JPS6369862A - Bitumen composition - Google Patents

Abstract

PURPOSE:To obtain a bitumen composition having excellent thermal aging resistance and weather resistance and suitable for water-proofing material, sealing material, etc., by compounding a hydrogenated product of hydroxyl- containing liquid polyisoprene and a polyisocyanate compound to a bituminous substance. CONSTITUTION:100pts.wt. of a bituminous substance (e.g. natural asphalt) is compounded with (A) 1-1,000pts.wt., preferably 5-200pts.wt. of a hydrogenated product of a hydroxyl-containing liquid polyisoprene having a number-average molecular weight of 300-25,000 and a hydroxyl content of 0.1-10meq/g in terms of OH value and (B) a polyisocyanate compound (e.g. tolylene diisocyanate). The molar ratio of the isocyanate group (NCO) of the component B to the hydroxyl group (OH) of the component A (NCO/OH) is 0.1-10.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel bituminous compositions.

More specifically, the present invention relates to a bituminous composition particularly excellent in heat aging resistance, which is suitable for use in waterproofing materials, sealing materials, road paving materials, and the like.

[Conventional technology]

BACKGROUND ART Compositions comprising a bituminous substance, liquid polybutadiene having a hydroxyl group, and a polyisocyanate compound are conventionally known as bituminous compositions used as waterproofing materials, sealing materials, road paving materials, and the like.

However, since this bituminous composition has the disadvantage of poor weather resistance and heat aging resistance, it has been proposed to use its hydride in place of the liquid polybutadiene. However, when using this hydride, although the weather resistance is improved to some extent, when polybutadiene, which is the raw material for this hydride, has a large number of 1.4-addition type skeletons, the hydride becomes solid and the 1.2-addition type skeleton becomes solid. - When having a large number of addition-type skeletons, the average number of functional groups (OH) becomes small, and due to these factors, heat aging resistance cannot be improved at all.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a bituminous composition particularly excellent in heat aging resistance, which can be suitably used in waterproofing materials, sealing materials, road paving materials, and the like.

[Means for solving problems]

As a result of extensive research to achieve the above object, the present inventors found that a composition in which a liquid polyisoprene hydride having a hydroxyl group and a polyisocyanate compound are blended with a bituminous substance is suitable for the purpose. The present invention was completed based on this finding.

That is, the present invention provides a bituminous composition containing a bituminous substance, a hydride of liquid polyisoprene having hydroxyl groups, and a polyisocyanate compound.

The present invention will be explained in detail below.

The bituminous substances used in the composition of the present invention include:
Examples include, but are not limited to, natural asphalt, straight asphalt, blown asphalt, semi-prone asphalt, petroleum asphalt such as solvent deasphalted asphalt, petroleum pitch, coal tar, coal pitch, and the like.

The hydrogenated liquid polyisoprene having a hydroxyl group used in the composition of the present invention has a number average molecular weight of 300 to 100 and has a hydroxyl group in the molecule or at the end of the molecular chain.
00 liquid polyisoprene hydride is used. This material can be obtained, for example, by hydrogenating liquid polyisoprene having hydroxyl groups. Liquid polyisoprene having hydroxyl groups is obtained, for example, by polymerizing isoprene in a liquid reaction medium in the presence of hydrogen peroxide. In this reaction, hydrogen peroxide is usually used in an amount of 0.5 to 200 parts by weight, preferably 1 to 50 parts by weight per 100 parts by weight of isoprene. There is no particular restriction on the reaction temperature at this time, but it is usually 20 to 300°C,
Preferably, the temperature is selected within the range of 30 to 200°C. In addition, the reaction may be carried out under normal pressure or under increased pressure, but when the reaction is carried out under increased pressure, 200 kg/kg
A pressure of less than cn+-G, preferably less than 50 kg/cJ-G is desirable. Furthermore, although the reaction time depends on the reaction temperature and reaction pressure, it is generally selected in the range of 0.1 to 100 hours, preferably 1 to 50 hours.

After carrying out the polymerization reaction in this way, the reaction-completed liquid is washed with water, and then the solvent, monomer, and low-boiling bones are distilled off under reduced pressure to obtain a liquid polyisoprene having hydroxyl groups. The number average molecular weight of this product is 300 to 25
000, preferably in the range of 500 to 10,000, and regarding the hydroxyl group content, the OH number is 0.1 to 10 m eq / g, preferably 0.
It is desirable to be in the range of 3 to 7 meq/H.

Next, the obtained liquid polyisoprene having hydroxyl groups is hydrogenated. In this hydrogenation reaction, although a solvent is not necessarily required, the reaction is usually carried out in a solvent. As the hydrogenation catalyst, catalysts commonly used in hydrogenation reactions, such as nickel-based, palladium-based,
A ruthenium-based catalyst, a platinum-based catalyst, or the like is used. These catalysts may be used alone or in combination of two or more, or may be supported on a carrier such as activated carbon.

There is no particular restriction on the temperature of the hydrogenation reaction, but it is usually 2
The temperature is selected within the range of 0 to 300°C, preferably 30 to 200°C. Further, the reaction may be carried out under normal pressure or under increased pressure, but when the reaction is carried out under increased pressure, the reaction rate is 200 kg/cJ -G or less, preferably 100 kg/cJ -G or less.
A pressure of less than g/cnl-G is desirable. The reaction time depends on the reaction temperature, reaction pressure, type of catalyst, etc.
Generally, the time is selected within the range of 0.1 to 100 hours, preferably 1 to 50 hours.

After separating the catalyst from the hydrogenation reaction completed liquid, the solvent is distilled off under reduced pressure to obtain a hydride of liquid polyisoprene having hydroxyl groups. The number average molecular weight of this product is 30
It is desirable that it is in the range of 0 to 25,000, preferably 500 to 10,000, and the hydroxyl group content is
OH value is 0.1-101, preferably 0.3-7 meq/
It is desirable that it be in the range of g.

The hydride of liquid polyisoprene having hydroxyl groups thus obtained is blended in an amount of, but not particularly limited to, usually 1 to 1000 parts by weight, preferably 5 to 200 parts by weight, per 100 parts by weight of the bituminous material.

Next, as the polyisocyanate compound used in the composition of the present invention, an organic compound having two or more isocyanate groups in one molecule is used. Examples of these include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate. , xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1°5-diisocyanate, isopropylbenzene-2,4-diisocyanate,
Examples include addition reaction products of polypropylene glycol and tolylene diisocyanate, and particularly preferred are MDI, liquid modified diphenylmethane diisocyanate, and tolylene diisocyanate.

There is no particular restriction on the ratio of the polyisocyanate compound and the polyisoprene hydride used, but usually the ratio of the isocyanate group (NGO) of the polyisocyanate compound to the hydroxyl group (OH) of the polyisoprene hydride (NGOloH) is It is desirable to use both in a molar ratio of 0.1 to 10.0, preferably 0.6 to 4.0.

Various additives may be added to the composition of the present invention, if desired. Additives to be added as desired include:
Examples include fillers such as mica, graphite, vermiculite, calcium carbonate, and slate powder.

In addition, plasticizers such as dioctyl phthalate are added as viscosity modifiers, softeners such as aromatic, naphthenic, and paraffin oils are added, and alkylphenol resins, terpene resins, and terpenephenol resins are added to adjust adhesive strength and adhesive strength. Tackifying resins such as resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and aromatic petroleum resins can also be added. Further, curing accelerators such as dibutyltin dilaurate, stannous octoate, and polyethylene diamine can also be added. Furthermore, an anti-aging agent may be added to improve weather resistance, and a silicon compound or the like may be added as an antifoaming agent.

The composition of the present invention can be prepared by mixing a bituminous substance, a hydride of liquid polyisoprene having a hydroxyl group, a polyisocyanate compound, and various optional additives, and thoroughly stirring and mixing.

The bituminous composition of the present invention prepared in this manner provides a cured product with excellent heat aging resistance, weather resistance, etc. by curing treatment. There are no particular restrictions on the conditions for the curing treatment, but the curing treatment is usually carried out at a temperature of 0 to 120°C, preferably 15 to 70°C, for 0.5 to 200 hours, preferably 1 to 1
Hardening treatment is performed by heating for 80 hours.

The bituminous composition of the present invention can be used in a wide range of applications, such as waterproofing materials, sealing materials, road paving materials, etc., since it provides a cured product with excellent properties through curing treatment.

〔Example〕

Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples in any way.

Production Example 1 Isoprene 200 was added to 11 stainless steel pressure-resistant reaction vessels.
g, 50% by weight hydrogen peroxide aqueous solution 16g and 5ec
-100 g of butyl alcohol was added, and a polymerization reaction was carried out at 120°C and a maximum pressure of 8 kg/ca -G for 2 hours.

After the reaction was completed, the reaction solution was taken out, shaken with 600 g of water in a separatory funnel, and left to stand for 3 hours to separate the oil layer. This oil layer was heated at 100°C under a reduced pressure of 2nHg.
The solvent, unreacted particles and low-boiling components were distilled off, and liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained in a yield of 68% by weight. This product had a number average molecular weight of 2150, an OH content of 0.96 meq/g, and a viscosity of 56 poise/30°C.

Next, 100 g of the thus obtained liquid polyisoprene having a hydroxyl group at the end of the molecular chain, 10 g of cyclohexane
0g and 10g of 5wt% Ru-C catalyst were placed in a stainless steel pressure-resistant reaction vessel of 11, and hydrogen was added at 50kg/cJ-c.
A diluted hydrogenation reaction was carried out at 140° C. for 5 hours while maintaining the pressure of .

After the hydrogenation reaction was completed, the reaction solution was taken out and the catalyst therein was separated using a 0.45μ membrane filter.The filtrate was treated for 2 hours at a vacuum of 2mmHg and a temperature of 110°C to remove the solvent. When distilled off, a hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain 101 was obtained.
g was obtained. The number average molecular weight of this product is 2210, O
The H content was 0.94 meq/g, the iodine value was 1 or less, and the viscosity was 383 poise/30°C.

Production Example 2 In Production Example 1, 50 g of 50% by weight hydrogen peroxide aqueous solution
, 300 g of 5ec-butyl alcohol.

A polymerization reaction was carried out in the same manner as in Production Example 1, except that the temperature was 115° C. and the reaction time was 2.5 hours, to obtain liquid polyisoprene having a hydroxyl group at the end of the molecular chain. The number average molecular weight of this product is 1380, and the OH content is 1.39 m eq /
g, and the viscosity was 23 voids/30°C.

Next, the obtained liquid polyisoprene was subjected to a hydrogenation reaction under the same conditions as in Production Example 1, and a hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained.

The number average molecular weight of this product is 1450, and the OH content is 1.3.
6 m eq / g, iodine value is 1 or less, viscosity is 2
The temperature was 4 days at 30°C.

Production Example 3 100 g of 1,4-addition type liquid polybutadiene having a hydroxyl group at the end of the molecular chain, 100 g of cyclohexane, and 10 g of 5 wt% Ru-C catalyst were placed in a 1β pressure-resistant reaction vessel.
Hydrogenation reaction was carried out at 14.0° C. for 4.5 hours while introducing hydrogen to maintain a pressure of 50 kg/cJ G.

After the hydrogenation reaction was completed, the reaction solution was taken out, 500 m 12 of toluene was added thereto, and the catalyst was separated using a 0.45 μm membrane filter. The treatment was carried out under the following conditions for 2 hours, and the solvent was distilled off to obtain 96 g of waxy solid. The number average molecular weight of this product was 2920, and the OH content was 0.80 m eq / g.

In addition, 1, 4 which has a hydroxyl group at the end of the molecular chain used as a raw material
- Addition type liquid polybutadiene is manufactured by Idemitsu Arco ■, R-
4,5HT, number average molecular weight 2800, OH content 0.8
2 meq/g, viscosity 50 poise/30°C, 1.4-content 80 mol%, 1.2-content 20 mol%.

Production Example 4 A 1,2-addition liquid polybutadiene having hydroxyl groups inside the molecular chain (not all at the ends) was hydrogenated and post-treated in the same manner as in Production Example 1 to produce a highly viscous liquid hydride. Obtained. The number average Q molecular weight of this product was 2080, the OH content was 0.84 meQ/g, and the viscosity could not be measured at 30°C using a B-type viscometer.

In addition, the 1°2-addition type liquid polybutadiene having a hydroxyl group inside the molecular chain of the raw material is manufactured by Nippon Soda, Nl5SOP.
BG-2000, number average molecular weight 2000. OH content 0.85meq/g1 viscosity 1930voices/30℃
, 1.2-content 90 mol%, 1.4-content 10 mol%.

Examples 1 to 3, Comparative Example 1.2 The ingredients shown in the attached table were placed in a container with the indicated amount, stirred and mixed at 120°C for 1 minute to prepare a composition, poured into a Teflon mold, and cured at 25°C for 168 hours. A cured product was obtained. The physical properties of this cured product are shown in the table.

(The following is a blank space) 1. [Effects of the invention] The bituminous composition of the present invention has improved heat aging resistance,
It can provide a cured product with excellent weather resistance, and is suitably used, for example, as a waterproofing material, a sealing material, a road paving material, etc., and its industrial value is extremely large.

Claims (1)

[Claims] 1. A bituminous composition containing a bituminous substance, a hydride of liquid polyisoprene having a hydroxyl group, and a polyisocyanate compound.