JPS6320315A - Liquid polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a liquid polymer excellent in reactivity and useful as a material for elastomers, adhesives, electrical insulating materials, waterproofings, etc., by hydrogenating a specified liquid polyisoprene and reacting the product with the polyisocyanate compound. CONSTITUTION:100pts.wt. isoprene is polymerized at 20-300 deg.C for 0.1-100hr in the presence of 0.5-200pts.wt. H2O2 to obtain a liquid hydroxyl group- terminated polyisoprene (A). Component A is hydrogenated at 20-300 deg.C for 0.1-100hr in the presence of a catalyst and a polyisocyanate compound in an amount equivalent to a molar ratio of the NCO groups to the OH groups of the hydrogenation product (B) of component A of 1.5-20 is added to the reaction system and reacted at 0-200 deg.C for 0.1-100hr to obtain a liquid polymer of number-average MW of 400-25,000, comprising 0.01-0.99 (molar fraction) of units of formula I and 0.01-0.99 (molar fraction) of units of formula II, having groups of formula III (wherein R is an alkyl, aryl or aralkyl group having at least one NCO group) on both ends and, preferably, represented by formula IV (wherein n is 2-500).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid polymer and a method for producing the same. More specifically, the present invention relates to a novel highly reactive liquid polymer useful as a raw material for elastomers, adhesives, electrical insulation materials, waterproofing agents, etc., and a method for effectively producing the same. be.

[Conventional technology]

Conventionally, liquid diene rubbers having functional groups such as hydroxyl, carboxyl, vinyl, amino, and mercapto groups at the end of the molecular chain have been known. isocyanate compound,
It is crosslinked and cured with epoxy compounds, vinyl monomers, etc., and is widely used, for example, as paints, adhesives, sealants, coating materials, electrical insulation materials, and modifiers for epoxy resins and unsaturated polyester resins.

By the way, among the liquid diene rubbers, it is known that liquid polyisoprene having a hydroxyl group at the end of the molecular chain can be obtained by polymerizing isoprene in the presence of hydrogen peroxide. Hydrogenated polyisoprene is also known.

This hydrogenated product of liquid polyisoprene, which has a hydroxyl group at the end of its molecular chain, is expected to be a raw material for elastomers with excellent weather resistance, but due to its relatively low reactivity, it is not limited in its use. In addition, they have disadvantages such as poor compatibility with other compounds, layer separation of prepared formulations, and poor storage stability.

[Problem that the invention seeks to solve]

The present invention overcomes the drawbacks of liquid polyisoprene hydride having a hydroxyl group at the end of its molecular chain, and has excellent reactivity and good compatibility with other compounds, making it suitable for various uses. The purpose of the present invention is to provide a novel liquid polymer useful for the purpose of the present invention and a method for producing the same.

[Means for solving problems]

As a result of extensive research to achieve the above object, the present inventors have discovered that an alkyl group, an aralkyl group, or an aralkyl group having at least one isocyanate group at both ends of the molecular chain via a urethane bond. A novel liquid polymer with a specific structure having a group is suitable for the purpose, and a typical example of this liquid polymer is a hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain, and a polyisocyanate compound. It was discovered that it could be easily obtained by reacting, and based on this knowledge, the present invention was completed.

That is, the first object of the present invention is the following general formula I,
A liquid polymer CH having a number average molecular weight of 1,400 to 25,000 and having terminal groups represented by the following general formula m at both ends of the polymer consisting of the structural unit and composition represented by the following.

1←C11z-C1l→-■ ÷CHz-CHz10 n R-HNCO-I (However, the molar fraction of units ■ and ■ is 0.01 to 1, respectively.
0.99, in which R is an alkyl group, an aryl group, or an aralkyl group having at least one isocyanate group, and the second purpose is to provide a compound having a hydroxyl group at the end of the molecular chain By hydrogenating liquid polyisoprene and then reacting this hydride with a polyisocyanate compound, a typical example of the liquid polymer of the present invention, which has the general formula % formula % () (R in the formula has the same meaning as above), is produced. and n is 2 to 500).

The present invention will be explained in detail below.

The liquid polymer of the present invention is a novel polymer having the above structure, in which an alkyl group having at least one isocyanate group, an alkyl group having at least one isocyanate group,
It has an aralkyl group or an aralkyl group.

In this polymer, a propylene equivalent unit IH3-4-CIl□-CH+ and an ethylene equivalent unit 1l-G-
CHz-CHz→ may be coupled alternately or randomly, or may be coupled by forming blocks, respectively.

Furthermore, the sum of the repeating number of propylene equivalent units and the repeating number of ethylene equivalent units is 2 to 500, preferably 1.
The range is from 0 to 400, and the mole fraction is from 0.01 to 0.
．． It is 09.

In this liquid polymer, the -i formula % formula % () (R and n in the formula have the same meanings as above) is a form in which propylene equivalent units and ethylene equivalent units are bonded alternately. These polymers are preferred because they can be easily produced using isoprene as a raw material. In this polymer, the repeating number n of isoprene units is 2 to 500, preferably 10 to 400.
selected within the range.

The liquid polymer represented by the general formula (IV) can be easily produced by reacting a hydrogenated liquid polyisoprene having a hydroxyl group at the end of its molecular chain with a polyisocyanate compound.

Liquid polyisoprene having a hydroxyl group at the end of its molecular chain can be obtained by polymerizing isoprene 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. Further, although a reaction solvent is not necessarily required, the reaction is usually carried out in a solvent. Examples of this solvent include n-hexane, n-
Aliphatics such as hebutane, cyclohexane, cycloheptane, benzene, toluene, xylene, ethylbenzene,
Alicyclic, aromatic hydrocarbons, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, 1SO-propyl alcohol, n-butyl alcohol, 1SO-butyl alcohol, 5eC-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketones such as cyclohexanone, esters such as methyl acetate, ethyl acetate, butyl acetate, and cellosolve acetate, and ethers such as diisopropyl ether, dioxane, and tetrahydrofuran.

There is no particular restriction on the reaction temperature, but it is usually 20 to 3
00°C, preferably in the range of 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,
0 kg/cJ -G or less, preferably 50 kg/a
A pressure below d-G is desirable. Furthermore, the reaction time is influenced by the reaction temperature and reaction pressure, but is generally 0.
．． The time is selected within the range of 1 to 100 hours, preferably 1 to 50 hours.

After carrying out the polymerization reaction in this manner, the reaction-completed liquid is washed with water, and then the solvent and the low-boiling point portion of 7mer 1 are distilled off under reduced pressure to obtain liquid polyisoprene having a hydroxyl group at the end of the molecular chain. It will be done. The number average molecular weight of this substance is
It is desirable that the OH value is in the range of 300 to 25,000, preferably 500 to 10,000, and the OH value is 0.1 to 10 m eq / g, preferably 0.3 to 7 m eq / g. It is desirable that it be within the range.

Next, the liquid polyisoprene having a hydroxyl group at the end of its molecular chain is hydrogenated. In this hydrogenation reaction, although a solvent is not necessarily required, the reaction is usually carried out in a solvent. As the solvent, the solvents mentioned in the above polymerization reaction can be used. As the hydrogenation catalyst, catalysts commonly used in hydrogenation reactions, such as nickel-based, palladium-based, ruthenium-based, platinum-based catalysts, are 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/crA -G or less, preferably 100 kg/crA -G or less.
A pressure of less than kg/coi-G is desirable. The reaction time depends on the reaction temperature, reaction pressure, type of catalyst, etc., but is generally 0.1 to 100 hours, preferably 1 to 5 hours.
Selected within the range of 0 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 a hydroxyl group at the end of the molecular chain. The number average molecular weight of this product is 300 to 25,000, preferably 500 to i
It is desirable that the hydroxyl group content is in the range of 0.1 to 10, preferably 0.0.
3~? It is desirable that the weight be in the range of 77g.

By reacting the thus obtained hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain with a polyisocyanate compound, a liquid polymer represented by the general formula (IV) can be obtained. This polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has an isocyanate group reactive with the hydroxyl group of the hydride of the hydroxyl group-containing liquid polyisoprene. Examples of polyisocyanate compounds include the customary aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MD 1) Methylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction product, etc., among others, MDI
, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like are preferred.

There is no particular restriction on the proportion of the polyisocyanate compound and the hydride used, but usually the water 9i (
Ratio of isocyanate iJ (N G O) of polyisocyanate compound to OH) (N G O10H)
It is desirable to use both in a molar ratio of 1.5 to 20, preferably 1.8 to 15.

This reaction may be carried out in the absence of a solvent or in a solvent. As the solvent, those mentioned in the case of the polymerization reaction can be used.

There is no particular restriction on the reaction temperature, but it is usually 0 to 200
℃, preferably in the range of 15 to 150℃. Furthermore, the reaction may be carried out under normal pressure or under increased pressure, but when the reaction is carried out under increased pressure, 100 kg
The pressure is desirably less than /c+d-G, preferably less than 50 kg/c+d-G. The reaction time depends on the reaction temperature and the like, but in terms of -i, it is selected in the range of 0.1 to 100 hours, preferably 1 to 50 hours.

After carrying out the reaction in this manner, the remaining polyisocyanate compound in the reaction-completed liquid is distilled off under reduced pressure to obtain a liquid polymer represented by the general formula (IV). The number average molecular weight of this material is desirably in the range of 400 to 26,000, preferably 500 to 10,000, and the content of isocyanate groups is in the range of O, 1 to 20% by weight, preferably 0.5 to 15% by weight. It is desirable that the

Further, the liquid polymer (rV) obtained from isoprene may contain a small amount of structural units resulting from 1,2 polymerization or 3.4 polymerization of isoprene.

The liquid polymer having a main chain consisting of propylene-equivalent units and ethylene-equivalent units of the present invention is not only produced from isoprene (for example, by copolymerizing ethylene and propylene in the presence of an azo compound containing a hydroxyl group). However, it can also be obtained by reacting the resulting copolymerization with a polyisocyanate compound.

The liquid polymer of the present invention obtained in this way is a novel polymer having an alkyl group, an aryl group, or an aralkyl group with a small number of isocyanate M (one isocyanate M) at both ends of the molecular chain via urethane bonds. It easily reacts with polyol compounds, polyamine compounds, etc. to give cured products, which can be used for various purposes.

〔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.

Example 1 Isoprene 200 was added to 11 stainless steel pressure-resistant reaction vessels.
g, 16 g of 50% by weight aqueous hydrogen peroxide solution, and 100 g of n-butyl alcohol, heated at 120°C, maximum pressure 8.
The polymerization reaction was carried out at kg/crA-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 to 2 mm and 1 g under reduced pressure at 100°C.
The solvent, unreacted monomers 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 and an OH value of 0.96 meq/g.

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 lj' stainless steel pressure-resistant reaction vessel, and hydrogen was added at 50kg/cd-
4. At 140° C. while maintaining the pressure of G.
The hydrogenation reaction was carried out for 5 hours.

After the completion of the hydrogenation reaction, 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 2mm, 11g, 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 10
1 g was obtained. The number average molecular weight of this product is 2210,
The OH value was 0.94 meq/g1 and the iodine value was 1 or less.

Next, 300mj! 50 g of the above hydride and tolylene diisocyanate (TDI) were placed in a separable flask.
20g was added thereto, and the reaction was carried out at 25°C for 2 hours and at 70°C for 4 hours under normal pressure. The reaction solution was heated under a reduced pressure of 2 nmHg at 11
The treatment was carried out at 0° C. for 4 hours to distill off the remaining tolylene diisocyanate to obtain 58.2 g of a hydrogenated liquid polyisoprene having an isocyanate group at the end of the molecular chain. The number average molecular weight of this product is 2610, and the NCO content is 3.45.
Weight% (theoretical value 3.39% by weight), nitrogen content is 2.2
0% by weight (theoretical value 2.26% by weight), the amount of free TDI is 0
．． It was less than 0.05% by weight. The number average molecular weight was determined using a paper pressure osmometer (VPO), the nitrogen content was determined by elemental analysis, and the amount of free TDI was determined by gel permeation chromatography (GPC) using diphenyl as an internal standard.

In addition, the infrared absorption spectrum confirmed the appearance of absorption due to NGO groups (peak 1720 (J-')) and absorption due to urethane bonds (peak 2250 cm-'). Figure 1 shows the infrared absorption spectrum chart. shows.

FIG. 2 is an infrared absorption spectrum chart of a hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain,
Absorption by hydroxyl group near 3360 cm-' and 29
Near 60C11-'~2860CI11-', 1465
Absorption by hydrocarbon skeletons was observed near c1m-' and 1380cm-'.

Example 2 Isoprene 200 was placed in a 1i stainless steel pressure-resistant reaction vessel.
g, 50% by weight hydrogen peroxide aqueous solution 50g and 5ec-
300 g of butyl alcohol was charged, and a polymerization reaction was carried out at 115° C. and a maximum pressure of cuff kg/cd G for 2.5 hours.

Next, post-treatment was carried out in the same manner as in Example 1 to obtain 116 g of 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 value is 1.39.
m eq / g T: Yes.

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 11 stainless steel pressure-resistant reaction vessels, and hydrogen was added at 50kg/cd.
5 at 140°C while maintaining the pressure of -G.
The hydrogenation reaction was carried out for an hour. Next, the same post-treatment as in Example 1 was performed to obtain 106 g of a liquid polyisoprene hydride having a hydroxyl group at the end of the molecular chain. This product had a number average molecular weight of 1450 and an OH value of 1.36 meq/g.

Next, 300mj! In a separable flask, 50 g of the hydrogenated Th and hexamethylene diisocyanate (H
Add 50g of MDI) and 50g of cyclohexane,
The reaction was carried out at 5°C for 2 hours and at 80°C for 7 hours under normal pressure. Subsequently, the same post-treatment as in Example 1 was performed to obtain 61.8 g of a hydrogenated liquid polyisoprene having an isocyanate group at the end of the molecular chain. The number average molecular weight of this product is 189
0, NCO content is 4.7% by weight (theoretical value 4.65% by weight), nitrogen content is 3.23% by weight (theoretical value 3.10% by weight), free HMD l amount is less than 1% by weight. there were.

Note that the number average molecular weight, nitrogen content, and free HMDI amount were determined by the same method as in Example 1. In addition, the infrared absorption spectrum shows that the absorption due to NGO group≠ (peak 172
5 c+++-') appearance, → absorption (
Peak 232 QC! 11-') was confirmed.

FIG. 3 shows this infrared absorption spectrum chart.

FIG. 4 is an infrared absorption spectrum chart of a hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain,
Absorption by hydroxyl group near 3270 cm-' and 29
Around 60-2860cm-', around 1460cm-',
Absorption due to the hydrocarbon skeleton was observed near 1380c111-'.

〔Effect of the invention〕

The liquid polymer of the present invention is a novel highly reactive polymer having at least one isocyanate group-containing alkyl group, aryl group, or aralkyl group at both ends of the molecular chain via urethane bonds. Therefore, it is useful as a raw material for, for example, elastomers, adhesives, electrical insulation materials, waterproofing agents, etc.

In addition, according to the method of the present invention, by reacting a polyisocyanate compound with a hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain, isocyanate is added to the end of the molecular chain, which is typical among the liquid polymers of the present invention. Hydrogenates of liquid polyisoprene having groups can be produced very easily.

[Brief Description of the Drawings] Figures 1 and 3 are infrared absorption spectrum charts of the hydride of liquid polyisoprene having an isocyanate group at the molecular chain end of the present invention in Examples 1 and 2, respectively, and Figure 2 shows and FIG. 4 are infrared absorption spectrum charts of hydrides of liquid polyisoprene having a hydroxyl group at the end of the molecular chain in Examples 1 and 2, respectively.

Claims (1)

[Scope of Claims] 1. A polymer having a structural unit and composition represented by the following general formulas I and II and having a terminal group represented by the following general formula III at both ends thereof and having a number average molecular weight of 400 to 400. 25,000 liquid polymers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I -(CH_2-CH_2)- II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ III (However, the mole fraction of units I and II is 0.01 each.
~0.99, and R in the formula is an alkyl group, aryl group, or aralkyl group having at least one isocyanate group) 2. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula The liquid polymer according to claim 1, wherein R is an alkyl group, an aryl group, or an aralkyl group having at least one isocyanate group, and n is 2 to 500. 3. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (where R in the formula is an alkyl group, an aryl group, or an aralkyl group having at least one isocyanate group, and n is 2 to 500.