JPH01287109A - Novel liquid polymer and composition - Google Patents

Abstract

PURPOSE:To obtain the title novel polymer having excellent operating characteristics such as molding, providing polyurethane having excellent water resistance, water-vapor resistance, heat resistance, weather resistance, strength and adhesiveness, by hydrogenating a specific hydroxyl group-containing liquid polyisoprene. CONSTITUTION:>=50% unsaturated bond of a liquid polyisoprene having 5-20mol% 1,2 bond or 3,4 bond, 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 polyisoprene of raw material, for example, is obtained by radically polymerizing isoprene monomer 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.

But traditional polyester.

Polyether polyols have not always had sufficient water resistance and moist heat resistance due to the ester and ether bonds present in their molecular chains. In recent years, polybutadiene polyols have been increasingly used, but although these have improved water stiffness and heat resistance, they have poor heat resistance and weather resistance due to the carbon-carbon double bond in the main chain. There is. In order to improve this side heat resistance and weather resistance, a method is used to hydrogenate the carbon-carbon subbond, but in the case of polybutadiene, hydrogenation changes the main chain to a polyethylene structure of +CH2-CH2+. Since it exhibits crystallinity, it is not solid at room temperature, and when used as a urethane raw material, it has extremely poor operability when mixed with compounding agents such as incyanate compounds and fillers, and when molded. becomes.

Attempts have been made to use hydrogenated liquid polyisoprene as a urethane raw material, 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 is easy to operate in mixing, molding, etc. when obtaining the polyurethane. The purpose is to provide raw materials for polyurethane that have excellent properties.

[Failure to solve the problem]

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

That is, the present invention provides 5 to 20 1, 2 or 3, 4 bonds.
mol%, has a number average molecular weight of 700 to 7.000, and has 91.5 to 4.0 hydroxyl groups per molecule, obtained by hydrogenating 50 or more of the unsaturated bonds of liquid polyisoprene. 1,2 or 3,4
Contains 5 to 20 mol% of bonds and has a number average molecular weight of 7.
00 to 7,000 and has 1.5 to 4.0 hydroxyl groups per molecule.
The present invention relates to a composition containing hydrogenated liquid polyisoprene containing hydroxyl groups obtained by hydrogenating % or more of hydrogenated polyisoprene, and a polyincyanate compound.

The vinyl bond-1 (1,2 or 3,4 bond amount) of the hydroxyl group-containing liquid polyisoprene used in the present invention is 5
It is necessary that the content be in the range of 20 mol%. When the amount of vinyl bonds is less than 5 mol %, problems arise in that the strength and elongation of the polyurethane finally obtained is low and the adhesion to metallic glass etc. is insufficient. Moreover, when it exceeds 20 molg6, mechanical properties such as rubber elasticity at low temperatures of polyurethane decrease by 5. Preferably, the vinyl bond amount is 7 to 15 mol%. In addition, 1
, 4-cis, 1,4-) lance, 1,2-vinyl, and 3,4-vinyl microstructures are based on values determined from 'H-NMR spectra.

In addition, the number average molecular weight of liquid polyisoprene containing hydroxyl groups is 7.
It must 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
,000, the polyisoprene will no longer exhibit good fluidity. Furthermore, hydrogenated polyisoprene obtained by hydrogenating this polyisoprene does not exhibit fluidity, and preferably has a number average molecular weight of 1,000 to 5,000.

The number of hydroxyl groups (=average number of hydroxyl groups per molecule) of the hydroxyl group-containing liquid polyisoprene is required to be 1.50 to 4.0. When the number of hydroxyl groups is less than 150, sufficient crosslinking cannot be obtained in the reaction with the polyisocyanate compound, resulting in problems such as poor mechanical strength of the polyurethane.

If the number of hydroxyl groups exceeds 40, the cured product with a high crosslinking density will no longer exhibit good rubber elasticity. Therefore, the number of hydroxyl groups must be within the above range, preferably 1.8 to 3.
It is 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 Inglene monomer can be replaced with hydrogen peroxide, an azo compound with a hydroxyl group (e.g. 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], etc.) or an arm-oxide with a hydroxyl group ( Hydroxyl group-containing liquid polyisoprene can be obtained by radical polymerization using cyclohexanone peroxide (for example, cyclohexanone peroxide, etc.) as a polymerization initiator.

The amount of polymerization initiator used is, for example, H2O212-1212,2'-azobis-
[2-Methyl-N'-(2-hydroxyethyl)-propionamide] 92-92 g, cyclohexanone R-
Oxides 7.6 to 769 are suitable. Although polymerization can be carried out without a solvent, it is preferable to use a solvent for ease of controlling the reaction. Ethanol, impropatol, etc. are usually used as the solvent. A suitable reaction temperature is 100 to 150° C. and a suitable reaction time is 5 to 15 hours.

Furthermore, hydroxyl group-containing liquid polyisoprene can also be obtained by anionically polymerizing isoprene monomers using a catalyst such as naphthalene dilithium to produce an in-prene living polymer, and then 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. A saturated hydrocarbon such as hexane or cyclohexane is used as the solvent.The 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-mentioned polyimprene is used after being hydrogenated. At this time, 5096 or more carbon-carbon double bonds in the polyimrene are hydrogenated.

If it is less than 50 cm, there will be a problem of deterioration of heat resistance and light resistance due to heat or light due to double bonds of the cured product with the polyisocyanate 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 liquid polyisoprene produced as described above by a known method using a homogeneous catalyst, a heterogeneous catalyst, etc. can.

When a homogeneous catalyst is used, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as pe/yne, toluene or xylene is used as a solvent, and hydrogen is added at a reaction temperature of from room temperature to 150°C and at a pressure of from normal pressure to 50 kg/-. The hydrogenation reaction is carried out under pressure. As a homogeneous catalyst, a Ziegler catalyst made of a combination of a transition metal halide and an alkylated product of aluminum, an alkaline earth metal, or an alkali metal, etc. is used in a zero reaction in which about 0.01 to 0.1 mol% of the double bond of the polymer is used. Usually completes in 1 to 24 hours.

When using a heterogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexane, benzene, and toluene.

Aromatic hydrocarbons such as xylene, diethyl ether, TH
F, ethers such as dioxane, alcohols such as ethanol, impropatol, etc., or a mixture thereof as a solvent, at a reaction temperature of from room temperature to 200°C and at normal pressure to 100°C.
The hydrogenation reaction is carried out under a hydrogen pressure of 'Q/ca.

As a heterogeneous catalyst, a catalyst such as nickel, cobalt, radium, 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 relative to the amount of polymer M. 0.5～
10 wt% is appropriate.

The reaction usually completes in 1 to 48 hours.

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 the ratio of incyanate groups to hydroxyl groups in polyisoprene, that is, NCO/OH
It is in the range of 2 to 5. If this ratio is smaller than 2, all the hydroxyl groups and incyanate groups cannot be reacted, and if it exceeds 5, gluing or the like may 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 incyanate groups in the molecule are used. Examples include evatolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and the like.

The hydroxyl group-containing hydrogenated liquid polyisoprene and the polyisocyanate compound react to produce an isocyanate group-containing hydrogenated liquid, ]-9reinprene, and the reaction conditions are those commonly used in the production of urethane prepolymers. get it.

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 lead compounds can be used as catalysts. 6. If unreacted isocyanate compounds are present after the reaction, they may be removed by reducing the pressure, extracting with a solvent, etc. It is also possible to use it in the next step.

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

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

Water, polyol compounds, and polyamine compounds are used for curing.

Examples of polyol compounds include 1,4-butanediol ethylene glycol and fluoropylene gellicol.

Bentanediol, etc. are still polyamine compounds, such as triethylene cyamine, tetraethylene diamine,
Examples include hexamethylene diamine.

When curing these compounds, the molar ratio of CO groups to hydroxyl or amino groups (Neolo
It is preferable from the physical properties of the cured product that H or NH2) is between about 0.5 and 2. In this case, it is also possible to additionally add an incyanato compound as required.

During curing, other additives used in the production of ordinary polyurethanes may be added in appropriate amounts.

Carbon black is an example.

Reinforcers such as silica and calcium carbonate, fillers, phenolic or amine anti-aging agents, and adhesive properties.

Tackifying resins such as rosin-based resins, terpene-based resins, oil-based resins, and naphthene-based resins to improve adhesion.

/4' Rough-in type and aroma type process oils are representative examples of softeners, and plasticizers such as dioctyl phthalate, dibutyl phthalate, and diallyl phthalate. The amounts used are for the purpose of this invention.

There is no limit as long as it does not impair the effect, and it is determined appropriately depending on the purpose, but reinforcing agents and fillers are usually 0 for the hydroxyl group-containing hydrogenated liquid polyiso, Prene 1po:fflfL part.
It is appropriate to use ~500 parts by weight of the anti-aging agent, 0-10 parts by weight of the tackifier, 0-250 parts by weight of the tackifying resin, 0-300 parts by weight of the softener, and 0-300 parts by weight of the plasticizer.

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, heat and humidity resistance, heat resistance, and weather resistance, and also has sufficient strength and adhesive properties, making it a sealing material.

Suitable for use as a coating material or potting material.

Example 1 and Comparative Examples 1 and 2 55 mmol of Km-divinylbenzene was dissolved in hexane, and this was cooled to -10°C, and 120 mm of n-BuLi was dissolved.
ol was added dropwise to generate m-di-lithiohexylbenzene, to which 2.2 mol of imprene monomer was added and polymerized at 40°C. Next, 4 mol of ethylene oxide was added to the reaction system, and the resulting product was poured into a large amount of methanol to obtain a liquid polyisoprene (1) having hydroxyl groups at both ends as a precipitate.

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

Similarly, 5 mol of diethyl ether was added during polymerization, and the molecular weight was 3,800 and the amount of 3,4 bonds was 2.
Liquid polyisoprene C) having 1.89 hydroxyl groups in one molecule was obtained.

Furthermore, natural rubber was purified by a method of dissolving it in hexane and reprecipitating with acetone, then dissolving it in chloroform, blowing ozone into it for ozonolysis, and further reducing it with lithium aluminum hydride.

The obtained reaction product was washed with methanol and then fractionated and precipitated with hexane-methanol to reduce the molecular weight to 4.1.
00 to obtain liquid polyisoprene (III) having 2.0 hydroxyl groups in one molecule. The microstructure of this liquid polyisoprene had 100 cis-1,4 bonds.

After dissolving the obtained liquid polyisoprene in dioxane, each was heated to 30% hydrogen pressure using Ru-C (5% Ru) as a catalyst.
The hydrogenation reaction was carried out at 11 kg/ct. After the reaction, the catalyst was separated by filtration and further vacuum-dried to obtain hydrogenated liquid polyisoprene (I), (2), ([ID).

100 parts by weight of each hydrogenated liquid polyimprene with TD1
After adding 15 parts by weight and reacting at 60°C for 3 hours, the temperature was increased to 80°C.
By reducing the pressure to 0.1 mrnHg and distilling off unreacted TDI, a liquid hydrogenated polyimprene containing isocyanate groups in the molecule was obtained.

The NCO content is 2.48%, 2.05%, and 2, respectively.
．． It was 01chi. The hydrogenation rate of each hydrogenated polyimprene was 95.96.95% as a result of iodine value measurement.

Using each of the isocyanate group-containing hydrogenated liquid polyisoprene obtained above, cured products were prepared according to the formulation method shown in Table 1, and their physical properties were evaluated.

The strength and elongation were measured according to JIS-6301. Also,
Adhesive strength is determined by applying 5cm thick to a degreased steel plate and curing.
Evaluation was made by measuring 0° peeling stress.

The measurement results are shown in Table 1.

Table 1 Example 1 Comparative Example 1 Comparative Example 2 Hydrogenated liquid polyisoprene (1) 100 Hydrogenated liquid polyisoprene (II) 100 Hydrogenated liquid polyisoprene (II) 10
01.4 Butanediol 5.3 4.
5 4.4 dibutyltin dilaurate 0.1
0.1 0.1 tensile strength (kg/d)
53 45 35 growth (%)
270 130 250 Adhesive strength to steel plate (lW%) 7.5 2.5
1.9 Comparative Examples 3 and 4 Polyisoprene (■) * (V) containing hydroxyl groups at both ends was prepared in the same manner as in Example 1 except that the use of m-divinylbenzene and n-BuLi was changed. .

The obtained liquid polyisoprene was hydrogenated according to the method of Example 1 to obtain hydrogenated liquid polyisoprene. By reacting the obtained hydrogenated liquid polyisoprene with TDI, a hydrogenated liquid polyisoprene containing incyanate in the molecule was obtained.

Table 2 shows the reaction conditions and analysis results of the products.

In addition, a cured product was prepared using the obtained hydrogenated liquid polyisoprene according to the formulation method shown in Table 3, and its physical properties were evaluated. The compound using liquid polyimprene has a significantly lower elongation and exhibits sufficient rubber elasticity.On the other hand, the compound using the hydrogenated liquid polyisoprene of Comparative Example 4, which has a high molecular weight, has significantly lower strength and physical properties. This is significantly lower than the formulation of Example 1 using hydrogenated liquid polyisoprene.

Table 2 Comparative Example 3 Comparative Example 4 (Polymerization) m-divinylbenzene (mmol) 300
16n-BuLi (z) 6
30 34 Inzolene monomer (mol)
2.2 2.2 Ethylene oxide (mo
1) 6 Number average molecular weight
510 9.8003.4-Bound amount (%
) 14 Hydroxyl group in 101 molecules (
) 1.95 1.89 (Hydrogenation) Number average molecular landscape of polymer after hydrogenation (%) 520 10.
2001 Hydroxyl groups (pieces) in molecule 1.94
1.88 yo vote price (,9/7ri 6
10 (hydrogenation rate (%)) (9
8) (97) (NCO addition) TDI (parts by weight) 67 3.
4NCO content (%) 0.16
0.77 Table 3 (Formulation) Hydrogenated liquid polyisoprene OV) 100 ff) 100 1.4 Butanediol 35 1.8 Digtyltin dilaure) 0.1 0
．． 1 tensile strength (kg/cfI) 62 1
8 growth (%) 25 3
50 Comparative Example 5 By stopping the reaction midway when hydrogenating the liquid polyisoprene obtained in Example 1, the shodine value was reduced to 220.9/1.
00.9 Hydrogenated liquid polyisoprene with a hydrogenation rate of 40% was obtained. By adding an amount of TD115Jk to this and reacting in the same manner as in Example 1, a number average molecular weight of 3,300, NC was obtained.
An incyanate-containing hydrogenated liquid polyimprene (M) having an O content of 2.46% was obtained. Using the obtained polyimprene, a cured product was prepared according to the compounding treatment shown in Table 4.
Table showing changes in condition after being heated in an oven at ℃ for one week
It can be seen that the polyisoprene shown in Comparative Example 5, which has a low hydrogenation rate, has significantly poor heat resistance.

Table Hide isocyanate-containing hydrogenated liquid polyisoprene (to) 100 (cho) I replacement 1001.4-
Butanediol 5.3 5.3 Dibutyltin dilaurate 0.1 0. i [Effects of the Invention] The present invention provides water resistance, moisture resistance, and heat resistance.

Provided is a raw material for polyurethane that provides polyurethane with excellent weather resistance, sufficient strength properties and adhesive properties, and also has excellent operability in mixing, molding, etc. when obtaining polyurethane.

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. Hydrogenated liquid polyisoprene containing hydroxyl groups obtained by hydrogenating 50% or more of the unsaturated bonds of liquid polyisoprene. 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, and a polyisocyanate compound. 3. 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.