JPH0255748A - Liquid polymer and composition thereof - Google Patents

Abstract

PURPOSE:To obtain a liq. polymer useful for providing a polyurethane with excellent water resistance, humidity resistance, heat resistance and weatherability by blending an antioxidant consisting of a specified hydrogenated liq. polyisoprene contg. hydroxyl groups with a compd. having a plurality of phenol residues. CONSTITUTION:100 pts.wt. hydrogenated liq. polyisoprene contg. hydroxyl groups obtd. by hydrogenating at least 50% unsatd. bonds of a liq. polyisoprene contg. 5-20mol% 1, 2 or 3, 4 bonds and having a number-average MW of 700-7,000 and 1.5-4 hydroxyl groups per molecule is blended with pref. 0.01-5 pts.wt. antioxidant consisting of a compd. having 2-4 phenol residues, e.g., 2,2-methylenebis-(4- methyl-6-t-butylphenol).

Description

[Detailed description of the invention] [Industrial application field] The present invention has excellent operability, and the cured product thereof has excellent heat resistance,
The present invention relates to a novel liquid polymer having weather resistance, water resistance, adhesiveness and rubber elasticity, and a composition containing the same.

[Conventional technology]

BACKGROUND ART Hitherto, I-urethane made of polyester and polyether polyols has been widely used for applications such as sealing materials, coating materials, and botting materials.

However, conventional polyester and polyether polyols do not necessarily have sufficient water resistance and heat and humidity resistance due to the ester and ether bonds present in their molecular chains. In addition, polybutanoene polyols have come into use in recent years, but although they have improved water resistance and moist heat resistance, they have poor heat resistance and poor heat resistance due to the carbon-carbon double bond in the main chain.
Weather resistance is poor. In order to improve this heat resistance and weather resistance, a method has been used to hydrogenate the carbon-carbon double bonds, but in the case of polybutanoene, by hydrogenating the di main chain is Because it has a structure of crystalline gold, it becomes solid at room temperature, and when used as a urethane raw material, it has extremely poor operability when mixed with compounding agents such as isocyanate compounds and fillers, and when molded. In addition, attempts have been made to use hydrogenated liquid polyisoprene, which does not have crystallinity, as a raw material for urethane.However, in this case, although the operability was sufficiently improved, the unsaturated bonds were removed at a hydrogenation rate of 1100 yen. Even if it is completely eliminated, the thermal stability and heat deterioration resistance in air at high temperatures are not necessarily sufficient.

[11 Problems to be Solved by the Invention] The present invention provides a polyurethane that has excellent water resistance, moisture resistance, heat resistance, weather resistance, sufficient strength and adhesive properties, and excellent thermal stability. Furthermore, it is an object of the present invention to provide a raw material for polyurethane that has excellent operability in mixing, molding, etc. when obtaining polyurethane.

[Means to solve the problem]

According to the present invention, the above object is achieved by a liquid polymer comprising a specific hydroxyl group-containing liquid hydrogenated polyisoprene and a specific antioxidant, or a composition containing the same.

That is, the present invention provides 1,2 or 3,4 bonds t-5 to 2
Contains 0 mot% and has a number average molecular weight of 700 to 7,00
Hydrogenated liquid polyisoprene containing hydroxyl groups obtained by total hydrogenation of 50 or more unsaturated bonds of liquid polyisoprene having 0 and 91.5 to 4.0 hydroxyl groups per molecule, and phenol residues. It relates to a liquid polymer containing an antioxidant consisting of a compound having 2 to 4 of the above, and also contains 1,2 or 3,4 bonds t-5 to 20 Mott4, and has a number average molecular cap of 700. ~7.
Hydrogenated liquid polyisoprene containing hydroxyl groups obtained by hydrogenating 50% or more of the unsaturated bonds of liquid polyisoprene having v1.5 to 4.0 hydroxyl groups per molecule and having v1.5 to 4.0 hydroxyl groups per molecule, phenol residue 'lk2 The present invention relates to a composition containing an antioxidant consisting of a compound having ~4 antioxidants, and a polyisocyanate compound.

Vinyl bond in the hydroxyl group-containing liquid polyisoprene used in the present invention! (1,2 or 3,4 bond f) needs to be in the range of 5 to 20 mol. If the amount of vinyl bonds is less than 5 molfa, problems arise in that the final polyurethane has low strength and elongation and does not have sufficient adhesive strength to metallic glass or the like. Moreover, when it exceeds 20 mo1%, mechanical properties such as rubber elasticity at low temperatures of polyurethane deteriorate. Preferably, the vinyl bond amount is 7 to 15 mol%. In addition, 1.4-cis,
1.4-) The microstructures of lance, 1,2-vinyl and 3,4-vinyl are based on the values determined from the 'H-NMR spectrum.

In addition, the number average molecular weight of liquid polyisoprene containing hydroxyl groups is 7.
It is necessary to be between 00 and 7.000.

When the number average molecular weight is less than 700, the cured product with the polyisocyanate compound does not have good rubber elasticity. Also 7
, OOO, the polyisoprene will no longer exhibit good fluidity. Hydrogenated polyisoprene obtained by hydrogenating this also does not exhibit fluidity. The number average molecular weight ffl of the polyisobure/isolite is preferably 1. OOO~5,
It is 000.

The number of hydroxyl groups (=average number of hydroxyl groups per molecule) of the hydroxyl group-containing liquid polyisoprene is required to be from 1.50 to 4.0. If the number of hydroxyl groups is less than 1.50Kf4,
Sufficient crosslinking is not obtained in the reaction with the polyisocyanate compound, resulting in the problem that the mechanical strength of the urethane is poor. When the number of hydroxyl groups exceeds 4.0, the crosslinking density becomes too high and the cured product does not exhibit good rubber elasticity. Therefore, the number of hydroxyl groups must be within the above range, preferably 1
．． 8-3,0.

This hydroxyl group may be located either at the end of the molecular chain or within the chain, but those located at both ends are preferably used.

Next, the method for producing the hydroxyl group-containing liquid polyisoprene and its hydrogenated product of the present invention will be described. The hydroxyl group-containing liquid polyisoprene referred to in the present invention is known or can be easily produced by known methods. For example, the isogrene monomer can be replaced with hydrogen peroxide, an azo compound having a hydroxyl group (for example, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-glopionamide], etc.) or a 4-oxide having a hydroxyl group. Hydroxyl group-containing liquid polyisoprene can be obtained by radical polymerization using (for example, cyclohexanone peroxide) as a polymerization initiator. The amount of the polymerization initiator to be used is, for example, H20□1.2 to 12 J, 2,2'-azobis-[2-methyl-N-(2-hydroxyethyl)-gropionamide) 9 to 1001 isogrene monomers. .2-92Il.

Cyclohexanone peroxide 7.6-761 is suitable. Although polymerization can be carried out without a solvent, it is preferable to use a solvent for ease of controlling the reaction.

Ethanol, ingropanol, etc. are usually used as the solvent. Reaction temperature: 100-150℃, reaction time: 5
~15 hours is appropriate.

Furthermore, hydroxyl group-containing liquid polyisoprene can also be obtained by anionically polymerizing Inglene monomer using a catalyst such as naphthalene dilithium to produce Inglene living polymer, and further reacting with a monoepoxy compound or the like. Although polymerization can be carried out without a solvent, it is preferable to use a solvent from the same viewpoint as in the case of radical polymerization. Saturated hydrocarbons such as hexane and cyclohexane are used as the solvent. Reaction temperature is 50-100
℃, and the reaction time is suitably 1 to 10 hours.

In some cases, a liquid polyisoprene having a hydroxyl group introduced into its side chain by an addition reaction may also be used (for example, JP-A-57-16003).

In the present invention, the above? Liisoprene is used after hydrogenation. At this time, 50 or more carbon-carbon double bonds in the polyisoprene are hydrogenated.

If it is less than 50%, there is a problem of deterioration of heat resistance and light resistance due to heat or light due to the double bond of the cured product with the I-lysocyanate compound. Preferably, the hydrogenation rate is 80% or more, more preferably 90% or more.

The hydroxyl group-containing hydrogenated liquid polyisoprene used in this invention can be obtained by hydrogenating the hydroxyl group-containing layered polyisoprene produced as described above by a known method using a homogeneous catalyst, a heterogeneous catalyst, etc. can.

When using a homogeneous catalyst, all solvents are saturated hydrocarbons such as hexane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, etc., and hydrogen at normal pressure to 50'Q/an2 is used at a reaction temperature of room temperature to 150°C. The hydrogenation reaction is carried out under pressure. As a homogeneous catalyst, a Ziegler catalyst made of a combination of an organic compound of a transition metal and an alkylated product of aluminum, an alkaline earth metal, or an alkali metal is used in an amount of 0.01 to 0.1 mo per double bond of the polymer.
Use approximately t%. The reaction usually completes in 1 to 24 hours.

When using a heterogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, THF and nooxane, ethanol, isoglopanol,
Using alcohols, etc. or a mixture thereof as a solvent, #/sub2
The hydrogenation reaction is carried out under a hydrogen pressure of .

As a heterogeneous catalyst, a catalyst such as nickel, cobalt, halazoum, platinum, rhodium, or ruthenium is used alone or supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon, and the amount used is 0 relative to the weight of the polymer. .5-1
0 wt% is suitable.

The reaction usually completes in 1 to 48 hours.

The compound having 2 to 4 phenol residues used as an antioxidant in the present invention is preferably added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the hydroxyl group-containing hydrogenated liquid polyisoprene. Examples of such antioxidants include 2,2'-methylene/-bis-(4-methyl-6-
t@rt-butylphenol), 2,2'-methylene-
Bis-(4-ethyl-6-tart-butylphenol), 4,4'-methylene-bis-(2,6-not@r
t-butylphenol), 2,2'-methylene-bis-
Bisphenol compounds such as (6-αmethyl-benzyl-p-cresol), 1,3.5-)limethyl-2,
4,6-! -Squirrel (3,5-Gt@rt-Butyl-4
-hydroxypencil)benzene, tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)
Trisphenol compounds such as butane, tetrakis-[
Examples include tetrakisphenol compounds such as methylene-3-(3',5'-di-tart-butyl-4'-hydroxyphenyl)propionate comethane. Monophenolic compounds, which have been most commonly used as phenolic antioxidants, are completely unsuitable for the purpose of the present invention. In addition, amine compounds, which are other types of antioxidants, have serious problems such as discoloration and staining, and are not suitable for the purpose of the present invention.

As mentioned above, the antioxidant is used in the range of 0.01 to 5 parts by weight. If the amount added is less than 0.01 parts by weight, no improvement in heat resistance can be obtained; Even if the amount is added in excess of this amount, the effect will be almost the same as if it is added in an amount less than that amount, and this is not preferable since it will actually impair economic efficiency.

The composition of the present invention contains the hydroxyl group-containing hydrogenated liquid polyisoprene obtained as described above and a polyisocyanate compound. The content ratio of both is in the range of 2 to 5 as the ratio of isocyanate groups to hydroxyl groups in polyynyl y, that is, NeoloH. If this ratio is less than 2, it will not be possible to react with all the hydroxyl groups with the incyanate group, and if it exceeds 5, there is a risk that gluing will occur during the addition reaction, which is not preferable.

Here, the polyisocyanate compound is not particularly limited, and 1
Isocyanate compounds containing two or more isocyanate groups in the molecule are used. Examples include tolylene diisocyanate, phenylene soisocyanate, diphenylmethanoisocyanate, modified zobuenylmethanezoisocyanate, dicyclohexylmethane diisocyanate, and the like.

The hydroxyl group-containing hydrogenated liquid polyisoprene and the polyisocyanate compound react to produce isocyanate group-containing hydrogenated liquid polyisoprene, and the reaction conditions can be those commonly used in the production of urethane prepolymers. .

That is, the reaction temperature is selected from the range of room temperature to 200°C, and the reaction time is selected from the range of 0.1 hour to 50 hours. At this time, tin and a cabin compound can be used as a catalyst. If an isocyanate compound from the bed reaction is present after the reaction, it may be removed by reducing the pressure, di-extracting with a solvent, etc., and used in the next step.

In this way, hydrogenated polyisoprene having inocyanate groups added to its molecule is obtained, which usually contains 1.5 or more isocyanate groups per molecule. This product may also contain an isocyanate compound that has not reacted with the OH group. HNCO as the amount of NCO in the product
It is preferable that the content of hydrogenated polyisosol is 10% by weight or less.

The isocyanate group-containing hydrogenated liquid polyisoprene polymer obtained as described above is cured and used by a method conventionally used in the production of polyurethane.

1 Water, a polyol compound, and a polyamine compound are used for curing.

Examples of polyol compounds include 1,4-butanediol, ethylene glycol, propylene glycol, pentanediol, etc., and examples of polyamine compounds include triethylenediamine, tetraethylenediamine, hexamethylenediamine, etc.

When curing these compounds, the molar ratio of NCO groups to hydroxyl or amino groups in polyisoprene (NC010
From the viewpoint of the physical properties of the cured product obtained, it is preferable that H or NH2) be between about 0.5 and 2. In this case, it is also possible to additionally add an incyanate compound if necessary.

At the time of curing, various other compounding agents used in the production of ordinary preurethane can be added and used.

Examples include reinforcing agents such as Cargen Black, silica, and calcium carbonate, fillers, rosin-based resins for improving tackiness and adhesion, tackifying resins such as terpene-based resins, petroleum-based resins, naphthenes, and halaffin-based resins. , softening agents typified by aromatic process oils, and plasticizers such as dioctyl phthalate, diptyl phthalate, and diallyl phthalate. There are no restrictions on how these can be used, as long as they do not impair the objectives and effects of the present invention, and may be determined as appropriate depending on the objectives, but hydroxyl group-containing hydrogenated liquid polyiso! Ren 10
Normally reinforcing agents and fillers are 0 to 500 parts by weight, anti-aging agents are 0 to 10 parts by weight, and tackifying resins are 0 to 2 parts by weight.
50 parts by weight, 0 to 300 parts softener, 1-0 plasticizer
It is appropriate to use up to 300 parts by weight.

The conditions for curing include a reaction temperature of room temperature to 250°C;
The reaction time is 0.1 to 50 hours.

The cured product (polyurethane) has excellent water resistance, moisture and heat resistance, heat resistance, and weather resistance, and also has sufficient strength and adhesive properties, making it suitable for sealing materials, coating materials, etc. It can be suitably used as a cutting material.

Example 1 100 parts by weight of isopropanol and 200 parts by weight of isoprene were charged into a pressure-resistant reactor equipped with a stirrer, and the temperature was raised to 80°C. Add to this 50% hydrogen peroxide solution 16.9',
The temperature was raised to 0° C., and the mixture was reacted for 3 hours with stirring. After the reaction was completed, the reaction mixture was poured into a large amount of methanol to precipitate the product. The obtained precipitate was dried under reduced pressure to obtain a hydroxyl group-containing liquid polyive grain. The yield of the product obtained was 71 cm. Analysis of the product revealed that the number average molecular weight was 2.8.
60, hydroxyl group-containing sites were 2.19/molecule, and 3.4 bond evidence was 12 mobs as a result of analysis by infrared absorption spectrum.

100 parts by weight of the obtained polymer was dissolved in 1 part by weight of cyclohexane, 10 parts by weight of Ru-C (Ru 5%) was added, and a hydrogen pressure of 50 kg 7 cm was applied to the mixture at 120°C for 6 hours.
Allowed time to react. The reaction product was further diluted with cyclohexane, the catalyst was filtered off, the filtrate was dried under reduced pressure, and the reaction product was recovered.

The number average molecular weight of the product is 2,920, and the hydroxyl group-containing eagle is 2.
．． 13 pieces/molecule, iodine value 1.1F/100. It was P. The hydrogenation rate based on the results of measuring the iodine value was 98.

Each phenolic antioxidant shown in Table 11C was added to the obtained polymer, a di-compound was prepared according to the formulation shown in Table 1, and a cured product was obtained by heating at 120°C for 30 minutes. Ta. Heat resistance was evaluated by heating the obtained cured product in an open environment at 100° C. and tracking changes in its shape. The results are shown in Table-2. Monophenol-based antioxidants deteriorate significantly with the passage of time, and amine-based antioxidants are significantly colored and cannot be put to practical use, but the polymer of the present invention has a 100% Almost no deterioration was observed even after 7 days at ℃.

Example 2 55 μm of m-novinylbenzene was dissolved in hexane, and this was cooled to −10° C., and 120 μm of m-Novinylbenzene was dissolved in hexane.
mmott was added dropwise to produce m-silithiohexylbenzene, to which 2.2 mol of imprene monomer was added and polymerized at 40°C. Ethylene oxide 4 mob was then added to the reaction system, and the resulting product was poured into a large amount of methanol to obtain a precipitate of liquid preisoprene having hydroxyl groups at both ends.

The molecular weight of the obtained polyisoprene is 3,200°3.4
The amount of bonds was 11, and the number of hydroxyl groups in one molecule was 1.93.

After dissolving the obtained liquid polyisoprene in dioxane, Ru
-C (Ru5T) as a catalyst, hydrogen pressure 30 kl/m
A hydrogenation reaction was carried out in step 2. After the reaction, the catalyst was separated by filtration and further vacuum-dried to obtain hydrogenated liquid polyisoprene containing 9-hydroxyl groups. The molecular weight of the product is 3,2
The number of hydroxyl groups per 50.1 molecule was 1.92, and the hydrogenation rate based on the measurement of the iodine value was 97.

The obtained product was treated as shown in Table 2 to obtain tetrakis-[methylene-3-(3',5'-di-t-rt-butyl-4
'-Hydroxyphenyl) f-ropionate]methane was added, and a cured product was prepared according to the formulation shown in Table 2, and the heat resistance was evaluated in the same manner as in Example 1.

As shown in Table 2, when the amount added is small, there is no effect of improving heat resistance at all, and when it is added in a large amount, the physical properties of the cured product actually deteriorate, which is not desirable. I understand.

Blank space below [Effects of the Invention] The present invention provides a polyurethane that has excellent water resistance, moisture resistance, heat resistance, weather resistance, sufficient strength and adhesive properties, and excellent thermal stability. A raw material for polyurethane is provided that has excellent operability in mixing, molding, etc. during production.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] Contains 5 to 20 mol% of 1, 1, 2 or 3, 4 bonds, has a number average molecular weight of 700 to 7,000, and has 1.5 to 4.0 hydroxyl groups per molecule. A liquid polymer containing a hydroxyl group-containing hydrogenated liquid polyisoprene obtained by hydrogenating 50% or more of the unsaturated bonds in a liquid polyisoprene, and an antioxidant consisting of a compound having 2 to 4 phenol residues. . Unsaturated bonds in liquid polyisoprene containing 5 to 20 mol% of 2, 1, 2 or 3, 4 bonds, a number average molecular weight of 700 to 7,000, and 1.5 to 4.0 hydroxyl groups per molecule A composition containing a hydroxyl group-containing hydrogenated liquid polyisoprene obtained by hydrogenating 50% or more of the polyisoprene, an antioxidant consisting of a compound having 2 to 4 phenol residues, and an isocyanate compound. 3. The liquid polymer according to claim 1, wherein the proportion of the antioxidant used is 0.01 to 5 parts by weight per 100 parts by weight of the hydroxyl group-containing hydrogenated liquid polyisoprene. 4. The composition according to claim 2, wherein the antioxidant is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the hydroxyl group-containing hydrogenated liquid polyisoprene. 5. The usage ratio of polyisocyanate compound to hydroxyl group-containing hydrogenated liquid polyisoprene is 2 in terms of NCO/OH molar ratio.
3. The composition according to claim 2, wherein the composition is 5 to 5.