JPH01287113A - Novel liquid polymer and composition - Google Patents

Abstract

PURPOSE:To obtain the title novel polymer having excellent operating characteristics, providing polyurethane having excellent water resistance, water- vapor resistance, heat resistance, weather resistance, strength and adhesiveness, by hydrogenating a specific hydroxyl group-containing liquid isoprene-butadiene copolymer. CONSTITUTION:>=50% unsaturated bond of a liquid isoprene-butadiene copolymer having the weight ratio of isoprene/butadiene of 95/5-70/30, 700-7,000 number- average molecular weight and 1.5-4 hydroxyl groups is hydrogenated to give the aimed polymer. The hydrogenation reaction, for example, is carried out by using a homogeneous system catalyst such as Ziegler catalyst in a solvent such as hexane at normal temperature - 150 deg.C under normal pressure - 50kg/cm<2>. The hydroxyl group-containing liquid isoprene-butadiene copolymer of raw material, for example, is obtained by radically polymerizing a mixture of isoprene and butadiene by using a polymerization initiator such as hydroxyl group-containing peroxide.

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]

Conventionally, polyurethanes such as polyester and polyether polyols have been widely used for applications such as sealing materials, coating materials, and potting materials.

However, conventional polyester and polyether polyols did not necessarily have sufficient T+ water resistance and moist heat resistance due to ester and ether bonds present in their molecular chains.

In addition, polybutadiene polyols have come into use in recent years, but although these have improved water resistance and heat and humidity resistance, they have poor heat resistance and weather resistance due to the carbon-carbon double bond in the main chain. . In order to improve this heat resistance and weather resistance, a method of hydrogenating the carbon-carbon double bond has been adopted, but in the case of polybutadiene, hydrogenation changes the main chain to a polyethylene structure of +CH2-CM2+. Because it exhibits crystallinity, it becomes solid at room temperature, and when used as a urethane raw material, it is mixed with compounding agents such as incyanate compounds and fillers, and hydrogenated liquid polyisoprene is used for molding. Attempts have been made to use urethane as a raw material for urethane, but as a result of studies conducted by the present inventors, it was found that sufficient strength and adhesive properties could not be obtained.

[Problem 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 properties and adhesive properties, and also has excellent operability in mixing, molding, etc. when obtaining polyurethane. The purpose is to provide raw materials for

[Means for Solving the Problems] According to the present invention, the above objects are achieved by a specific hydroxyl group-containing liquid hydrogenated isoprene-citadiene copolymer or a composition containing the same.

That is, in the present invention, the weight ratio of Imprene/2Tajinka is in the range of 9515 to 70/30, the number average molecular weight is 700 to 7,000, and 1.5 to 4.0 in one molecule.
The present invention relates to a liquid hydrogenated copolymer obtained by hydrogenating 50 or more unsaturated bonds of a liquid isoprene-butadiene copolymer having hydroxyl groups, and further relates to the liquid hydrogenated copolymer, The present invention relates to a composition containing an isocyanate compound.

Hydroxyl group-containing liquid isoprene used in the present invention
In the butadiene copolymer, the isoprene/butadiene ratio by weight must be in the range of 9515 to 70/30. If the amount of butadiene is less than the above range, there will be no effect of improving the strength properties of urethane obtained by using the obtained hydrogenated product as a raw material, and conversely, if it exceeds the above range, it will be reduced to the hydrogenated part of butadiene. Due to the crystallinity caused by this, it becomes solid or its viscosity increases significantly, impairing operability, which is undesirable.

The liquid imprene-butadiene copolymer used has a number average molecular weight of 700 to 7,000. When the number average molecular weight is less than 700, the polyurethane obtained using the hydrogenated product does not have good physical properties. Also, 7
,000, the copolymer and its hydrogenated product will not exhibit good fluidity, and the operability in obtaining polyurethane will be extremely poor, which is undesirable. From this point of view, the number average molecular weight must be within the above range, and is particularly preferably from 1,000 to 5,000.

The hydroxyl group-containing liquid isoprene-butadiene copolymer must have 1.5 to 4.0 hydroxyl groups in one molecule. If the number of hydroxyl groups is less than 1.5, sufficient crosslinking cannot be achieved in polyurethane using the hydrogenated product, resulting in insufficient strength properties. Still 4.0
If it exceeds 100%, the crosslinking density will be too high and a cured product exhibiting good elasticity will not be obtained. Therefore, the amount of hydroxyl group must be within the above range, and is particularly preferably within the range of 1.8 to 3.0.The hydroxyl group may be located either at the end of the molecular chain or within the chain, but at least Those having one at the end are most preferably used. Such a hydroxyl group-containing liquid isoprene-butadiene copolymer can be obtained by a known method. For example, a mixture of isoprene and butadiene can be mixed with hydrogen peroxide, an azo compound having a hydroxyl group (e.g. 2,2
'-Azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], etc.) or a peroxide having a hydroxyl group (for example, cyclohexanone peroxide, etc.) is used as a polymerization initiator at a concentration of 0.0% relative to the isoprene monomer.
A hydroxyl group-containing liquid isoprene-butadiene copolymer can be obtained by radical copolymerization using 1 to 50 moles of the copolymer.

Further, a mixture of isoprene and butadiene is anionically polymerized using a catalyst such as naphthalene dilithium or m-dilithiohexylbenzene in an amount of 0.1 to 5 parts by weight per 100 parts by weight of imprene monomer. , propylene oxide, etc. is added in an amount of 1 to 500 mol per 1 mol of the polymerization catalyst, and the temperature is 0.1 to 500 mol at room temperature to 200°C.
If the reaction is carried out for a long time, liquid isoprene-butadiene containing hydroxyl groups can be obtained. Although this reaction can be carried out without a solvent, it is often preferable to use a solvent, which allows the reaction to be easily controlled. In this case, the same solvent as used in polymerization is used.

In both radical polymerization and anionic polymerization, it is necessary to use a solvent that is inert to the catalyst. Examples of solvents used in radical polymerization include alcohols such as ethanol and Glonol, aliphatic and alicyclic hydrocarbons such as hexane, hezotane, and cyclohexane, benzene, and aromatic hydrocarbons such as toluene. In the case of anionic polymerization, aliphatic hydrocarbons such as pentane and hexane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene and toluene are used.

The amount of solvent can be determined arbitrarily, but in consideration of efficiency, it is preferably 80% or less of the entire polymerization system.

The conditions for carrying out the polymerization are also not particularly limited, but any polymerization method can be carried out within the range of about 0.degree. C. to 200.degree. C. for about 0.1 to 100 hours.

In the case of copolymerization, it is preferable that the form of copolymerization of isoprene and butadiene is random copolymerization. In the case of block copolymerization, the chain length of butadiene must be short enough to not exhibit crystallinity after hydrogenation.
It is preferable that the number of butadiene units is 10 or less.

A liquid imprene-butadiene copolymer having a hydroxyl group at the end of the molecular chain can be obtained by the above method, but
In addition, a copolymer polymerized by a radical catalyst that does not have a hydroxyl group, or a copolymer obtained without anionic polymerization and a reaction to introduce a hydroxyl group is used, for example, in JP-A-57-1.
A copolymer in which a hydroxyl group is introduced into the side chain by a method such as that shown in No. 6003 may also be used.

In the present invention, the liquid isoprene-tutadiene copolymer is hydrogenated before use. At this time, 50% or more of the carbon-carbon double bonds in the copolymer must be hydrogenated.

Hydrogenation rate is 50%! F) If it is small, the polyurethane obtained using it will suffer from a decrease in heat resistance and weather resistance due to heat or light due to double bonds. From this point of view, the hydrogenation rate must be 50% or more, preferably 80%.
More preferably, it is 90% or more. Hydrogenation of the copolymer can be carried out using known methods, such as a Ziegler homogeneous catalyst or a solid unbound catalyst.
Touch.

A method of carrying out catalytic hydrogenation using a medium is adopted.

When using a homogeneous catalyst, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene is used as a solvent, and the reaction temperature is from room temperature to 150°C under a hydrogen pressure of from normal pressure to 50 kg/cd. A hydrogenation reaction takes place. As a homogeneous catalyst, a Ziegler catalyst made of a combination K of a transition metal halide and an alkylated product of aluminum, alkaline earth metal, or alkali metal, etc., can be used to react with the double bond of the polymer. 110.01~0.1 m
Use about 1% o.

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 and toluene and xylene, ethers such as diethyl ether, THF and dioxane, alcohols such as ethanol and impropanol, etc. Using a mixed system of these as a solvent, a hydrogenation reaction is carried out at a reaction temperature of room temperature to 200° C. and under a hydrogen pressure of normal pressure to 100 kg/cJ. As a heterogeneous catalyst, catalysts such as nickel, cobalt, base radium, platinum, rhodium, and ruthenium are used alone or supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon, and the amount used is determined by the weight of the polymer. A suitable amount is 0.5 to 1 wt%. The reaction usually completes in 1 to 48 hours.

Another object of the present invention is a composition using the hydrogenated copolymer, which contains the hydrogenated copolymer and an organic polyisocyanate compound having two or more isocyanate groups in one molecule. It is a composition.

This composition can be crosslinked and cured to form polyurethane for various uses. Examples of the organic polyisocyanate compound used here include tolylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, phenylene diisocyanate, dicyclohexylmethane diisocyanate, and the like. When curing, a method of curing by mixing a hydrogenated liquid isoprene-butadiene copolymer and a polyisocyanate compound (one-shot method) or a method of curing by mixing a hydrogenated liquid isoprene-butadiene copolymer with a hydroxyl group of a hydrogenated liquid isoprene-butadiene copolymer and an isocyanate group of a polyisocyanate compound Aaraka L
A method (prepolymer method) is adopted in which a copolymer having an isocyanate group is produced by a reaction, and the copolymer is cured using a curing agent.

When using the one-shot method, hydroxyl groups (
OH) and isocyanate group (NCO) in a molar ratio of NCO
/OH is used in a range of about 0.5 to 5.0.

If the ratio is less than 0.5, the cured product will not have sufficient strength, and if it exceeds 5, the crosslinking density will be too high and a cured product with sufficient elasticity will not be obtained. This ratio is preferably in the range of 0.8 to 2.0.

In addition to polyisocyanate compounds, polyols and polyamine compounds can also be used in combination during curing.

There is no particular restriction on the amount of the polyol or polyamine compound used, but it is used in the range of 1 to 250 parts by weight per 100 parts by weight of the liquid copolymer.

In the case of the prepolymer method, this NCO/OH molar ratio is carried out in the range of 2.0 to 5.0. If the ratio is less than 2.0, unreacted hydroxyl groups will remain, causing problems such as a significant increase in viscosity or hardening during the reaction, or progressing in hardening during storage, which is undesirable. If it exceeds,
The cured product loses its rubber elasticity. Depending on the case, a method may be used in which a larger amount of NCO is used, and after the reaction, excess isocyanate compound is removed by means such as reducing the pressure. The reaction temperature in this first half of the prepolymer method is from room temperature to 200°C, and the reaction time is from 0.1 to 50 hours. At this time, it is also possible to use compounds such as tin and lead as catalysts.

The hydrogenated liquid isoprene-butadiene copolymer containing isocyanate groups obtained by the prepolymer method is used after being crosslinked and cured using water, a polyol compound, a polyamine compound, etc. When these are used as crosslinking agents, the amount used is such that the molar ratio of hydroxyl or amino groups to isocyanate groups (OH or NH2/NC0) is 0.5 to 5.
Used in the range 0.

Here, in both the prepolymer method and the one-shot method, the polyamine compounds include 1,4-butanediol, bentanediol, hexanediol, ethylene glycol, and propylene gellicol, and the polyamine compounds include tetramethylene diamine and hexamethylene. Diamine, 4,4'-diaminodiphenyl, etc. are used. In addition, in either the one-shot method or the prepolymer method, various other compounding agents used in producing ordinary polyurethane can be added and used.

Examples include reinforcing agents such as carbon black, silica, and calcium carbonate, fillers, phenol-based and amine-based anti-aging agents, rosin-based resins for improving tackiness and adhesion, terpene-based resins, petroleum-based resins, etc. Typical examples include tackifying resins, naphthenic, paraffinic, and aromatic process oils, softeners, and plasticizers such as dioctyl phthalate, dibutyl hepthalate, and diallyl phthalate. There is no limit to the amount of these used as long as it does not impair the purpose and effect of the present invention, and it is determined appropriately depending on the purpose, but usually hydrogenated liquid isogrene-butadiene copolymer
0 parts by weight, the reinforcing agent/filler is 0 to 500 parts by weight,
Anti-aging agent: 0 to 10 parts by weight, tackifier resin: 0 to 25 parts by weight
0 parts by weight, 0 to 300 parts by weight of softener, 0 to 3 parts of plasticizer
It is appropriate to use 0.00 parts by weight.

The conditions for curing are: room temperature to 200°C, in both the prepolymer method and the one-shot method;
Preferably, it is carried out at a temperature of 80 to 150°C for a period of 0.1 to 20 hours.

The polyurethane obtained using the copolymer or composition according to the present invention has excellent heat resistance and weather resistance, good water resistance and moist heat resistance, and has sufficient strength for washing. It can be suitably used as materials, waterproof sheets, electrical materials, automobile materials, etc.

Example 1 100 parts by weight of isopropanol, 170 parts by weight of Inglene, and 30 parts by weight of butadiene were charged into a pressure-resistant reactor equipped with a stirrer, and the temperature was raised to 80°C. Add 1 part of 50% hydrogen peroxide to this
61! was added, heated to 120°C, and reacted for 3 hours with stirring. After the reaction was completed, the mixture in one reactor 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 imprene-butadiene copolymer. The yield of the product obtained was 69%.

As a result of analysis of the product, the number average molecular weight was 850, the hydroxyl group content was 2.18/molecule, and the isogrene butadiene ratio was 86/14 as a result of analysis by infrared absorption spectrum.

100 parts by weight of the obtained copolymer was dissolved in 50 parts by weight of cyclohexane, 10 parts by weight of Ru-C (5% Ru) was added, and a hydrogen pressure of 501Xg/(-J) was applied to react at 120°C for 6 hours. . The reaction product was further diluted with cyclohexane, the catalyst was filtered off, and the filtrate was dried under reduced pressure to obtain a hydroxyl group-containing hydrogenated liquid isogrene-butadiene copolymer (I).

The number average molecular weight of the product is 2,910, and the hydroxyl group content is 2.
．． 13 pieces/molecule, iodine value 1.2I! /100. It was F. The hydrogenation rate based on the measurement results of the iodine value was 98%.

Comparative Examples 1 and 2 Isoprene/butadiene ratio 98/2, 50150
The reaction was carried out in the same manner as in Example 1, except that the isogrene butadiene ratio was 98/2, the number average molecular weight was 2,760, the hydroxyl group content was 2.21, the iodine value was 0.9, the imprene/butadiene ratio was 52/48, and the number Average molecular weight 2,980. Hydroxyl group-containing hydrogenated liquid isoprene-butadiene copolymers ω) and (1) having a hydroxyl group content of 2.16 and an iodine value of 1.4 were obtained, respectively.

The hydrogenated copolymer with an imprene/butadiene ratio of 52/48 was solid at room temperature and had no fluidity. The hydrogenation rate based on the iodination measurement results is 97% (
II) and 99% (III).

Example 2 Using the hydroxyl group-containing hydrogenated liquid isoprene-butadiene copolymer obtained in Example 1 and Comparative Examples 1 and 2, a mixture was prepared according to the formulation shown in Table 1 and heated at 120°C for 30 minutes. Table 1 shows the results of preparing hardened products and measuring the strength and elongation according to JIS K 6301.

The blend of the copolymer of Comparative Example 2 could not be mixed at room temperature, and when it was mixed under heating, sulfurization occurred during mixing, and it could not be subjected to the following test.

As shown in Table 1, it can be seen that the compositions according to the examples of the present invention have excellent strength properties.

Margin below Table 1 Example 1 Comparative example 1 Comparative example 2 Hydrogenated liquid inglene Butadiene copolymer (I) 1o.

l mark) 100 (g)
1001.4-butanediol 3.3 3.6 3
．． 3 dibutyltin dilaure) 0.1
0.1 0.1 Tolylene diisocyanate
12.7 13.9 12.6 Tensile strength (
carpet/m) 78 36 *Strength
(%) 290 250 Comparative Examples 3 and 4 By polymerizing isoprene-butadiene mixtures in the same manner as in Example 1, the molecular weights were 11,000 and 580, respectively, and the hydroxyl group contents were 1.93 and 2.29 per molecule. Ratio of isogrene butadiene i1'183/17.85/15
An isoprene/butadiene copolymer was obtained.

The obtained copolymer was dissolved in cyclohexane, and Example 1
Hydroxyl group-containing hydrogenated liquid isoprene-butadiene copolymers (IV) and (V) were obtained by hydrogenation using Ru-C (Ru 5%) as a catalyst in the same manner as above. The number average molecular weight of the product is 11,800.590, and the hydroxyl group content is 1°9.
2 pieces, 2.28 pieces/molecule, iodine value is 2.11!71
00 F, 1.3, F/100, F.

Comparative Example 5 The hydroxyl group-containing isoprene-butadiene copolymer obtained in Example 1 was reacted in the same manner as in Example 1, and one reaction was stopped midway to obtain a shodine value of 21017100 F.
A hydroxyl group-containing hydrogenated isoprene butadiene copolymer (b) with a hydrogenation rate of 45% was obtained. The number average molecular weight was 2,890, and the hydroxyl group content was 2.16/molecule.

Comparative Example 6 Using the hydroxyl group-containing hydrogenated isoprene-butadiene copolymer obtained in Comparative Examples 3, 4.5 and Example 1,
A compound was prepared according to the formulation shown in Table 2, and a cured product was prepared by heating at 120°C for 30 minutes.
The strength and elongation were measured according to 1.

Furthermore, the compositions of the copolymers obtained in Comparative Example 5 and Example 1 were heated in an oven at 120° C. for one week to examine changes in shape and evaluate their heat resistance.

As shown in Table 2, the composition using the copolymer obtained in Comparative Example 3 does not exhibit sufficient elasticity. Further, the composition made of the copolymer obtained in Comparative Example 4 did not exhibit any strength.

It can be seen that the copolymer with a low hydrogenation rate has a strength and elongation value close to that of the hydrogenated copolymer, but the deterioration after heating is large and the heat resistance is inferior.

Margin table below 2 Hydrogenated liquid polyimprene-butadiene
3.3 3.3 dibutyltin dilaure)
' o, i o, to, i
o, i Million MTL* 4.7 111
．． 8 21.6 21.1 Tensile strength (kgA)
21 95 76 81* Carbodiimide-modified MDI NC029% [Effects of the invention] The present invention provides a polyurethane that has excellent water resistance, moisture resistance, heat resistance, and weather resistance, and has sufficient strength and adhesive properties. The present invention provides a raw material for polyurethane that has excellent operability in mixing, molding, etc. when obtaining polyurethane.

Patent applicant: RiRashi Co., Ltd.

Claims (1)

[Claims] 1. Isoprene/butadiene weight ratio is 95/5 to 7
It is in the range of 0/30, and the number average molecular weight is 700 to 7,0.
00, and is obtained by hydrogenating 50% or more of the unsaturated bonds of a liquid isoprene-butadiene copolymer having 1.5 to 4.0 hydroxyl groups in one molecule. 2. Isoprene/butadiene weight ratio is 95/5 to 7
It is in the range of 0/30, and the number average molecular weight is 700 to 7,0.
00, hydrogenated liquid isoprene-butadiene copolymer obtained by hydrogenating 50% or more of the unsaturated bonds of a liquid isoprene-butadiene copolymer having 1.5 to 4.0 hydroxyl groups in one molecule. A composition containing an organic polyisocyanate compound. 3. The molar ratio of the hydroxyl group (OH) in the hydrogenated liquid isoprene-butadiene copolymer to the isocyanate group (NCO) in the organic polyisocyanate compound is NCO/OH = 0.5.
3. The composition of claim 2, which has a molecular weight of 5.0.