JPH0275657A - Polymer composition - Google Patents

Abstract

PURPOSE:To form a polymer composition having excellent water stop performances and hydrogen absorptive properties and used for packing the space of an optical fiber cable by mixing a reaction product of a specified polyol component with an isocyanate-terminated prepolymer with a double bond-containing hydrocarbon oil and a hydrogenation catalyst. CONSTITUTION:This polymer composition is prepared by mixing a reaction product of a hydroxy-terminated prepolymer comprising a polyhydroxyhydrocarbon polymer and a polyisocyanate or a polyol component (A) comprising a polyhydroxyhydrocarbon polymer and an at least trifunctional polyol and having at least two, on the average, hydroxy groups per molecule (A) with an isocyanate-terminated prepolymer (B) comprising a polyhydroxyhydrocarbon polymer and a polyisocyanate with a hydrocarbon oil having a double bond in the main chain or a side chain and a hydrogenation catalyst.

Description

[Detailed description of the invention] [Industrial application field] FIELD OF THE INVENTION This invention relates to polymer compositions.

Specifically, the present invention relates to a polymer composition having excellent water-stopping performance and hydrogen absorption performance.

[Prior art and problems to be solved by the invention] Conventional optical fibers have been designed to prevent optical loss from occurring over time during transmission under normal circumstances. It has been confirmed that hydrogen is generated through electrolysis, and this hydrogen permeates into the optical fiber, increasing the loss in the amount of transmitted light.

The applicant has discovered that a polymer composition consisting of a reaction product of a specific polyhydroxy hydrocarbon polymer and a specific isocyanate group-containing prepolymer, a specific hydrocarbon oil, and a hydrogenation catalyst is hydrogenated. Invented that it has absorption performance,
A patent application was filed earlier (% Nishō 6--, 3233Al
).

On the other hand, a polymer composition containing a reaction product of a specific polyol component and a specific isocyanate group-terminated prepolymer and a hydrocarbon oil has water-stopping performance, and is a water-retaining agent for submarine optical fiber cables. It is known to be used as (JP-A-62-G/2/;).

The present inventor has provided a polymer composition having the above-mentioned water-stopping performance,
The present invention was completed based on the discovery that a polymer composition having excellent water-stopping performance and hydrogen absorption performance could be obtained by applying the previously filed polymer composition having hydrogen absorption performance. did.

An object of the present invention is to provide a polymer composition having excellent water-stopping performance and hydrogen absorption performance, which is used to fill voids in optical fiber cables.

[Means to solve the problem]

That is, the present invention provides a reaction product of the following polyol component (A) and an isocyanate group-terminated prepolymer (B),
The gist of the invention is a polymer composition comprising a hydrocarbon oil having a double bond in the main chain or side chain and a hydrogenation catalyst.

(A) Consisting of a hydroxyl-terminated prepolymer or a polyhydroxyhydrocarbon-based polymer consisting of a polyhydroxy hydrocarbon polymer and a polyisocyanate, and a polyol with J functionality or higher, the average number of hydroxyl groups is p2 per molecule of polyol.
The above polyol component (B) isocyanate group-terminated prepolymer consisting of a polyhydroxy hydrocarbon polymer and polyisocyanate The polyhydroxy hydrocarbon polymer used in the present invention has an average of 7 molecules The number of hydroxyl groups (hereinafter simply referred to as "number of hydroxyl groups") is i, s or more, preferably 8f
-ff, 0, number average molecular weight is SOO~koo,
ooo, the main chain structure is a hydrocarbon, the iodine value is less than ioo, preferably less than 10, more preferably less than 5, and is liquid or brittle waxy at room temperature.

Such polyhydroxy hydrocarbon polymers include:
For example, hydrogenated products of polyhydroxydiene polymers, hydrogenated products of oxidative decomposition and reduction products of inbutylene-diene monomer copolymers, α-olefins (such as ethylene and propylene) and non-conjugated dinones (or Examples include hydrogenated products of oxidative decomposition and reduction products of [conjugated diene] copolymers. Among these, hydrogenated products of polyhydroxydiene-based polymers are particularly preferred.

Examples of other hydroxy hydrocarbon polymers include those obtained by subjecting a copolymer of an α-olefin to another heptamer to an oxidative decomposition treatment and then reducing the copolymer. For example, inbutylene and butadiene or he3-
Examples include polyhydroxy polyimbutylene obtained by further subjecting a butyl rubber-based polymer obtained by cationic polymerization of pentadiene to an ozone decomposition treatment and then reducing it with lithium aluminum hydride.

Note that a part of the polyhydroxy hydrocarbon polymer used in the present invention can be replaced with another polyol. Examples of other polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, polyester polyols such as polycaprolactone glycol and castor oil-based polyols, ethylene glycol, -monoethyl-J-hexanediol, etc. Examples include lower polyols. As the amount that can be substituted, an amount up to about the weight of SO of the polyhydroxy hydrocarbon polymer can be added.

If it exceeds this range, it is not preferred because the characteristics of polyhydroxy hydrocarbon polymers such as hydrolysis resistance, weather resistance, heat resistance, electrical properties, etc. will be inferior.

Next, the polyisocyanates used in the present invention include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, inphorone diisocyanate, and hiscyphenylmethane diisocyanate. Examples include liquid modified products.

The trifunctional or higher functional polyol used in the present invention includes:
Low molecular weight polyols such as trimethylolpropane, glycerin, triethanolamine, 8-16-hexanetriol, pentaerythritol, diglycerin, dipentaerythritol, or similar low molecular weight polyols with ethylene oxide or propylene oxide added, Addition of similar alkylene oxide to ethylene diamine, dipentaerythritol alkyl ester polyols such as dipentaerythritol heptanooctoate, dipentaerythritol dioctoate, dipentaerythritol trioctoate, diglycerin alkyl such as diglycerin monooctoate Ester polyols, ester polyols made by reacting shhentaerythritol with a dicarboxylic acid such as adipic acid and a monocarboxylic acid such as octyl acid at a molar ratio of J:/:4 to 1:1, diglycerin and adipine. Ester polyols formed by reacting a dicarboxylic acid such as an acid with a monocarboxylic acid such as octylic acid at a molar ratio of 2:/:, 2 to 2:/:, 7 may be mentioned. These ester polyols can be easily produced by known ester-forming reactions such as dehydration condensation of carboxylic acid and polyol in the presence of an acid catalyst or a suitable metal catalyst, or reaction of carboxylic acid halide with polyol. Can be manufactured.

The amount of these trifunctional or higher functional polyols to be used is SO% or less based on the total weight of component (A), preferably JO'1
Can list 6 or less.

The hydroxyl-terminated prepolymer composed of a polyhydroxy hydrocarbon polymer and a polyisocyanate contained in component (A) is reacted at a reaction temperature of room temperature to 200° C., preferably in the presence or absence of a hydrocarbon oil. is 50-150
It is obtained by reacting in the range of ℃ for ~ -〇 hours.

Regarding the mixing of both components, in order to suppress side reactions such as crosslinking reactions, it is possible to mix them at low temperature and then raise the temperature while stirring, or to mix the polyhydroxy polymer first and then add the polyisocyanate. A method of gradually adding the compound is preferred.

Further, the mixing ratio of both components is preferably in the range of Oo- or more and o and g or less in terms of the equivalent ratio of isocyanate groups to hydroxyl groups (NC010H).

The average number of hydroxyl groups in the polyol component contained in component (A) must be adjusted to be much larger, preferably much larger. The method for its preparation is as follows: (1) A polyhydroxy hydrocarbon polymer having a relatively large average number of hydroxyl groups is used as the polyol component.

(2) As a polyol component, a polyhydroxy hydrocarbon polymer having an average number of hydroxyl groups of 2 or less and a polyol having 3 or more functional groups are mixed to increase the average number of hydroxyl groups to υ.

(3) bonding a polyhydroxy hydrocarbon polymer and a trifunctional or higher functional polyol with polyisocyanate,
Increase the average number of hydroxyl groups.

(4) A trifunctional or higher functional polyol is added to a prepolymer polyol, which is a reaction product of a polyhydroxy hydrocarbon polymer and a polyisocyanate, to increase the average number of hydroxyl groups.

There are methods such as, but the method is not limited to these.

Among these methods, preferably the average number of hydroxyl groups is 7. j
A mixture of a hydroxyl group-terminated prepolymer obtained by reacting a polyhydroxy hydrocarbon polymer in the range of -.O with a diisocyanate and a trifunctional or higher functional polyol is used.

In the present invention, the isocyanate group-terminated prepolymer (B) consisting of a polyhydroxy hydrocarbon polymer and a polyisocyanate preferably has an equivalent ratio of isocyanate groups to hydroxyl groups in the range of /, 3 or more gy or less. The two are mixed together, and further the reaction temperature is from room temperature to 200°C, preferably from 50 to 750°C, in the presence or absence of hydrocarbon oil.
It is obtained by reacting at a temperature in the range of 2 to 20 hours.

Regarding the method of mixing both components, in order to suppress side reactions such as crosslinking reactions, the two components may be mixed at a low temperature and then heated while stirring, or the polyisocyanate may be added first, and then the polyisocyanate may be added. A method of gradually adding and reacting the hydroxy saturated polymer is preferred.

It is also possible to use multiple types of polyisocyanates in combination. That is, 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 adding another kind of polyisocyanate can also be adopted.

These polyisocyanates can be used as appropriate depending on restrictions such as pot life, but in the present invention it is preferable to select a polyisocyanate so that the pot life is O, S hours or longer at room temperature.

Hydrocarbon oils containing double bonds in the main chain or side chains used as plasticizers in the present invention include alkyldiphenylethane (trade name: 8 stone condenser oil S), alkylbenzene, alkylnaphthalene (trade name). Examples include prefectural chemistry KIS'100), dioctyl phthalate, phenylxyl sulfone, alkylindene monoisoglobylbiphenyl, various aromatic oils such as ethyl diphenylmethane, myrcene, allocimene, diintene, r-thyl♂ene, α- Chir♂nene, Terhyolene, α-pinene, β-eonene, Karenne,
Examples include various chillin compounds such as cadinene, apietadiene, chillin dimer (trade name: cheap crude oil YS Oil D), and the above-mentioned diene oligomers. Hydrocarbon oils containing heavy bonds can be used alone or in combination of two or more. Furthermore, if necessary, a plasticizer containing no double bonds, such as a hydrocarbon oil such as paraffinic process oil, naphthenic process oil, or polybutene oil, can be used in combination.

Further, the hydrogenation catalyst used in the present invention includes nickel,
Examples include transition metal catalysts such as palladium, rhodium, and ruthenium. A preferred catalyst is metal ruthenium. It is generally used supported on carbon, silica, etc.

As a method of adding a plasticizer, component (A) or component (B
) is preferably added in advance. The amount used is the content of component (A), o-go% by weight, preferably lθ
-70% by weight, content in component (B) / -90% by weight, preferably 10-70% by weight. Hydrocarbon - By adjusting the amount of oil used within the above range, the viscosity of component (A) and component (B) can be adjusted at room temperature.
From Ps to 100.000 CPS, or the hardness of the cured product is JISK6JO1, A standard 70 or less, or the initial elastic modulus is 2 o O kg/cn! Hereinafter, it is possible to arbitrarily adjust it preferably within the range of qO or less according to the JIsK&,30/A standard, or within the range of uooky/crl or less in terms of the initial elastic modulus. Typically, 1 is included in the polymer composition.
Preferably, 0 to 0% by weight of oil is contained.

The amount of the hydrogenation catalyst used is preferably o, oos to 0.1% by weight, based on the plasticizer.

The method of mixing the hydrogenation catalyst is when adding the plasticizer (component CA).
Alternatively, it may be added to component (B). Alternatively, the plasticizer and hydrogenation catalyst can be mixed separately and then added by the above method.

Next, component (B) and component (A) obtained as described above
Regarding the blending ratio, the total amount of hydroxyl groups in the polyhydroxy hydrocarbon polymer in component (B) and component (A),
The ratio of the total amount of isocyanate groups (equivalent ratio) is 0.7 to /,
! , more preferably in the range of o, g to l-λ. Outside this range, curing will not proceed completely or only a cured product with poor mechanical strength will be obtained.

In addition, the blending ratio of component (A) and component (B) is
Although it varies depending on the composition of component (B), the weight ratio of component (A/component (B)) is preferably in the range of /10-10//.

The polymer composition obtained as described above can be heated at 20°C from room temperature.
Curing proceeds in the 0°C range. The curing time is shortened as the temperature increases, but it may be determined as appropriate depending on the application.

Additionally, if necessary, curing time can be shortened by adding a catalyst commonly used in the urethane industry, such as dibutyltin laurate. The catalyst can be added by adding it at the time of blending component (A) and component (B), or by adding it to either component (A) or component (B) in advance. good.

The polymer of the present invention includes silica, hydrated silica, alumina,
Klee, Merck, calcium carbonate, magnesium carbonate,
Fillers such as carbon blanks, organic fibers, and glass fibers, as well as flame retardants, stabilizers, crosslinking agents, and known additives used in the urethane industry, rubber industry, etc., may be used as necessary. can.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example/Production of component (A) Polytail ■H as a polyhydroxy hydrocarbon polymer
A (manufactured by Mitsubishi Kasei Corporation, number average molecular weight 2000, iodine value +,!, hydroxyl group concentration 0.90 grams) 3009
, paraffin oil P-200 (manufactured by Kyodo Oil Co., Ltd.,
Paraffinic process oil) ssJy is mixed in room m, and then toluene diisocyanate! ?・Add Sl
The temperature was raised to ro°C. After reacting for g hours, abucafuodrol (ethylene diamine propylene oxide adduct manufactured by Asahi Denka Co., Ltd., q-functional polyol, hydroxyl group concentration/
J,! J meq/l) J O, 7t, YS Resin PX-100 (manufactured by Yasushi Oil Industries Co., Ltd., terpene-based oligomer) itoy and carbon-supported ruthenium C!
%) Catalyst C (manufactured by Nippon Engelhard Co., Ltd.) 6 and 12 were added, and these were stirred and mixed at SO° C. until uniform, to obtain component (A).

What is the average number of hydroxyl groups per molecule of polyol contained in component (A)? It was j.

Production of component (B)Polytail used in component (A) ■HA300? and paraffin oil P-100 3g, l? and mixed at room temperature,
Next, 7 g and 7 f of toluene diisocyaner were added, the temperature was raised to 0.degree. C., and the reaction was carried out for S hours to produce component (B).

Example: Preparation of component (A) Paraffin oil P-200 was mixed with 6931? , Abu Kahuodoror ll? ,/t, YS resin≠Jinchuken-xP
The same procedure as in Example 1 was carried out except that X-100 was changed to λOO12 and the carbon-supported ruthenium catalyst was changed to g and 22.

The average number of hydroxyl groups per polyol/molecule contained in component (A) is 3. Production of component (B) was carried out in the same manner as in Example 1 except that paraffin oil P-200 was changed to JII/9.

Example 3 Aromatic oil 5A instead of YS resin PX-ioo
The same procedure as in Example 1 was conducted except that S-LH (manufactured by Nippon Petrochemicals Co., Ltd.) was used.

The average number of hydroxyl groups per polyol/molecule contained in component (A) was -095.

Example Production of component (A) Polytail ■ HA 3009, paraffin oil P-Cooo'5 (sqgt, toluene diisocyanate /9
．． 7t, diventaerythritol dioctoate (q-functional polyol, hydroxyl group concentration 7.g 9 meq/?) J /, A to the base of abucafuodrol.
Further, YS resin PX-100 was added at 90.t. ! ;
? The same procedure as in Example 1 was carried out except that the carbon-supported ruthenium catalyst was changed to 3.62.

The average number of hydroxyl groups per molecule of polyol contained in component (A) was 1.4 Io.

Manufacture of component (B) Polytail ■HA! ;00t and paraffin oil P-λ
oo, ytsy are mixed at room temperature, then toluene diisocyanate t, 4t, q? Add it and raise the temperature to 5°C.
Allowed time to react. Next, l5ONATE / 4 (J L
(Diphenylmethane diisocyanate liquid modified product manufactured by MD Kasei Co., Ltd.) Co/, fr were added and mixed with stirring at SO° C. for 1 hour to produce component (B).

Example j Production of component (A) Paraffin oil 37r, YS Resin PX-100
The same procedure as in Example G was carried out except that the carbon-supported ruthenium catalyst was changed to /J31 and the carbon-supported ruthenium catalyst was changed to 5.31.

The average number of hydroxyl groups per molecule of polyol contained in component (A) was 2.17.

Production of component (B) Paraffin oil P-, 200 + 9 t.

Toluene diisocyanate 70. lIt, l5ONA
TE/q, y L to 23. The same procedure as in Example 1 was carried out except that Jl was used.

Example 6 Production of component (A) Paraffin oil P-λoo was set to s, 2Of, and dipentaerythritol-based ester polyol (dipentaerythritol, adipic acid, octylic acid was added to a base of diventaerythritol dioctoate). : I, a difunctional polyol produced by reacting at a molar ratio of 2.7 !; meq/? ) / 72 ? with a hydroxyl group concentration of 2.7? using
Further, the same procedure as in Example D was carried out except that the YS resin PX-ioo was changed to G/AP, and the carbon-supported ruthenium catalyst was changed to IT and 6y.

The average number of hydroxyl groups per molecule of polyol contained in component (A) was 0,000.

Production of component (B) Paraffin oil P-co. 'wo J A i y, AIA f toluene diisocyanate.

l5ONATE/4I,? The same procedure as in Example q was carried out except that L was changed to i and tr t.

Example 7 Production of component (A) The dipentaerythritol-based ester polyol used in Example 6 was heated to
2. The same procedure as in Example 6 was carried out except that the carphone-supported ruthenium catalyst was changed to Co1.62.

What is the average number of hydroxyl groups per molecule of polyol contained in component (A)? , 09.

Production of component (B) Paraffin oil P-1. The same procedure as in Example 6 was carried out except that Ot-'l4SP was used.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the carbon-supported ruthenium catalyst was not used.

Comparative Example The same procedure as in Example D was carried out except that the cocarbon-supported ruthenium catalyst was not used.

Comparative Example J The same procedure as in Example 6 was carried out except that the carbon-supported ruthenium catalyst was not used.

Comparative Example Manufacture of component (A)Polytail ■HA300? , paraffin oil P-CoO
O Coco Jf, YS resin PX-ioo 3 pieces It, carbon-supported ruthenium catalyst/1.4 t were mixed at room temperature,
Next, the temperature was raised to SO°C and stirred for 1 hour to obtain component (A).

The average number of hydroxyl groups per molecule of polyol contained in component (A) was i, tr.

Preparation of component (B)Polytail ■HAsooy, Pa, Ffin oil P-co00jTOOf are mixed at room temperature, and then toluene dipentaanor) I O,! ; r wo plus i, yo℃
The temperature was raised to 1, and the mixture was reacted for 3 hours.

Next, Polytail HAB (manufactured by Mitsubishi Kasei Corporation, polyolefin with a number average molecular weight of 2000) 3 pieces 5? , l5ON
ATE/g, 7L, 7/g, and AIF were added and stirred and mixed at SO°C for 1 hour to obtain component (B).

[Blend of component (A) and component (B)]

The components (A) and (B) of Examples 7 to 7 and Comparative Examples/-1 are mixed at the compounding ratio shown in Table 1, defoamed, and poured into a mold (I). It was heated at 100° C. for a period of time to obtain a cured sheet of l colo×/coα×/crIL.

In addition, the similarly mixed and defoamed liquid was added to the depth & CIrL% base area 2.
The mixture was poured into a 0d cylindrical mold (II) to a depth of α and heated at ioo°C for ti and g hours to obtain a cured product.

Measurement of Hydrogen Absorption Performance SO was cut out from the cured sheet produced in the mold (I), placed in a Niro flask, and the inside of the system was evacuated.

Next, hydrogen was introduced to the extent of SOOH1, and the flask was
The tube was placed in an oil bath at 0.degree. C., and the decrease in hydrogen pressure was monitored using a manometer. Table 7 shows the hydrogen pressure at the beginning and after 7 hours.

Compressive Elasticity Modulus Using the cured product produced in the mold (II), the compressive elasticity modulus when 7% compressive deformation was applied was measured using an Ometer manufactured by Fudo Kogyo ■. The results are shown in Table 7.

The polymer composition of the present invention has hydrogen absorption performance as shown in Table 1, and also has a compression modulus of 10 kg/crI1 or more and 50 kg/crtlJJ lower fkf-T:l:>D
It is considered suitable as a high-performance water-stopping material for optical fiber submarine cables.

〔Effect of the invention〕

The polymer composition of the present invention has good hydrogen absorption performance and water stoppage performance.

In addition, it has a long pot life, and its viscosity can be adjusted as appropriate depending on the application, so it has good workability.

Furthermore, since the hardness of the cured product can be adjusted over a wide range, it is possible to provide detailed support for various uses.

Furthermore, it has excellent mechanical properties, heat resistance, weather resistance, hydrolysis resistance, electrical insulation properties, etc., so it can be used as a vibration damping agent for electrical and electronic industries, including as a sealant for semiconductor electronic components. waterproof·
Moisture-proof botting agents, waterproof coatings for marine equipment,
Potting agents, potting agents and adhesives for electronic parts and electrical components used in the automobile industry, as well as waterproof filling, anti-vibration, and moisture-proof potting agents for these cable inlets, interlayer insulation materials for electric wire coils, water-stopping agents for optical cables, etc. It can be used as adhesives and coating agents, and is extremely important industrially.

Applicant: Mitsubishi Kasei Corporation Representative Patent Attorney Hase - Others/Names

Claims (1)

[Claims] (1) A polymer composition consisting of a reaction product of the following polyol component (A) and an isocyanate group-terminated prepolymer (B), a hydrocarbon oil having a double bond in the main chain or side chain, and a hydrogenation catalyst. . (A) Consisting of a hydroxyl-terminated prepolymer or a polyhydroxyhydrocarbon polymer consisting of a polyhydroxy hydrocarbon polymer and a polyisocyanate, and a trifunctional or higher functional polyol, the average number of hydroxyl groups is 2 or more per polyol molecule. The polyol component (B) is an isocyanate group-terminated prepolymer consisting of a polyhydroxy hydrocarbon polymer and a polyisocyanate.