JPH02102256A - Hydrogenated ring-opening polymer composition - Google Patents

Abstract

PURPOSE:To make it possible to form a hydrogenated ring-opening polymer composition excellent in impact resistance as well as in heat resistance, thermal aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., by mixing a specified hydrogenated ring-opening polymer with an elastomer. CONSTITUTION:100 pts.wt. hydrogenated ring-opening polymer which is a polymer obtained by hydrogenating a ring-opening polymer comprising at least one member selected from among cycloolefin components represented by formulas I and II (wherein n and m are each 0 or a positive integer; l is an integer >=3; and R1-R10 are each a hydrogen atom, a halogen atom or a hydrocarbon group) and having an intrinsic viscosity [eta] in the range of 0.05-10dl/g as measured in decalin at 135 deg.C, and a softening temperature (TMA) >=70 deg.C is mixed with an elastomer one of whose glass transition points is below 70 deg.C.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a hydrogenated ring-opening compound that has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity, as well as excellent impact resistance. The present invention relates to polymer compositions.

=2 [Prior art] Japanese Patent Application Laid-open No. 127728/1983 includes 1, 4, 5.
8-dimethano-1,2,3,4,4a,5,8,8a-
A ring-opened homopolymer of octahydronaphthalene or a ring-opened copolymer of the above-mentioned cyclic olefin and a norbornene type comonomer has been proposed as a resin having excellent chemical resistance, solvent resistance, and the like. However, such ring-opened polymers have an unsaturated bond in the polymer main chain, and therefore have a problem of poor heat resistance and heat aging resistance.

On the other hand, JP-A-60-26024 proposes a hydrogenated ring-opening polymer obtained by hydrogenating the ring-opening polymer as a resin with improved heat resistance and heat aging resistance. The problem is that it is brittle and has poor impact resistance.

[Problem to be solved by the invention]

The present inventors have improved impact resistance without impairing the excellent properties of the hydrogenated ring-opening polymer described above, such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties. As a result of intensive studies, we discovered that a composition consisting of a hydrogenated ring-opening polymer with a specific softening temperature (TMA) and an elastomer with a specific glass transition temperature has the excellent properties described above. The present invention has now been completed.

The purpose of the present invention is to solve the problems associated with the prior art as described above, and to provide a material that has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., as well as excellent impact resistance. An object of the present invention is to provide a hydrogenated ring-opening polymer composition.

[Means to solve the problem]

The hydrogenated ring-opening polymer composition according to the present invention is obtained by hydrogenating a ring-opening polymer consisting of (A) at least one cyclic olefin component represented by the following general formula [1] or [■]. A hydrogenated ring-opening polymer having an intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.05 to 10 dQ/g and a softening temperature (TMA) of 70°C or higher. (B) one of which is formed from an elastomer having a glass transition temperature of less than 70°C, based on 100 parts by weight of component (A) above;
A composition in which component B) is present in an amount of 5 to 100 parts by weight.

General formula [where n and m are both 0 or a positive integer, a is an integer of 3 or more, and R1 to Rio each represent a hydrogen atom, a halogen atom, or a hydrocarbon group.

] The hydrogenated ring-opening polymer composition according to the present invention is formed from the above-mentioned component (A) and component (B),
Since component (B) is present in an amount of 5 to 100 parts by weight per 00 parts by weight, heat resistance, heat aging resistance, chemical resistance,
It has excellent solvent resistance, dielectric properties, rigidity, etc., as well as excellent impact resistance.

The hydrogenated ring-opening polymer (A) constituting the hydrogenated ring-opening polymer composition according to the present invention before being subjected to the hydrogenation reaction is a ring-opening polymer composed of a specific cyclic olefin component. It is a combination.

The above cyclic olefin component has the general formula [I] or [
■] In the ring-opening polymer before hydrogenation reaction, the cyclic olefin component forms a structure represented by the following general formula [l11) or [■]. .

General formula [where n, m, Q and R1 to RIO are the same as above]. ] The cyclic olefin of the hydrogenated ring-opening polymer component (A) constituting the hydrogenated ring-opening polymer composition according to the present invention before the hydrogenation reaction has the general formula [I] and (I
T) is at least one type of cyclic olefin selected from the group consisting of unsaturated monomers represented by T), and the unsaturated monomer component may consist of one type alone;
and [II].

The cyclic olefin represented by the general formula [1] is prepared by combining cyclopentadiene and the corresponding olefin with the Diels method.
It can be easily produced by condensation by Alder reaction. Similarly, the cyclic olefin represented by the general formula [11] can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

Specifically, the cyclic olefin represented by the general formula (1) is a compound listed in Table 1 or l.

4.5.8-dimethano-1,2,3,4,4a,5,8
, 8a-octahydronaphthalene, as well as 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,5
, 8.8a-octahydronaphthalene, 2-ethyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8,8a octahydronaphthalene, 2-propyl-1,
4,5,8 dimethanol-1,2,3,4,4a,5,8,
8a-octahydronaphthalene, 2-hexyl-1,4
,5,8-dimethano-1,2,3,4゜4a,5,8,
8a-octahydronaphthalene, 2,3-dimethyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8,8a-octahydronaphthalene, 2-methyl-3-
Ethyl-1,4,5,8-dimethano-1,2,3,4,
4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4
a.

5.8,8a-octahydronaphthalene, 2-bromo-
1,4゜5.8-dimethano-1,2,3,4,4a,5
, 8,8a-octahydronaphthalene, 2-fluoro-
1,4,5,8-dimethano-1,2゜3.4,4a,5
, 8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a
, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5°8-dimethano-1,2,3,4
, 4a, 5,8,8a-octahydronaphthalene, 2-
n-Butyl-1,4,5,8-dimethano-1,2,3°4.4a,5,8,8a-octahydronaphthalene, 2
-isobutyl-1,4,5,8-dimethano-1,2,3
, 4,4a+5.8.8a-octahydronaphthalenes such as octahydronaphthalene, and the compounds listed in Table 2.

Further, specific examples of the cyclic olefin represented by the general formula (n) include the compounds shown in Tables 3 and 4.

20- The ring-opening polymer (A) constituting the hydrogenated ring-opening polymer composition according to the present invention before being subjected to the hydrogenation reaction has the general formulas [1] and (n ) is an essential component, but in addition to the above-mentioned essential components, other copolymerizable cyclic olefin components may be used as necessary to the extent that the object of the present invention is not impaired. may contain. Specifically, the optionally copolymerizable cyclic olefins include cyclobutene, cyclopentene, cycloheptene, in an amount less than equimolar to the cyclic olefin component units represented by general formulas [I] and [II] in the copolymer to be produced. cyclooctene, cyclononene,
Cyclodecene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene,
Methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, ethylcyclooctene, dimethylcyclopentene, dimethylcycloheptene, dimethylcyclooctene,
Examples include monocyclic olefins having 4 or more carbon atoms, such as dimethylcyclononene, dimethylcyclodecene, cyclooctadiene, and cyclodecadiene.

The ring-opening polymer before the hydrogenation reaction of the hydrogenated ring-opening polymer component (A) constituting the hydrogenated ring-opening polymer composition according to the present invention is selected from the general formulas [1) and [II]. It can be produced by a conventional ring-opening polymerization method for cyclic olefins using monomer components and other monomer components copolymerized if necessary as raw materials. Examples of polymerization catalysts include systems consisting of halides such as ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum, and tungsten, nitrates or acetylacetone compounds, and reducing agents such as alcohols and tin compounds, or titanium,
A system consisting of a halogen compound such as vanadium, zirconium, tungsten, or molybdenum, an acetylacetone compound, and an organic aluminum compound can be used.

The hydrogenated ring-opening polymer (A) in the present invention is obtained by hydrogenating the ring-opening polymer obtained as described above.

Hydrogenation of the ring-opened polymer is carried out by conventional hydrogenation methods.

As the hydrogenation catalyst, those used in the hydrogenation of olefin compounds can generally be used. Specifically, heterogeneous catalysts include nickel, palladium, platinum, etc., or solid catalysts in which these metals are supported on supports such as carbon, silica, diatomaceous earth, alumina, titanium oxide, etc., such as nickel/silica, nickel, etc. /diatomaceous earth, palladium/carbon, palladium/silica, palladium/diatomaceous earth, palladium/alumina, etc. Homogeneous catalysts include those based on metals from group Ⅰ of the periodic table, such as nickel naphthenate/triethylaluminum, cobalt octenoate/n
Examples include those consisting of Ni and Co compounds such as -butyllithium, nickel acetylacetonate/triethylaluminum, and organometallic compounds of metals from Groups 1 to 1 of the periodic table, or Rh compounds.

The hydrogenation reaction of the ring-opening polymer is carried out in a homogeneous or heterogeneous system depending on the type of catalyst, under a hydrogen pressure of 1 to 150 atmospheres, at a temperature range of 0 to 180°C, preferably 20 to 100°C. It will be done. The hydrogenation rate depends on hydrogen pressure, reaction temperature,
This can be adjusted by adjusting the reaction time, catalyst concentration, etc., but in order for the hydride to exhibit excellent heat deterioration resistance and light deterioration resistance, the main chain double bonds in the polymer should be at least 50%, preferably at least 80%. , more preferably 90% or more is hydrogenated.

The hydrogenated ring-opening polymer (A) constituting the hydrogenated ring-opening polymer composition according to the present invention has an intrinsic viscosity [η] of 0.05 to 10 dQ/g, preferably measured in decalin at 135°C. It is in the range of 0.08 to 5 molecules/g.

Further, the softening temperature (TMA) of the hydrogenated ring-opening polymer (A) measured with a thermo-mechanical analyzer is 70°C or higher, preferably 90 to 300°C, more preferably 100°C or higher.
-250°C. Also, hydrogenated ring-opening polymer (A)
The glass transition temperature (Tg) of is usually in the range of 50 to 250°C, preferably 70 to 230°C.

Further, the crystallinity of this hydrogenated ring-opening polymer (A) measured by X-ray diffraction is usually 0 to 10%, preferably 0.
-7%, particularly preferably 0-5%.

The elastomer component (B) constituting the hydrogenated ring-opening polymer composition according to the present invention has one glass transition temperature (Tg).
is less than 70°C, preferably in the range of -100°C to 40°C, more preferably in the range of -80°C to 10°C.

Specifically, such elastomer component (B) includes ethylene/propylene random copolymer, ethylene/propylene random copolymer, and ethylene/propylene random copolymer.
Butene random copolymers, ethylene/propylene/diene ternary copolymers, propylene/butene random copolymers, and other olefinic di-stomers, butyl rubber, styrene/butadiene rubber, styrene/butadiene/styrene block copolymers (SBS), styrene・Isoprene・
Styrenic elastomers such as styrene block copolymers (SIS), hydrogenated products of SBS, hydrogenated products of SIS, diene elastomers such as natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, Acrylic rubber, fluoro rubber,
Examples include silicone rubber.

The hydrogenated ring-opening polymer composition according to the present invention is prepared by adding 100 parts by weight of the hydrogenated ring-opening polymer (A) to the hydrogenated ring-opening polymer (B).
) is present in an amount of 5 to 100 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 10 to 70 parts by weight.

If the amount of the elastomer (B) is less than 5 parts by weight with respect to 100 parts by weight of the hydrogenated ring-opening polymer (A), although the rigidity is excellent, the impact resistance is unfavorable.
If it exceeds 0.00 parts by weight, although the impact resistance is excellent, the rigidity is low and the balance between rigidity and impact strength is poor, which is not preferable.

The method for producing the hydrogenated ring-opening polymer composition according to the present invention includes:
Known methods can be applied, including a method in which hydrogenated ring-opening polymer (A) and elastomer (B) are blended in an extruder or the like, and (A) and (B) are mixed in a suitable solvent such as heptane, hexane, A solution blending method is carried out by sufficiently dissolving a saturated hydrocarbon such as decane or cyclohexane, or an aromatic hydrocarbon such as toluene, benzene, or xylene, or an extruder etc. The method of kneading can be mentioned.

The softening temperature (TMA) measured by a thermomechanical analyzer of the hydrogenated ring-opening polymer composition according to the present invention
) is usually 80 to 270°C, preferably 100 to 230°C.
in the range of ℃.

The hydrogenated ring-opening polymer composition according to the present invention contains a hydrogenated ring-opening polymer (A) and an elastomer (B) as essential components, and also contains a heat-resistant stabilizer, a weather-resistant stabilizer, and an antistatic agent. agent, slip agent, anti-blocking agent, anti-fog agent,
Lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended, and their blending ratios are appropriate. For example, specific stabilizers that may be added as optional ingredients include tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, β-(3,5- di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2'-oxamidobis[ethyl-3(3,5-di-t-butyl-
Phenolic antioxidants such as 4-biloxyphenyl) propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, penta Examples include polyhydric alcohol fatty acid esters such as erythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, such as tetrakis[methylene-3(3,5-di-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate, and glycerin]. Examples include combinations with monostearate.

The hydrogenated ring-opening polymer composition according to the present invention contains the hydrogenated ring-opening polymer (A) and the elastomer (B) as essential components, but fillers may also be added to the composition. The proportions are appropriate amounts. For example, fillers that can be added as optional ingredients include silica, diatomite, alumina, titanium oxide, magnesium oxide, pumice particles, pumice balloons, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, Calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass peas, calcium silicate, monomolinite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber , silicon carbide fiber, silicon nitride fiber, polyethylene fiber, polypropylene fiber, polyamide fiber, polyester fiber, carbon fiber, etc.

The hydrogenated ring-opening polymer monomer composition of the present invention can be used for resin molded products and other uses similar to conventional ones.

The hydrogenated ring-opening polymer composition of the present invention can be used for instrument panels, console boxes, meter clusters,
Automotive parts such as column covers, grills, door mirrors, fenders, bonnets, and radiator grills; housings for office equipment such as power tools, word processors, personal computers, copiers, and printers; cameras;
Housings for various instruments, housings for home appliances such as microwave ovens, electric kettles, refrigerators, pots, vacuum cleaners, washing machines, etc.
It can be used in a variety of fields, including sirocco fans for near conditioners, water tanks for electric irons, microwave oven supplies, LCD display boards, printed circuit boards, high-frequency circuit boards, films, sheets, and helmets.

〔Effect of the invention〕

The hydrogenated ring-opening polymer composition according to the present invention has heat resistance, heat aging resistance, chemical resistance, and It has excellent solvent resistance, dielectric properties, rigidity, and impact resistance.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition,
The methods for measuring and evaluating various physical property values in the present invention are shown below.

(1) Heat distortion temperature (TMA): Seiko Electronics TM
AIO (Thermo mechanical Analyzer)
The thermal deformation behavior of a 1 mm thick sheet was measured using a 1 mm thick sheet. That is, a quartz needle is placed on a sheet, a load of 50 g is applied, and the temperature is raised at a rate of 5°C/min until the needle reaches zero.
．． The temperature at which 1 mm penetrated was defined as TMA.

(2) Impact strength: Using an Izotsu impact tester manufactured by Toyo Seiki Co., Ltd., a length of 63 mm was measured from a 2 mm thick press sheet.
Punch out a sample with a diameter of 8 mm and a width of 12.7 mm.
A mH notch was inserted and the measurement was performed at 23°C.

(3) Rigidity modulus (flexural modulus): Using an Instron tensile tester, a length of 63.8 m was measured from a 2 mm thick press sheet.
Punch out a sample with a width of 12.711 Im and a compression speed of 5.
Measurement was performed at 23° C. with a distance of 32 mm between supports.

The Izot impact test and bending test were conducted 3 days after press molding.

(Synthesis of ring-opening polymer) Toluene 700 mf1. 1, 4, 5
．． 8-dimetator, 1,2,3,4,4a,5,8,
8a-octahydronaphthalene (DMON) 93ml
ll, 2-norbornene (NB) 7 mQ, 1-hexene 0,5 mm, and wcn6 of 0.1 mmoQ
and tetraphenyltin were added, and polymerization was carried out at 50°C for 2 hours.

The polymerization solution was poured into a large amount of methanol to precipitate the polymer, and after washing three times each with methanol and acetone,
It was dried under reduced pressure at 80° C. overnight to obtain 98 g of a polymer.

Intrinsic viscosity of polymer measured in toluene at 30°C [η]
is 0.48dρ/g, “N measured by C-NMR
B content was 10 mol%.

(Hydrogenation reaction of ring-opening polymer) Catalyst 1. 20 g of ring-opening polymer was dissolved in 250 mA of tetrahydrofuran and 1 g of Pd was supported on 50 g of silica.
5g was charged into an IQ autoclave, and 5g was
After pressurizing to 0 kg/cJG, the temperature was raised to 50°C, and 15
Stirring was continued for an hour. The polymer was filtered from the obtained slurry solution, dissolved in cyclohexane, and the catalyst was filtered off.
It was dried under reduced pressure at 0° C. day and night. The hydrogenation rate was 97%.

The glass transition temperature (
Tg) was 155°C.

Example 1 The hydrogenated ring-opening polymer (A) and ethylene-
Propylene random copolymer (ethylene/propylene =
80/20 mol%, glass transition temperature (Tg) -55°C)
40g and 10g of (B) respectively (weight ratio (A) / (B)
) = g.

/20) was added to cyclohexane IQ and dissolved at about 70°C with thorough stirring. The obtained homogeneous solution was poured into acetone 2Q to precipitate the (A)/(B) blend. The obtained blend was dried at 120° C. under reduced pressure for one day and night.

Tetrakis [
Methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane is blended as a stabilizer at 0.5% based on the total amount of resins (A) and (B), and Brabender Plast After crosstalk at 190℃ using the graph, 2
Compression molding was performed at 40°C to obtain a press sheet with a thickness of 2 mm. Test pieces were punched out from this sheet and subjected to impact strength, bending tests, and TMA measurements. The Izot impact strength of this polymer composition is 6 kgan/an, and the initial bending modulus is 2.
2,000kg/aI, bending yield stress 720kg/aI
aI, TMA was 164°C. A polymer composition with excellent rigidity, heat resistance, and impact strength was obtained.

Examples 2 to 7 A hydrogenated ring-opening polymer (A) obtained in the same manner as in Example 1 and various nidistomers (B) were mixed in the proportions shown in Table 5, and tetrakis[methylene-3 (3,5-
Di-t-butyl-4-hydroxyphenyl)propionate comethane was mixed as a stabilizer at 0.5% based on the total amount of resins (A) and (B), and mixed at 190°C using a Brabender plastograph. Thereafter, evaluation was performed in the same manner as in Example 1. The results are shown in Table 5.

A polymer composition with excellent rigidity, heat resistance, and impact resistance was obtained.

Comparative Example 1.2 The same measurements as in Example 1 were carried out using a 2 mm thick press sheet obtained by compression molding the hydrogenated ring-opening polymer (A) used in Examples 1 and 6 at 240°C. Ta.

Izotsu impact strength is 1.0.1.2kgcm, respectively.
/cm, one word - initial bending modulus is 38,000.26,000kg/
cnt, bending yield point stress is 890.800kg/cJ
, TMA was 165.145°C, and although it had excellent rigidity and heat resistance, it had low impact resistance and was a brittle sample.

The above results are summarized in Table 5.

Claims (1)

[Claims] (1) (A) A polymer obtained by hydrogenating a ring-opening polymer consisting of at least one cyclic olefin component represented by the following general formula [I] or [II], comprising:
Intrinsic viscosity [η] measured in decalin at 35°C is 0.0
5 to 10 dl/g, and (B) a hydrogenated ring-opening polymer having a softening temperature (TMA) of 70°C or higher, and (B) an elastomer having one glass transition temperature of lower than 70°C; A) For 100 parts by weight of component (
A hydrogenated ring-opening polymer composition characterized in that component B) is present in an amount of 5 to 100 parts by weight. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, n and m are both 0 or a positive integer, and l is 3 or more is an integer between R^1 and R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ]