JPH0459218A - Molded product of hydrogenated polymer - Google Patents

Abstract

PURPOSE:To manufacture a hydrogenated polymer having superior heat resistance and mechanical physical properties by extrusion molding or blow molding a ring opening polymer of a monomer composed of a norbornane derivative having a polar substituent, or a hydrogenated polymer prepared by hydrogenation, a mixture of said hydrogenated polymer and a rubber polymer or resin. CONSTITUTION:A polymer blended material having the melting viscosity of 2X10<3> poise or above at 300 deg.C containing a component (a)of at least 50wt.% is extrusion molded or blow molded at 240-360 deg.C to manufacture the subject molded product. The heat deformation temperature of said molded body is at least 100 deg.C, and elastic modulus in flexure is 1.5X10<4>kgf/cm<2> or above. The component (a) is a monomer composed of at least one kind of norbornane derivative represented by the formula. In the formula, A and B represent a hydrogen atom or C1-10 hydrocarbon, X and Y represent a hydrogen atom, halogenated atom or a monovalent organic group, and at least one of X and Y represents a group having the polarity other than hydrogen atom or hydrocarbon, and (m) is 0 or l.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is an extrusion or extrusion method with excellent heat resistance consisting of a specific hydrogenated polymer alone or a mixture (or alloy) of this and a rubbery polymer or resin. Regarding blow molded products.

[Prior Art] Extrusion molded products, blow molded products, etc. are manufactured using general-purpose resins such as polybutylene terephthalate, vinyl chloride, ABS, polyethyl, and polypropyl, but the temperature range for practical use is narrow due to low heat resistance. Therefore, they may not be suitable as automobile parts, electrical/electronic parts, or OA equipment parts.

[Means for Solving the Problems] As a result of extensive research into the above-mentioned problems, the present invention provides a hydrogenated product obtained by further hydrogenating a monomeric ring-opening polymer made of a norbornene derivative having a polar substituent. Extrusion molded products or blow molded products obtained from a polymer alone or a mixture of this polymer and a rubbery polymer or resin exhibit excellent heat resistance and solve the above problems.

That is, the present invention is directed to a composition containing at least 50% by weight of the following component (a) and having a melt viscosity of 2 x 1 at 300°C.
03poise or higher polymer blend at 240-360℃
The molded product is a molded product formed by extrusion molding or blow molding, and the heat distortion temperature of the molded product is at least 10
0℃ or higher, bending elastic modulus is 1. 5 x 10' kg
The present invention provides a molded article of a hydrogenated polymer characterized in that it has a f/cd or higher.

Component (a): A monomer consisting of at least one norbornene derivative represented by the following general formula (I), or this monomer and a copolymerizable monomer copolymerizable therewith by ring-opening polymerization. A hydrogenated polymer obtained by further hydrogenating the resulting ring-opened polymer.

[In the formula, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom, a halogen atom, or a monovalent organic group, and at least one of X and Y is It represents a polar group other than a hydrogen atom or a hydrocarbon group, and m is 0 or 1. ] Note that the melt viscosity (η), heat distortion temperature,
The flexural modulus is based on the following measurement method.

Melt viscosity (η) is S D R (Slit Die Re
hometer (manufactured by Shima Tagiken Co., Ltd.) at 300°C, and from equations (1) to 4), the shear strain rate (te) = 103
Expressed as a value.

Q=πR2V (1) Te=6Q/
WH2 (2) τ=(ΔP)H/2.5X2 (3) η=τ/
γ 4) Here, W: Width of slit (1,2 cm) H: Thickness (cm) R: Radius of cylinder (required) V: Speed of plunger (cm/5ee) ΔP: Pressure difference Pa/cd Te ; Shear rate τ; Stress η; Melt viscosity (at 300°C) Heat distortion temperature: ASTM D648 (HDT) (1
/4') , or hydrogenation obtained by further hydrogenating a ring-opening polymer obtained by ring-opening copolymerization of a specific monomer with a copolymerizable monomer that can be copolymerized with the specific monomer using a metathesis polymerization catalyst. It is a polymer, and is also referred to as a "hydrogenated polymer (a)" below.

The molecular weight of this hydrogenated polymer (a) is from 20,000 to 700.0 in weight average molecular weight in terms of polystyrene.
00, especially 30,000 to 50o, ooo.

In the present invention, the hydrogenated polymer (a) includes, for example, a polymer obtained by hydrogenating a ring-opened (co)polymer of a compound having a norbornene ring described in JP-A-1-132626. I can do it.

Among these specific monomers, the specific monomer in which X or Y in the above general formula (I) is a carboxylic acid ester group represented by the formula (CH2)C0OR' has a high glass transition temperature of the resulting polymer. This is preferable because it has low hygroscopicity. In particular, it is preferable that one polar substituent consisting of a carboxylic acid ester group is contained per molecule of the specific monomer, since the resulting polymer has low hygroscopicity.

Further, among the carboxylic acid ester groups represented by the formula (CHz) COOR', those with a smaller value of n are preferable because the glass transition temperature of the obtained polymer becomes higher, and furthermore, specific monomers in which n is 0 are preferable. , is preferred because its synthesis is easy and the resulting polymer has good properties.

In the above formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms, which is preferable in that the greater the number of carbon atoms, the lower the hygroscopicity of the resulting polymer.

However, from the viewpoint of balance with the glass transition temperature of the obtained polymer, a chain alkyl group having 1 to 4 carbon atoms or a (poly)cyclic alkyl group having 5 or more carbon atoms is preferable, particularly a methyl group. It is preferable that

Furthermore, to the carbon atom to which the carboxylic acid ester group is bonded,
At the same time, a specific monomer to which a hydrocarbon group having 1 to 10 carbon atoms is bonded as a substituent is preferable because it lowers the hygroscopicity without lowering the glass transition temperature of the resulting polymer.

In particular, a specific monomer in which the substituent is a methyl group is preferable because it is easy to synthesize.

The ring-opening polymer according to the hydrogenated polymer (a) in the present invention may be one obtained by ring-opening polymerizing a specific monomer alone, but it may also be a polymer that is copolymerizable with the specific monomer. It may be ring-opening copolymerized with. When a copolymerizable monomer is used in this way, the proportion of the specific monomer in the ring-opening polymer is 5 mol% or more, preferably 20 mol% or more. The copolymerizable monomers used include monomers that can undergo ring-opening polymerization with a metathesis polymerization catalyst, and partially polymerized low polymers having a carbon-carbon double bond in the main chain of the polymer. can be mentioned.

Among the above-mentioned specific monomers, a tetracyclododecene derivative in which m is 1 in the above general formula (I) is preferred in that a polymer having a high glass transition point can be obtained. General formula (I
), among the tetracyclododecene derivatives in which m is 1, preferred compounds include 8-carboxymethyltetrasif[4,4,0,1,1-3-dodecene, 8 -Methyl-8-carboxymethyltetracy2.5 7.10 Chloro[4,4,0,1,1-3-dodecene, 5-carboxymethyl-bicyclo[2,2゜1]-2-heptene, etc. can be mentioned.

The specific monomer can also be copolymerized with a cyclic olefin compound. Specific examples of such cyclic olefin compounds include cycloolefins such as cyclopentene, cyclooctene, 1,5-cyclooctadiene, and cyclododecatriene; bicycloheptene, tricyclodecene, tricycloundecene, tetracyclododecene, and pentacyclo Mention may be made of polycycloalkenes such as pentadecene, pentacyclohexadecene, pentacyclopentadecene, dicyclopentadiene, and pentacyclopentadeca-4,11-diene.

Furthermore, examples of copolymerizable monomers that can be copolymerized with the specific monomer include polymers such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer. Unsaturated hydrocarbon polymers containing a carbon-carbon double bond in the main chain can also be mentioned.

The ring-closing polymerization method and hydrogenation method of a specific monomer and a copolymerizable monomer copolymerizable therewith are described in JP-A-1-13
A method similar to the method described in No. 2626 can be mentioned.

The hydrogenation rate of the obtained hydrogenated polymer (a) is usually 5
0% or more, preferably 70% or more, more preferably 8
It is considered to be 0% or more. If the hydrogenation rate is less than 50%, the thermal stability will be low, which is not preferable.

The rubbery polymer to be mixed with component (a) of the present invention includes ordinary rubbery polymers and thermoplastic elastomers.

Examples of rubbery polymers include ethylene-α-olefin rubbery polymers; ethylene-α-olefin-polyene copolymer rubbers; combinations of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymers; copolymers of ethylene and vinyl fatty acids, such as ethylene-vinyl acetate; polymers of alkyl acrylates, such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, etc. ; Polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene-(meth)acrylic acid alkyl ester copolymer, butadiene-(meth)acrylic Diene rubbers such as acid alkyl ester-acrylonitrile copolymer, butadiene-(meth)acrylic acid alkyl ester-acrylonitrile-styrene copolymer, and hydrogenated products thereof; butylene-
There are hydrogenated products such as isoprene copolymers and block copolymers of aromatic hydrocarbon compounds such as styrene and aliphatic diene hydrocarbon compounds such as butadiene and isoprene. More than one species can also be used.

The rubbery polymer may be obtained by crosslinking the above rubbery polymer using a known crosslinking agent such as divinylbenzene.

The above-mentioned butadiene-styrene copolymers include styrene-butadiene copolymers having at least one styrene block and hydrogenated products thereof.

The rubbery polymer made of the above-mentioned rubbery polymer preferably has a Mooney viscosity (ML, 100° C.) of 5 to 1÷4200.

Examples of thermoplastic elastomers used as rubbery polymers include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated styrene-butadiene block copolymers.
Aromatic vinyl-conjugated diene block copolymers such as isoprene block copolymers, low-crystalline polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, ethylene-based ionomer resins, etc. I can do it.

The aromatic vinyl-conjugated diene block copolymer is AB
It may be of any type, ABA type, ABA taper type, radial teleblock type, etc.

The amount of rubbery polymer mixed in component (a) is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less.
% by weight or less. If it exceeds 50% by weight, the heat resistance and flexural modulus of the extrusion molded product or blow molded product manufactured therefrom will be low, which is not preferred from a practical standpoint.

Next, the resin to be mixed with component (a) has a glass transition temperature of 2.
It is a polymer with a temperature of 5°C or higher, and includes non-quality polymers, crystalline polymers, liquid crystal polymers, etc. Specifically, styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polycarbonate resins, polyester resins, polyamide resins, polyethersulfone resins, polysulfone resins, polyimide resins, etc. be able to.

The amount of resin mixed in component (a) is 50% by weight or less, preferably 45% by weight or less, more preferably 40% by weight or less. If it exceeds 50% by weight, the heat resistance of the molded product will decrease by 10%.
The temperature may drop below 0°C, which is not practical.

When molding an extrusion molded product or a blow molded product from a mixture of component (a) and a rubbery polymer, a mixture of component (a) and a resin, or a mixture of component (a) and a rubbery polymer and resin,
The physical properties of the molded article will be more uniform if these mixtures are thoroughly kneaded in a processing machine such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, mixing roll, etc., and then molded. As an example of kneading in this case, the components are mixed in a mixer and then melted and kneaded in an extruder at 240 to 360°C to obtain granules. As a more simplified molding method, the mixture of each component may be directly put into an extrusion molding machine or a blow molding machine and molded.

By extrusion molding or blow molding component (a) alone or a mixture of component (a) and a rubbery polymer or resin, a molded product that passes both appearance and physical properties can be obtained. The molding temperature is in the range of 240 to 360°C, more preferably 260°C.
The temperature is 0 to 330°C.

If the temperature is below 240°C, the compound will not be melted uniformly, which may result in uneven wall thickness of the processed molded product, poor appearance, and deterioration of physical properties.

A temperature of 360° C. or higher is not preferable because the melt deteriorates in the air, resulting in poor appearance (coloring) and deterioration of physical properties of the molded product.

During extrusion and blow molding, the shear rate (7") experienced by the melt is 102-103 (see"). Therefore, the melt viscosity (η) of the blend is te=103se
The value of c-' is used (at 300°C).

η=103) is at least 2X103poise
If it is above, the thickness of the product will be uniform, and a good molded product without defects will be obtained. More preferably 3
X 103 to I X 10'poise. η
If it is less than = 2 x 103 poise, the fluidity is too good and the molding temperature dependence of the compound η is large, the wall thickness is not uniform, and the physical properties are greatly deteriorated.

In addition, in the case of extrusion molding or blow molding, a suitable molding machine may be used.

High heat resistance is required in order to use extrusion-molded or blow-molded products of component (a) alone or a mixture of component (a) and a rubbery polymer or resin as automobile parts, electrical parts, or mechanical parts. . Therefore, it is necessary that the heat distortion temperature is at least 100°C or higher, and more preferably 120°C or higher. When the heat deformation temperature is 100° C. or lower, when the molded product is used as a heat-resistant material, it will undergo thermal deformation, resulting in a defective product in terms of appearance and practical performance.

In addition, from the viewpoint of practical performance, that is, mechanical properties, the bending elastic modulus of the molded product is at least 1.5 x 104 kgf/csf.
f or more is required. If it is lower than 1.5xlO')cgf/c-, it cannot be used as molded products such as automobile parts, electrical parts, and mechanical parts.

The molded article of the present invention can be produced by kneading component (a) alone or component (a) and rubber or resin in a single-screw extruder, twin-screw extruder, or kneader to form pellets, and extruding the pellets. It is produced by molding, or component (a) alone, (
a) A molded article is produced by extrusion molding the component and rubber or resin.

The composition serving as a raw material for the molded article of the present invention includes an antioxidant,
For example, 2,6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,2-methylene-bis-(4-ethyl-6-t-butylphenol) ), tris (di-nonylphenyl phosphite); ultraviolet absorbers, such as p-t
-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxy-benzophenone, 2-(2'dihydroxy-4'-m-octoxyphenyl)benzotriazole; lubricants such as paraffin wax, stearic acid, hydrogenated oils, stearamide , methylene bisstearamide, m-butyl stearate, ketone wax, octyl alcohol, hydroxystearic acid triglyceride, silicone oil; flame retardants such as antimony oxide, aluminum hydroxide, zinc oxalate, chlorinated paraffin, tetrabromobutane , hexabromobenzene, tetrabromobisphenol A; antistatic agents, such as stearamidopropyldimethyl-β-hydroxyethyl, ammonium drate; colorants, such as titanium oxide, carbon black; fillers, such as calcium oxide, clay.
Silica, glass fiber, glass spheres, carbon fiber; pigments, etc. can be added as necessary.

[Example Production of component (a) (Production of rubbery polymer (a-1)) In a reaction vessel purged with nitrogen gas, the specific monomer 8-methyl-8-carboxymethyltetracyclo[4 ,4,0,
12°j 17-10] 3-dodecene 500g
, 2000 ml of 1,2-dichloroethane, 3.8 g of 1-hexene as a molecular weight regulator, 91.6 ml of a chlorobenzene solution of tungsten hexachloride as a catalyst with a concentration of 0.05 M/g, and paraaldehyde with a concentration of 0.05 M/g. 1M/
By adding 68.7 ml of a 1,2-dichloroethane solution of 1 and 37 ml of a toluene solution of triisobutylaluminum with a concentration of 0.5 M/(l and reacting at 60°C for 10 hours, the intrinsic viscosity (ηinh) was 0.56 dR.
/g (in chloroform, 30°C, concentration 0.5g/c
450 g of ring-opened polymer W) was obtained. This ring-opened polymer is 9
45 g of a palladium-alumina catalyst dissolved in 1,000 ml of tetrahydrofuran and having a palladium concentration of 5% by weight was added, hydrogen gas was charged at a pressure of 100 kgf/(!-), and a hydrogenation reaction was carried out at 150° C. for 5 hours.

After the hydrogenation reaction, the catalyst was separated from P, and the P solution was poured into a large excess of methanol acidified with hydrochloric acid to form the hydrogenated polymer a.
-1 was manufactured. The hydrogenation rate of this polymer a-1 was substantially 100%.

(Manufacture of rubbery polymer (b-1)) (1) After charging 2500 g of degassed and dehydrated cyclohexane and 100 g of styrene into an autoclave with an internal volume of 5 g, 9.8 g of tetrahydrofuran and 0.2 g of n-butyllithium were added. was added to carry out isothermal polymerization at 50°C (
1st stage polymerization).

After the polymerization addition rate reached almost 100%, 1,
A mixture of 325 g of 3-butadiene and 75 g of styrene was added to 1
While continuously adding at a rate of 75g per minute,
Polymerization was carried out at 0°C (second stage polymerization).

(2) After the conversion rate of the added monomer reached approximately 100%, the reaction solution was cooled to 70°C, and 0.0% n-butyllithium was added.
6g and 2.6-t-butylcresol 0.6g and bis(cyclopentagenyl)titanium dichloride 0.2
Add 8 g and 1.1 g of diethyl aluminum, and add 1.1 g of hydrogen gas. The hydrogenation reaction was carried out for 1 hour while maintaining the pressure at 0 kg/cd.

Next, the reaction solution was cooled to room temperature, taken out from the autoclave, and desolvated by steam stripping.
It was dried with a roll at 0°C to obtain the following hydrogenated block copolymer (b-1).

Total bound styrene content % 35 Ratio of first stage polymer 20 blocks to total polymer (%
) Butadiene moiety in block polymer 40 Vinyl bond gold content (%) Hydrogenation rate (%) 98 Molecular weight (X104) 16 Melt flow rate (230°C, 5 kg) 30 Refractive index η, 1.515 Example 1 Hydrogenated polymer (a-1) (η=3.2×103poi
se, at 300°C) in an extruder at 270°C, 33
The test piece was extruded at 0℃, and the appearance, heat distortion temperature (
HDT) and flexural modulus (F Mo ) were measured.

Test piece shape: For HDT 1/4' x 1/2' S T M D 79
0 Appearance Visual observation O Pass 270℃, 33
Extrusion molding was carried out at 0°C.

Examples 4 to 6, Comparative Example 2 Polymer (a-1) and polypropylene (Mitsubishi Yuka BC)
-8) A rubbery polymer was mixed in the proportions shown in Table 1 to prepare pellets, and extrusion molded at 270°C and 330°C.

Example 7, Comparative Example 4 Ring-opened polymers with different molecular weights were synthesized by varying the molecular weight regulator 1-hexene in the production of polymer (a-1), and these were hydrogenated. Hydrogenation rate 99% (a-2)
, 99.5% (a-3). These were molded in the same manner as in Example 1 and extruded using test pieces.

Comparative example 3 Polymer (a-1) was extrusion molded at 370°C.

Examples 8 to 10, Comparative Example 5 The formulations shown in Table 2 were blow molded at 280°C and 370°C to form bottles.

Heat resistance: The sample was left at each temperature for 2 hours, and the highest temperature without deformation was determined.

The component (a-4) used in Comparative Example 5 was a polymer (a-4).
-1) The molecular weight regulator 1 in the production of hexene was varied to synthesize ring-opened polymers with different molecular weights, which were hydrogenated, and η=1. 1×103poise (30° C.) and a hydrogenation rate of 99.3%. When this was extruded, the thickness was uneven.

Blank space below [Effects of the Invention] According to the present invention, a hydrogenated polymer obtained by further hydrogenating a monomeric ring-opened polymer made of a norbornene derivative having a polar substituent, or a rubber-like polymer obtained in combination with the hydrogenated polymer A mixture with a polymer or resin having a melt viscosity of at least I
X 103 poise (at 300° C.) or higher, and extrusion-molded or blow-molded molded products exhibit excellent heat resistance and mechanical properties.

That is, the molded article of the present invention can be used in fields that utilize excellent heat resistance and mechanical properties.

For example, it is useful for interior and exterior parts of automobiles, electrical/electronic parts, and mechanical parts such as OA equipment.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) Contains at least 50% by weight of component (a) below and has a melt viscosity of 2 x 10^3 poise at 300°C
A molded product formed by extrusion molding or blow molding the above polymer blend at 240 to 360°C, and the molded product has a heat distortion temperature of at least 100°C or higher and a flexural modulus of 1.5×10 A molded article of a hydrogenated polymer characterized by having a tensile strength of ^4 kgf/cm^2 or more. Component (a): A monomer consisting of at least one norbornene derivative represented by the following general formula (I), or this monomer and a copolymerizable monomer copolymerizable with it, by ring-opening polymerization. A hydrogenated polymer obtained by further hydrogenating the resulting ring-opened polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and X and Y are hydrogen atoms, halogen atoms, or monovalent organic groups. At least one of X and Y represents a polar group other than a hydrogen atom or a hydrocarbon group, and m is 0 or 1. ]