from Groups 1 to 3 of the periodic table.

The norbornene derivative in the above copolymer can be arbitrarily selected depending on the purpose of use and the type of polymer to be blended, and two or more types of norbornene derivatives may be copolymerized if necessary.

The proportion of the norbornene derivative in the copolymer can be arbitrarily selected, but it must be within the range of not losing the properties of the ring-opening polymer containing synchropentadiene as the main component, that is, 50%.
It is preferably less than % by weight. In the resin composition of the present invention, a copolymer of one type of synchropentadiene and a norbornene derivative may be used, or a copolymer of two or more types may be used.

Furthermore, a mixture of these and a synchropentadiene ring-opening polymer may be used. In the ring-opened copolymer of synchlopentadiene and monocycloolefin used in the present invention, the monocycloolefin used as a comonomer is, for example, cyclobutene, cyclobenzene, cyclooctene, cyclododecene, 1,5-cycloocta diene, 1-5,9-cyclododecatriene, and the like.

A ring-opened copolymer of monocycloolefin and synchropentadiene can be synthesized using the same method as for the ring-opened synchropentadiene polymer;
9312, (A) a soluble catalyst component of a reaction product obtained by reacting tungsten oxide or a salt thereof with a Lewis acid and molecular oxygen in a ~logenated hydrocarbon solvent, and (B) It can also be synthesized using a catalyst system comprising a combination of at least one type of organometallic compound from Group 1 to Group 1 of the periodic table.

The monocycloolefin in the copolymer has a purpose of use,
It can be selected arbitrarily depending on the type of polymer to be blended.
If necessary, two or more types of monocycloolefins may be copolymerized.

Furthermore, the proportion of monocycloolefin in the copolymer can be arbitrarily selected, but the proportion of monocycloolefin in the copolymer can be selected as desired without losing the properties of the ring-opening polymer whose main component is synchropentadiene.
It is preferably 0% by weight or less. In the resin composition of the present invention, a copolymer of one type of synchropentadiene and a monocycloolefin may be used, or a copolymer of the above types may be used.

Furthermore, a ring-opening polymer of synchropentadiene alone or a copolymer of synchropentadiene and a norbornene derivative may be used at the same time. The molecular weight of the synchropentadiene ring-opening (co)polymer used in the resin composition of the present invention can be selected from the range of 1,000 to 1,000,000 depending on the intended use of the composition and the type of polymer to be blended.

Examples of the styrene homopolymer or copolymer used in the present invention include polystyrene, styrene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/butadiene/acrylonitrile copolymer, styrene/acrylonitrile copolymer, and styrene/acrylonitrile copolymer.
Examples include styrene copolymers such as butadiene/methyl methacrylate copolymers, and graft or block copolymers containing styrene;
Examples include copolymers substituted with methylstyrene, but the present invention is not limited thereto. These styrene resins can be arbitrarily selected depending on the purpose of use and the properties of the synchropentadiene ring-opening (co)polymer to be blended, and can be used alone or in a mixture of two or more.

The blending ratio of the synchropentadiene ring-opening (co)polymer and styrene alone or copolymer is arbitrary, and the proportion of the synchropentadiene ring-opening (co)polymer in the composition can be determined depending on the properties of the resin used and the intended use of the blend. The proportion can be selected in the range of 99 to 1% by weight.

When a small amount of styrene-based resin is blended into a synchropentadiene ring-opening (co)polymer, processability is improved without impairing the excellent heat resistance of the synchropentadiene ring-opening (co)polymer. When a small amount of synchropentadiene ring-opening (co)polymer is blended with the resin, heat resistance or mechanical properties can be improved without reducing processability. Furthermore, by appropriately selecting the type of synchropentadiene ring-opening (co)polymer, the mixing ratio thereof, the type or mixing ratio of the styrene resin to be blended, and the blending ratio of both, heat resistance, processability, and mechanical properties can be improved. A desired resin composition with excellent physical properties can be obtained.

Any commonly used method may be used to mix the synchropentadiene ring-opened (co)polymer and the styrene resin.

Examples include melt-kneading using an extruder, mill, Banbury mixer, kneader blender, etc., and a method in which both resins are made into a solution or emulsion and then mixed and dried. This allows you to choose the most suitable method from among these. Stabilizers, ultraviolet absorbers, colorants, plasticizers, lubricants, flame retardants, fillers, and the like may be added to the resin composition thus obtained, if necessary. Compression molding of the resin composition obtained by the present invention,
It can be easily molded into various shapes by molding methods such as extrusion molding, injection molding, and blow molding, and any molding method can be selected depending on the properties of the resin composition and the purpose of use.

Furthermore, by utilizing double bonds in the synchropentadiene ring-opening (co)polymer contained in the present composition, crosslinking and curing can be performed during or after molding, thereby further improving heat resistance.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Example 1 (
a) 800 ml of dehydrated and purified toluene and 200 ml of synchropentadiene were charged into a sufficiently dried 1.51 autoclave which had been purged with nitrogen, and to this were added 0.74 mm of 1-hexene, 0.739 mm of tungsten hexachloride, 1.48 mm of tetraethyltin, as a molecular weight regulator.
1 was added, and polymerization was carried out at room temperature for 5.0 hours.

After the polymerization reaction was completed, the polymerization system was a homogeneous and viscous solution.

After adding 5 ml of monoethanolamine to this to stop the polymerization and adding BHT3y as a stabilizer, the reaction solution was poured into a large amount of methanol to precipitate the polymer, and the obtained polymer was vacuum-dried at 60°C. . Polymerization conversion rate is 10
At 0%, no gel was contained, and the [η] of the polymer in toluene at 30°C was 0.98. (b) The synchropentadiene ring-opening polymer obtained by the above method and polystyrene (trade name: Kostyrene GP) were each dissolved in toluene to prepare a solution having a concentration of 5% by weight.

Next, both solutions were uniformly mixed at a predetermined ratio, and then poured into methanol to precipitate the polymer, followed by drying to obtain a resin composition. This was pressed under pressure at 200° C. to produce a film with a thickness of about 0.2 ml, and the softening point under 4k9/Cd tension was measured, and the results shown in the table below were obtained. Example 2 The softening point of the resin composition was determined in the same manner as in Example 1, except that rubber-modified polystyrene (trade name S5OO) was used instead of the polystyrene used in Example 1.

Example 3 Each of the compositions used in Examples 1 and 2 was tested using a Koka-type flow tester (nozzle 1×1 mm, load 100 k9/Crl), and the temperature at which the plunger dropped by 4 mm was determined.

Example 4 Using phenylnorbornene (5-phenylubicyclo[2.2.1]-heptene-2) as a comonomer, dicyclopentadiene-phenylnorbornene ring opening was performed in the same manner as in Example 1. A copolymer (phenylnorbornene content: 10 mol%) was synthesized.

This copolymer was mixed with polystyrene and polystyrene in the same manner as in Example 1.
The softening point and plunger drop temperature (41n0) of the composition were investigated by mixing it with rubber-modified polystyrene.Example 5 Using cyclobenzene as a comonomer,
A dicyclopentadiene-cyclopentene copolymer containing synchropentadiene as a main component was synthesized by the method described in No. 9312.

Claims (1)

[Scope of Claims] 1. 1 to 99% by weight of a homopolymer of dicyclopentadiene or a ring-opened copolymer with a cycloolefin copolymerizable with dicyclopentadiene and 1 to 99% by weight of a homopolymer or copolymer of styrene. % by weight. 2. The resin composition according to claim 1, wherein the cycloolefin is a norbornene derivative. 3. The resin composition according to claim 1, wherein the cycloolefin is a monocycloolefin. 4. The resin composition according to claim 1, wherein the cycloolefin is a mixture of a norbornene derivative and a monocycloolefin. 5. The resin composition according to claim 1, wherein a predominant amount of the ring-opened copolymer is a dicyclopentadiene unit represented by the following structural formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼