JP2615718B2 - Polymer composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a soft curable polymer composition having a hydrogen absorbing performance useful as a liquid casting agent, a sealing agent, and the like. More specifically, (A) a composition containing a polyhydroxyhydrocarbon polymer and, if necessary, a hydrocarbon oil having a double bond, and (B) a prepolymer of a polyhydroxyhydrocarbon polymer and di- or triisocyanate. And a hydrocarbon composition having a double bond, and a hydrogenation catalyst.

[Conventional technology]

2. Description of the Related Art In an optical communication system using an optical fiber, a system having a relay interval of several tens km or more is being realized due to its low-loss characteristics. Conventionally, it has been considered that transmission characteristics of an optical fiber hardly change with time under a normal environment. However, recently, an increase in loss due to permeation of hydrogen into the optical fiber has been confirmed, and the long-term reliability of the optical fiber cable has become a problem.

[Object of the invention]

The present inventors have conducted intensive studies to prevent diffusion of hydrogen into the optical fiber, and have reached the present invention.

That is, the gist of the present invention is (A) a number average molecular weight of 500 to 20,000 and an iodine value of 100
(B) a number average molecular weight of 500 to 20,000 and an iodine value of 100
An isocyanate group-containing prepolymer comprising the following polyhydroxy hydrocarbon-based polymer and polyisocyanate, a reaction product of the above (A) and (B), and a hydrocarbon containing a double bond in a main chain and / or a side chain A polymer oil comprising a base oil and a hydrogenation catalyst.

[Configuration of the invention]

 Hereinafter, the present invention will be described in more detail.

The polyhydroxy hydrocarbon-based polymer used to produce the polymer composition of the present invention has an average number of hydroxyl groups per molecule (hereinafter, simply referred to as "number of hydroxyl groups") of 1.5 or more, preferably 1.8 to 8.0. With a number average molecular weight
Those having a hydrocarbon of 500 to 20,000, a main chain structure of 100 or less, preferably 20 or less, more preferably 5 or less, and a liquid or brittle wax at room temperature are used.

Various examples of such a polyhydroxy hydrocarbon polymer are given. For example, a hydrogenated product of a polyhydroxydiene-based polymer, a hydrogenated product of an oxidative decomposition reduction product of an isobutylene-diene-based monomer copolymer, α
-Olefin (for example, ethylene, propylene, etc.)-
Examples include hydrogenated products of oxidation decomposition reduction products of a non-conjugated diene (or conjugated diene) copolymer.

Of these, a hydrogenated product of a polyhydroxydiene polymer is particularly preferred.

The polyhydroxydiene-based polymer is produced by using a conjugated diene or a conjugated diene and a vinyl monomer as raw materials by a known method such as a radical polymerization method or an anion polymerization method. In the case of radical polymerization, a conjugated diene-based polymer or copolymer having a hydroxyl group at the terminal can be obtained directly by polymerizing hydrogen peroxide as a polymerization initiator.However, in the case of anionic polymerization, first, an alkali metal is used at the terminal using an anionic polymerization catalyst. A living polymer having a bonded structure is produced and then reacted with a monoepoxy compound, formaldehyde and the like. As the raw material conjugated diene, isoprene, chloroprene and the like may be used, but 1,3-
Butadiene is preferred. Styrene, acrylonitrile, methyl (meth) acrylate,
And vinyl monomers such as vinyl acetate. The use amount of the copolymer component is preferably 30% by weight or less of the total monomer amount.

In addition, hydrogenation at the time of producing a hydrogenated product of a polyhydroxydiene-based polymer includes nickel, cobalt, platinum,
The reaction may be carried out in a conventional manner under hydrogen using a catalyst such as palladium, ruthenium, rhodium alone or supported on a carrier. Further, a polymer obtained by partially hydrogenating a polyhydroxydiene-based polymer can also be used.

As another method for producing a hydrocarbon polymer having a hydroxyl group, a method in which a copolymer of an α-olefin and another monomer is subjected to oxidative decomposition treatment and then reduced. For example, a polybutylpolyisobutylene can be obtained by subjecting a butyl rubber-based polymer obtained by cationic polymerization of isobutylene and butadiene or 1,3-pentadiene to an ozonolysis treatment and then reducing it with lithium aluminum hydride.

In the present invention, a part of the polyhydroxy hydrocarbon-based polymer can be replaced with another polyol. Examples of other polyols include polyethylene glycol,
Examples thereof include polyalkylene glycols such as polypropylene glycol and polytetramethylene glycol, polycaprolactone polyols, castor oil, lower polyols such as ethylene glycol and trimethylolpropane, and those obtained by adding ethylene oxide and the like to trimethylolpropane and the like. The amount that can be substituted is 0 to 49% by weight of the polyhydroxyhydrocarbon polymer. Exceeding this range is not preferable because the hydrolysis resistance, weather resistance, heat resistance, and the like, which are characteristics of the polyhydroxy hydrocarbon-based polymer, are poor.

Next, as a plasticizer used in the present invention, as a hydrocarbon-based oil containing a double bond in a main chain and / or a side chain, alkyl diphenyl ethane (trade name: Nisseki condenser oil S), alkyl benzene, alkyl naphthalene (Product name is Kureha Chemical KIS400), various aromatic oils such as dioctyl phthalate, phenylxylsulfone, alkylindenemonoisopropylbiphenyl, ethyldiphenylmethane, myrcene, allocymene, dipentene, γ-terpinene, α-terpinene, terpinolene, α-pinene, β-pinene, karen, kadinen,
Various terpene compounds such as abietadiene and terpene dimer (trade name: Yasuhara Yushi YS Oil D) and the above-mentioned diene oligomers are exemplified.

For example, hydrocarbon oils such as paraffin-based process oils, naphthene-based process oils, and polybutene-based oils can be used.

Nickel as the hydrogenation catalyst used in the present invention,
Transition metal catalysts such as palladium, rhodium, ruthenium and the like can be mentioned. A preferred catalyst is metal ruthenium. Generally, it is used by being supported on carbon, silica or the like.

As a method of adding the plasticizer, it is preferable to add the plasticizer to the component (A) and / or the component (B) in advance. The amount used is 0 to 80% by weight, preferably 10 to 70% by weight in terms of the content of the component (A), and 1 to 90% by weight in the content of the component (B).
%, Preferably in the range of 10 to 70% by weight. By adjusting the amount of hydrocarbon oil used within the above range, the viscosity of component (A) and component (B) can be increased from 500 CPS at room temperature.
100,000 CPS, or the hardness of the cured product is JIS K6301, 70 or less in A standard, or 2,000 kg / cm ² or less in initial elastic modulus, preferably 40 or less in JIS K6301 A standard, or in initial elastic modulus.
It can be arbitrarily adjusted within a range of 400 kg / cm ² or less. Usually, it is preferable that the polymer composition contains 10 to 70% by weight of oil.

The amount of the hydrogenation catalyst used is generally 0.001 to 1.0% by weight, preferably 0.005 to 0.5% by weight, based on the plasticizer containing a double bond.

As a method of mixing the hydrogenation catalyst, it may be added to the component (A) and / or the component (B) at the time of adding the plasticizer. Alternatively, the plasticizer and the hydrogenation catalyst may be separately mixed and then added by the above method.

Next, the polyisocyanate used in the component (B) of the present invention includes hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate, and polymeric diphenylmethane diisocyanate. Is mentioned. These polyisocyanates are appropriately used depending on the limitation of the pot life and the like, but in the present invention, it is preferable to select the polyisocyanate so that the pot life is 0.5 hours or more at room temperature.

In the present invention, the prepolymer of the polyhydroxyhydrocarbon polymer and the polyisocyanate contained in the component (B) is preferably a hydroxyl group in the polyhydroxyhydrocarbon polymer and an isocyanate group in the polyisocyanate. In an equivalence ratio of 2 and 8 or less, both are mixed, and further, in the presence or absence of a hydrocarbon oil, at a reaction temperature, from room temperature to 200 ° C., preferably from room temperature to 150 ° C.,
It is obtained by reacting for 2 to 20 hours.

Regarding the method of mixing both components, in order to suppress side reactions such as a crosslinking reaction, after mixing both at a low temperature, a method of gradually raising the temperature under stirring, or first, charging the polyisocyanate into the reactor, Next, a method in which a polyhydroxy polymer is gradually added and reacted is preferable.

It is also possible to use a plurality of kinds of polyisocyanates in combination. A method of making a prepolymer from two kinds of polyisocyanates, or a method of making a prepolymer with one kind of polyisocyanate, and then making another kind of polyisocyanate A method of adding a nart can also be adopted.

Next, regarding the mixing ratio of the component (B) and the component (A) obtained as described above, the components (B) and (A)
In a ratio (equivalent ratio) of the total amount of hydroxyl groups in the polyhydroxyhydrocarbon polymer to the total amount of polyisocyanate groups in component (B) in the range of 0.7 to 1.5, more preferably 0.8 to 1.2. .

Outside this range, the curing does not proceed completely or only a cured product having poor mechanical strength is obtained.

The blending weight ratio of the component (A) and the component (B) varies depending on the composition of the component (A) and the component (B).
It is preferable that the weight ratio of / component (B) is in the range of 1/1 to 10/1.

The polymer composition obtained as described above is from room temperature to 20
Curing proceeds in the range of 0 ° C. Although the curing time is shortened as the temperature increases, it may be appropriately determined according to the application.

In the polymer of the present invention, fillers such as silica, hydrated silica, alumina, clay, talc, calcium carbonate, magnesium carbonate, carbon black, organic fibers, glass fibers, and the like, a flame retardant, a foam stabilizer, a crosslinking agent And known additives used in the urethane industry, rubber industry, and the like can be used as necessary.

〔The invention's effect〕

As described above, the polymer composition of the present invention as described above has a good hydrogen absorbing ability, and thus maintains a long-term stable high sealing performance. In addition, the workability is good because the pot life is long and the viscosity can be appropriately adjusted according to the application.

Further, since the hardness of the cured product can be adjusted over a wide range, it is possible to respond finely to various uses.

In addition, it has excellent mechanical properties, heat resistance, weather resistance, hydrolysis resistance, and electrical insulation properties.・
Potting agent for moisture proof, waterproof coating of marine equipment,
Potting agents, electronic components used in the automotive industry, potting agents for electrical components, adhesives, as well as waterproof filling, anti-vibration, moisture-proof potting agents for these cable joints, interlayer insulation materials for wire coils, optical cable waterproofing agents, various types It can be used as an adhesive and a coating agent, and is extremely important in industry.

〔Example〕

Next, the present invention will be specifically described with reference to Examples and Production Examples (Reference Examples) of raw materials for the polymer composition of the present invention. However, the present invention is restricted by these Examples unless exceeding the gist thereof. Not something.

Example 1 Preparation of Component (A) Polytail as polyhydroxyhydrocarbon polymer
HA (Mitsubishi Kasei Kogyo Co., Ltd., number average molecular weight 2,000,
7.47 kg of urine value 3.5) and K-stone process oil P-200
Paraffin-based process oil manufactured by Sekiyu K.K.
39kg, YS Resin PX-100 (made by Yasuhara Yushi Kogyo Co., Ltd.
4.18 kg of ruthene-based oligomer) and ruthenium supported on carbon
(5%) catalyst (Nippon Engelhard Co., Ltd.)
167kg, These are mixed by stirring at room temperature for 10 hours
Thus, component (A) was obtained.

Production of component (B) Polytail HA 14.10kg, Kyoishi process oil P-2
14.06 kg of 00, saturated hydrocarbon polymer polytail HA−
8.87 kg of B (with no terminal hydroxyl group manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)
2.2316 kg of toluene diisocyanate and diphenylmeth
0.727 kg of tandiisodianate, these at 60-80 ° C for 1
The reaction was carried out for 0 hour to obtain a component (B).

Temporal change of hydrogen gas pressure 25 g of the component (A) and 25 g of the component (B) were placed in a double-necked flask, mixed well with a spatula, and the system was evacuated.

Then, about 100 mmHg of hydrogen was introduced, the flask was placed in an oil bath at 150 ° C., and the decrease in hydrogen pressure was tracked by a manometer.

Comparative Example 1 Components (A) and (B) were produced in exactly the same manner as in Example 1 except that no ruthenium catalyst was added during the production of component (A). After 480 minutes, the hydrogen pressure did not change at all.

Example 2 Preparation of Component (A) Polytail as polyhydroxy hydrocarbon polymer
7.47 kg of HA (number average molecular weight 2,000, iodine value 3.5), Kyoishi
3.39 kg of process oil P-200, aromatic oil (JP
4.18 kg of SAS-LH) manufactured by the Petrochemical Company and loaded on carbon
0.167kg of ruthenium (5%) catalyst
The mixture was stirred and mixed at room temperature for 10 hours to obtain component (A).

Production of component (B) Polytail HA 14.10kg, Kyoishi process oil P-2
14.06 kg of 00, saturated hydrocarbon polymer polytail HA−
8.87 kg of B, 2.2316 kg of toluene diisocyanate and
0.727 kg of diphenylmethane diisocyanate and 6
The reaction was carried out at 0 to 80 ° C for 10 hours to obtain a component (B).

Temporal change of hydrogen gas pressure 25 g of the component (A) and 25 g of the component (B) were placed in a double-necked flask, mixed well with a spatula, and the system was evacuated.

Then, about 100 mmHg of hydrogen was introduced, the flask was placed in an oil bath at 150 ° C., and the decrease in hydrogen pressure was tracked by a manometer.

Comparative Example 2 Components (A) and (B) were produced in exactly the same manner as in Example 2 except that the ruthenium catalyst was not added during the production of the component (A). The hydrogen pressure did not change at all even after 180 minutes.

Claims (5)

(57) [Claims] (A) a number average molecular weight of 500 to 20,000,
A polyhydroxy hydrocarbon polymer having an iodine value of 100 or less, (B) a number average molecular weight of 500 to 20,000, and an iodine value of 100
An isocyanate group-containing prepolymer comprising the following polyhydroxy hydrocarbon-based polymer and polyisocyanate; a reaction product of the above (A) and (B); and a hydrocarbon-based polymer containing a double bond in a main chain and / or a side chain. A polymer composition comprising an oil and a hydrogenation catalyst. 2. The polymer according to claim 1, wherein the hydrocarbon oil containing a double bond in the main chain and / or the side chain is a finger ring or aromatic hydrocarbon oil. Composition. 3. The polymer composition according to claim 1, wherein the hydrogenation catalyst is ruthenium metal. 4. The polyhydroxy hydrocarbon-based polymer according to claim 1, wherein the iodine value is 20 or less.
Item 8. The polymer composition according to Item 1. 5. The polyhydroxy hydrocarbon-based polymer according to claim 1, wherein the iodine value is 5 or less.
Item 8. The polymer composition according to Item 1.