JP2562648B2 - Method for producing hydroxyl group-containing liquid polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a hydroxyl group-containing liquid polymer, and more specifically to a hydroxyl group having a high average number of functional groups (hydroxyl groups) without excessive viscosity increase or gelation. The present invention relates to a method for producing a contained liquid polymer.

[Problems to be Solved by the Related Art and Invention] When a diene polymer having a hydroxyl group is used as a raw material for a urethane resin, a urethane resin excellent in water resistance, low temperature characteristics and electrical characteristics can be obtained. The normally used hydroxyl group-containing diene polymer has two hydroxyl groups per molecule.
As the raw material for urethane foam or rigid urethane, the number of which has an average number of hydroxyl groups of 2.5 or more is desired.

Conventionally, as a method for obtaining a diene polymer having an average number of hydroxyl groups of 2.5 or more, a method of reacting a hydroxyl group-containing diene polymer having an average number of hydroxyl groups of about 2 in the presence of a cationic polymerization catalyst has been known (JP-A-55). -116702 publication). However, since this method is intended to increase the average number of hydroxyl groups per molecule by intermolecular cross-linking reaction, the viscosity of the product is remarkably increased, and the average number of hydroxyl groups is about 4.0 at the maximum, so that the thermal stability is improved. It also had the drawback of being inferior. Further, there was a serious problem that when the average number of hydroxyl groups was 4.0 or more, the whole system was gelated and turned into a solid state.

[Means for Solving the Problems] Then, the present inventor investigated a method for producing a liquid polymer having a high average number of hydroxyl groups without increasing the viscosity or causing gelation. As a result, the liquid diene polymer was epoxidized. Later, it was found that the object could be achieved by performing a ring-opening treatment, and the present invention was completed based on this finding.

That is, the present invention provides a method for producing a hydroxyl group-containing liquid polymer, which comprises subjecting an epoxidized liquid polymer obtained by epoxidizing a liquid diene polymer to a ring-opening treatment.

The liquid diene polymer used in the present invention has a number average molecular weight of 300 to 25,000, preferably 500 to 10,000, and these liquid diene polymers have 4 to 12 carbon atoms.
And diene copolymers, and copolymers of these diene monomers with C2-C22 α-olefin addition polymerizable monomers. Specifically, butadiene homopolymer, isoprene homopolymer, chloroprene homopolymer, butadiene-styrene copolymer,
Examples thereof include butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, and butadiene-n-octadecyl acrylate copolymer. Among these, those having a hydroxyl group inside the molecular chain or at the terminal of the molecular chain are preferable.

First, in the present invention, the liquid diene polymer is epoxidized with an epoxidizing agent to obtain an epoxidized liquid polymer. Examples of the epoxidizing agent used in the present invention include performic acid, peracetic acid, perbenzoic acid, perphthalic acid, m-chloroperbenzoic acid, p
Examples thereof include organic peracids such as -nitroperbenzoic acid and trifluoroperacetic acid, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and hydrogen peroxide. The epoxidation conditions are 100 parts by weight of the liquid diene polymer, 1 to 100 parts by weight of the epoxidizing agent, preferably 5 to 60 parts by weight,
Temperature -10 to 150 ℃, preferably 0 to 100 ℃, pressure 0 to 30 kg
/ cm ² G, preferably 0 to 10 kg / cm ² G for 0.1 to 200 hours, preferably 0.5 to 50 hours. A solvent is not always necessary for the epoxidation, but if desired, an organic solvent such as benzene, chloroform, carbon tetrachloride may be used.

Next, the epoxidized liquid polymer thus obtained is subjected to a ring-opening treatment to obtain a hydroxyl group-containing liquid polymer. The ring-opening treatment is carried out by adding 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, of a hydrogenation catalyst such as nickel, palladium, platinum or ruthenium to 100 parts by weight of the epoxidized liquid polymer, and at a temperature of 0 to 250 ° C. , Preferably 20-150 ℃, pressure 0-200kg / cm
^The reaction is carried out at ² G · H ₂ , preferably 1 to 100 kg / cm ² G · H ₂ for 0.1 to 200 hours, preferably 0.5 to 100 hours. In addition,
A solvent is not always necessary for the ring-opening treatment, but if desired, an organic solvent such as hexane, cyclohexane, isopropyl alcohol, 2-butanol may be used.

After completion of the ring-opening treatment, a hydroxyl group-containing liquid polymer is obtained by post-treatment according to a conventional method. The hydroxyl group-containing liquid polymer obtained by reacting under the above conditions has a hydroxyl group content (0HV) of 0.1 to 20.0 meq / g and a number average molecular weight (n) of 500 to 200.
00, average number of hydroxyl groups (n) 2.5 or more (3.0 to 8.0), viscosity 0.
It is from 1 to 10,000 poise / 30 ° C. The average number of hydroxyl groups was calculated by the following formula.

EXAMPLES Next, the present invention will be described with reference to examples.

Production Example 1 (Production of Epoxidized Liquid Polymer) 225 g of acetic anhydride was placed in a 500 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and 30% by weight of peroxide was added from the dropping funnel while maintaining the temperature at 40 ° C. 50 g of hydrogen water was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour, cooled to room temperature and left overnight to prepare a peroxide.

On the other hand, 2 equipped with a stirrer, thermometer and dropping funnel
Liquid polybutadiene with hydroxyl groups at the end of a 3-neck flask (Idemitsu Arco, R-45HT, number average molecular weight 280
0, hydroxyl content 0.79 meq / g) 200 g and cyclohexane 2
00 g was collected, and the above-mentioned peroxide was added dropwise from the dropping funnel over 2 hours while maintaining the temperature at 30 ° C. After dropping, 30
Stirring was continued at 0 ° C for 10 hours. After completion of the reaction, the reaction mixture was put in a separating funnel 3 and water of 1.5 was added and shaken for separation treatment. The operation of precipitating the upper phase in a large excess of hexane and then dissolving it in toluene was repeated, and finally the light boiling point was distilled off to obtain a colorless and transparent epoxidized liquid polymer. The properties of the obtained epoxidized liquid polymer were epoxy equivalent 420, hydroxyl group content 0.74 meq / g, number average molecular weight 2990, and viscosity 510 poise / 30 ° C.

Production Example 2 (Production of Epoxidized Liquid Polymer) In Production Example 1, the amount of acetic anhydride used was 45 g, 30% by weight.
An epoxidized liquid polymer was obtained in the same manner as in Production Example 1, except that the amount of hydrogen peroxide solution used was 10 g.
The property of the obtained epoxidized liquid polymer is epoxy equivalent.
1180, hydroxyl content 0.77 meq / g, number average molecular weight 2860, viscosity 16
It was 5 poise / 30 ° C.

Production Example 3 (Production of Epoxidized Liquid Polymer) In Production Example 2, instead of liquid polybutadiene R-45HT having a hydroxyl group at the terminal, polybutadiene R-15HT having a hydroxyl group at the terminal (manufactured by Idemitsu Arco Co., Ltd., number average molecular weight) An epoxidized liquid polymer was obtained in the same manner as in Production Example 2 except that 1220, hydroxyl group content 1.88 meq / g) was used. The properties of the obtained epoxidized liquid polymer were epoxy equivalent 1120, hydroxyl group content 1.82 meq / g, number average molecular weight 1260, and viscosity 52 poise / 30 ° C.

Production Example 4 (Production of Epoxidized Liquid Polymer) Isoprene 200 g, 5 in a stainless steel pressure-resistant reaction vessel of 1.
16g of 0% by weight hydrogen peroxide and 100g of n-butyl alcohol as a solvent were charged, and the temperature was 120 ° C and the pressure was Max 8kg / cm ^2.
G was allowed to react for 2 hours. After completion of the reaction, the reaction product was extracted from the reaction container, placed in a separating funnel together with 600 g of water and shaken, and allowed to stand for 3 hours to separate an oil phase. The obtained oil phase
The solvent, the monomer and the low boiling point components were distilled off by evaporating at 100 ° C. and 2 mmHg for 2 hours to obtain liquid polyisoprene having a hydroxyl group at the molecular chain end in a yield of 68% by weight. The properties of the obtained liquid polyisoprene are number average molecular weight 2150, hydroxyl group content.
It was 0.96 meq / g.

Next, 50 g of liquid polyisoprene having a hydroxyl group at the end of the molecular chain and 100 ml of chloroform obtained in the pressure resistant reaction vessel were taken, and a solution of 12.5 g of metachloroperbenzoic acid in 300 ml of chloroform was stirred therein to obtain 2 Dropped over time. After completion of dropping, the mixture was refluxed at 25 ° C. for 3 hours, then cooled to room temperature and left standing for 24 hours. continue,
After cooling the reaction vessel and separating the precipitated crystals of metachlorobenzoic acid, the liquid was saturated with a 20 wt% aqueous sodium hydrogen sulfite solution (50 ml once) and with a 10 wt% sodium hydrogen carbonate aqueous solution (100 ml) three times, using a separating funnel. It was washed once with 100 ml of saline and twice with 200 ml of pure water. In addition, wash the liquid with 100
Evaporated at 1 ° C and 1 mmHg for 2 hours to distill off the low boiling fraction to obtain an epoxidized liquid polymer. The properties of the obtained epoxidized liquid polymer have an epoxy equivalent of 629 and a hydroxyl group content of 0.95 meq /
g, number average molecular weight 2220, viscosity 214 poise / 30 ℃.

Production Example 1 using the stainless steel pressure-resistant reaction vessels of Examples 1 to 41
The catalysts and solvents shown in Table 1 were added to 100 parts by weight of the epoxidized liquid polymer obtained in Examples 1 to 4 and the ring-opening treatment was carried out at the temperature, time and pressure shown in Table 1. After the ring-opening treatment, the catalyst was removed with a 1 μm membrane filter, followed by evaporation at 100 ° C. and 1 mmHg for 2 hours to distill away the solvent and low-boiling components to obtain a hydroxyl group-containing liquid polymer. The properties of the obtained hydroxyl group-containing liquid polymer are shown in Table 1.

Comparative Example 1 A diene polymer Poly bd R-45HT (manufactured by Idemitsu Arco Ltd., average molecular weight 2800, hydroxyl group content 0.79 meq / g, per molecule) was placed in a three-necked flask with a capacity of 300 ml equipped with a thermometer and a stirrer. 50 g of hydroxyl group 23), 100 g of ethylene chloride and 0.1 g of boron trifluoride-dimethyl ether complex were charged and reacted in a 500 ml glass three-necked flask made of glass under a nitrogen stream at 0 ° C. for 3 hours. Then, the reaction product was gradually poured into 200 ml of methanol while stirring, and after standing, the product was separated. The separated product was dried under reduced pressure at 40 ° C. to obtain 48 g of a colorless and transparent hydroxyl group-containing liquid polymer. The properties of the resulting hydroxyl group-containing liquid polymer are shown in Table 2.

Comparative Example 2 A hydroxyl group-containing liquid polymer was prepared in the same manner as in Comparative Example 1 except that 0.05 g of aluminum chloride was used in place of the boron trifluoride-dimethyl ether complex and the reaction temperature was 5 ° C. I got 47g. The properties of the resulting hydroxyl group-containing liquid polymer are shown in Table 2.

[Effect of the Invention] According to the present invention, a liquid polymer having a high average number of hydroxyl groups can be obtained without causing an excessive increase in viscosity or gelation. Moreover, since the obtained hydroxyl group-containing liquid polymer has good thermal stability, it is useful as a raw material for urethane foam and rigid urethane.

Claims (2)

(57) [Claims] 1. A process for producing a hydroxyl group-containing liquid polymer, which comprises subjecting an epoxidized liquid polymer obtained by epoxidizing a liquid diene polymer to ring-opening treatment. 2. The method according to claim 1, wherein the liquid diene polymer contains a hydroxyl group.