JPH01118A - Manufacturing method of polycarbonate polyol - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to a polycarbonate having a nonahydrous group at the end, which is excellent in heat resistance and hydrolysis resistance, and is suitable for economically producing high-grade polyurethane. The present invention relates to a method for producing natepolyol.

(Prior art and its problems) Is it possible to form a dialkyl carbonate by transesterifying a diaryl carbonate and a polyhydroxy compound? It is already known to produce licargenate I reol. However, if the dialkyl carbonate is nate, the ratio of polyhydroxy compound to diaryl carbonate is equal to the stoichiometric amount, or the chemical
4 recarpnate I obtained because it is close to the stoichiometric amount
If a part of the terminal hydroxyl group of the liol is an alkyl group or an aryl group of the starting material, ~ polycargenate I obtained when the polyhydroxy compound of the starting material is a diol.
Since the number of terminal hydroxyl groups in Liol is less than 2, there is a drawback that the molecular weight of polyurethane produced using Liol is not sufficiently large. Furthermore, it is already known to use a titanium-based catalyst in the transesterification reaction of a 4-hydroxy compound with a carbonate or diaryl carbonate in a sial. However, since the amount of titanium-based catalyst used is extremely small, the 3-ester exchange reaction is extremely slow, and the yield of the obtained polycarbonate podiol is extremely low, making it difficult to economically produce it.

(Problems to be Solved by the Invention) In order to solve these problems, the inventors of the present invention have conducted intensive research and have found that high-quality... We have discovered a method for economically producing recarbonate/diol, leading to the present invention.

(Means for Solving the Problems) That is, the present invention involves transesterifying a dialkyl carzanate or a diaryl carzanate into a polyhydroxy compound by transesterifying the polyhydroxy compound in the presence of an all-titanium catalyst. In the method for producing ol, the ratio of the polyhydroxy compound to the dialkyl carbonate or diaryl carbonate is 1.01 to 1.30 times the stoichiometric amount, and the amount of the titanium catalyst is expressed as titanium to the dialkyl carbonate or diaryl carbonate. This invention provides a method for producing a polycarbonate polyol, characterized in that the polyhydroxy compound is added in a stoichiometric amount of 1.01 Q% to the dialkyl carbonate or diaryl carbonate.
The terminals of the polycarbonate podiol obtained by using 1.30 to 1.30 times the amount of titanium can be almost completely converted into hydroxyl groups. 0.0005 to 0.0 for diaryl carbonate
By using 5% by weight, the diester exchange reaction can proceed smoothly and polycarbonate diol can be obtained in high yield.

The dialkyl carbonate or t here refers to the stoichiometry n of the polyhydroxy compound relative to the diaryl carbonate.
For example, when the polyhydroxy compound is a diol, nR-Cos-R+(n+1)HO-R'-OH→HO
+ R'-COs % R'-OH+ 2 n R-O
H (R is an alkyl group, R' is an aryl group, R' is a diol residue, a number corresponding to the molecular weight of the nFi target polycargenate diol) - all meaning O (constituent) Dialkyl used in the present invention Carbonate, or diaryl carbonate, dimethylo-M)
, diethyl cargenate, sea n-butyl cargenate, di-1go-butyl carbonate, diphenyl cardanate and the like are preferred.

The hydroxy compound used in the present invention is 1.3
-gulononediol, 1,4-butanediol, 1.
5-bentanediol, 1, 6-hexanediol, 1
, 7-hebutanediol, l,8-octanediol,
2-ethyl-1,6-hexanediol, 2-methyl-
1,3-7'ropanediol, neointhyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2'-bis-(4-hydroxycyclohexyl)-furonone, P--? Silediol, p-tetrachloroxylene diol, 1,4-dimethylolcyclohexane.

Bis-hydroxymethyltetrahydrofuran, di(2-
Hydroxyethyl) dimethylhydantoin, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, d? These include polylopylene glycol, polytetramethylene glycol, thioglycol, trimethylolethane, trimethylolethane, hexanetriol, intererythritol, and the like. These hydroxy compounds can be used alone or in combination in the transesterification reaction.

The titanium compounds used in the present invention include organic titanium, halogenated titanium, titanic acid, and other inorganic titanium compounds such as tetraethyl titanate, tetra-Lao-propyl titanate, tetra-n-butyl titanate, acetylacetone titanium, and titanylammonium oxalate. , titanium trichloride, titanium tetrachloride, titanium tetrafluoride, sodium titanate chloride, anthoniwam titanate chloride, ammonium titanate fluoride, titanic acid, titanium sulfate, etc.
Preferred are titanium tetrachloride and tetra-1-butyl titanate, or tetra-1 go-7'o hir titanate.

The ratio of polyhydroxy compound to dialkyl carbonate or diaryl carbonate should be 1.01 to 1.30 times the stoichiometric amount. If the ratio of the polyhydrochloric compound to the diaryl carbonate is less than 1.01 times the stoichiometric amount, the terminal hydroxyl group of the resulting polycarbonate polyol is preferably 1.05 to 1.25 times. A part of it becomes an alkyl group or an aryl group, and there is a drawback that the molecular weight of the polyurethane produced using this polycarbonate podiol is not sufficiently large. On the other hand, if the molecular weight is more than 1.30 times, it is necessary to use a large excess of the polyhydroxy compound in order to obtain a polyol having the desired molecular weight. However, the yield of polycarbonate podiol is also reduced, and it cannot be said to be an economical production method.

That is, in order to fully produce a polycarbonate polyol whose terminals are almost completely hydroxyl groups, the ratio of polyhydrochloric compound to dialkyl carbonate or diaryl carbonate is 1630 times the stoichiometric amount.

The amount of titanium-based catalyst is 0.0005% of titanium based on dialkyl carbonate and diaryl carbonate.
and 0.05% by weight. Preferably it is 0.0010 to 0.01.

If the amount of titanium-based catalyst is less than 0,000% by weight of titanium relative to the sialyl carbonate or diaryl carbonate, the transesterification reaction between the diaryl carbonate or diaryl carbonate and the polyhydroxy compound will be extremely slow, and the polycarbonate The disadvantage is that the yield of nate-diol is reduced due to the colored polycarbonate polyol. On the other hand, the amount of titanium catalyst is 0.05 as titanium! If the amount is too large, the polycargonate diol will be noticeably colored, and will it be produced using a tube?
The disadvantage is that the urethane resin becomes colored.

The manufacturing conditions of the present invention are not particularly limited, but are usually 18
The transesterification reaction is carried out at a low temperature of 0°C or lower for about 1 to 15 hours, and further at 150 to 280°C, preferably at 18°C.
The reaction is carried out at about 0 to 240°C for several hours, and then the reaction is carried out at the same temperature for several hours under a pressure that finally reaches 20 W@Hg or less.

The polycarnate 4-liol having hydroxyl groups at the ends produced according to the present invention exhibits extremely excellent heat-and-moisture resistance and hydrolysis resistance by reacting with diincyanate. EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited thereto. "Part" and "Regret" in the text are based on weight.

Example 1 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 771 parts of diethyl carbonate (produced by the reaction of ethyl alfur and phosgene), 991 parts of 1,6-hexanediol, and tetra-1go- provir tetane)
0.071 part of 125
It was kept at ℃ for 1 hour. Furthermore, the temperature was gradually increased to 1 gO℃,
After keeping this temperature for 2 hours, the temperature was raised to 200°C and kept for 2 hours. After that, the degree of vacuum was gradually increased while keeping the temperature at 200℃, and finally, after reacting for 2 hours at a pressure of 10℃,
The temperature was raised to 20°C and part of the 1,6-hexanediol was distilled off to form polycarbonate d? with a molecular weight of 2000. I7
Got the oars. The hydroxyl value of this diol was 54.2, and the melting color (Gardner) at 75°C was 3.

The results are shown in Table-1.

Comparative Example 1 723 parts of jetelcargeneate, 841 parts of 1,6-hexanediol, and tetra-1go- produced by the reaction of ethyl alcohol and phosgene were placed in a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column. provir titanium)
Add 0.01 part of the mixture and heat to 125°C while distilling off the ethyl alcohol produced by the transesterification reaction.
It was held for 1 hour. Furthermore, the temperature was gradually raised to 180'C,
After keeping at this temperature for 2 hours, the temperature was raised to 200°C and kept for 8 hours. Afterwards, the degree of vacuum was gradually increased while maintaining the temperature at 200°C, and finally the reaction was carried out for 2 hours at a pressure of 1OxmHg.
The temperature was raised to 220°C and part of the 1,6-hexanodiol was distilled off to obtain je17-triol with a molecular weight of 1000.The hydroxyl value of this polyol was 114.
．． 5, and the melting color (Gardner) at 75°C was 6. Table 1 shows all the results.

Comparative Example 2 Into a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 771 parts of diethyl cargone (produced by the reaction of ethyl alcohol and phosgene), 1.6-? ll
908 parts of Dashiel and 1.63 parts of titanium tetrachloride were charged in total, heated, and held at 125° C. for 1 hour while distilling off ethyl alcohol produced by the transesterification reaction.

The temperature was further increased to 180°C and kept at this temperature for 2 hours.
Gradually raise the temperature to 00°C and keep at this temperature for 2 hours.Then, keep it at 200°C and gradually increase the degree of vacuum.Finally, react at a pressure of 1101H for 3 hours, then raise to 220°C. A part of the 1,6-hexanediol was distilled off to obtain a polycargonate polyol having a molecular weight of 2000. The hydroxyl value of this polyol is 5.1, and the melting color (Gardner) at 75°C is 7, which is 9. The results are shown in Table-1.

Example 2 In a glass reaction vessel equipped with a stirrer, a thermometer, a distillation column, and a nitrogen inlet tube, 1049 parts of diphenyl carbonate produced by the reaction of phenol and phosdan, 1.6-h+? :/Pour 706 parts and 0.24 parts of tetra-n-propyl titanate into Jio, heat it, and distill out the phenol produced by the transesterification reaction.210
The temperature was raised to "C".In addition, in order to help the distillation of phenol, a small amount of nitrogen was passed through and the temperature was kept at this temperature for 10 hours.
The temperature was raised to 220°C and maintained for 2 hours. The degree of vacuum was gradually increased while maintaining the temperature, and finally the pressure was 10 niHg.
, 6-hexanediol is partially distilled to give a molecular weight of 10
00 polycarbonate polyol was obtained. The hydroxyl value of this I diol was 111.2, and the melt color (Gardner) at 75°C was 2. The results are shown in Table 1.

Example 3 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 578 parts of diethyl carzanate produced by the reaction of ethyl alcohol and phosgene, 903 parts of 1#4-cyclohexane dimetatool, and tetra- 1.00 parts of n-butyl titanate) was charged, heated, and 12
It was held at 5°C for 1 hour. Further, the temperature was gradually raised to 180°C, kept at this temperature for 2 hours, and then raised to 200°C and kept for 2 hours. After that, the degree of vacuum was gradually increased while it was kept at 200 °C, and finally, after reacting for 2 hours at a pressure of 10 wHg, the temperature was raised to 220 °C to distill off a part of the 1,4-cyclohexane dimetatool. A polycargonate polyol having a molecular weight of 1000 was obtained. The hydroxyl value of this polyol is 1
21.0, the melting color (Gardner) at 75°C is 2
Met. The results are shown in Table 1.

Comparative Example 3 694 parts of diethyl carbonate produced by the reaction of ethyl alcohol and phosgene, 1115 parts of 1,6-hexanediol, and tetra-1so-propyl were placed in a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column. Pour 0.082 parts of titanate, heat, and distill off the ethyl alcohol produced by the transesterification reaction.
It was held at 5°C for 1 hour. The temperature was further raised to 180°C and held at this temperature for 2 hours, then gradually raised to 200°C and held at this temperature for 2 hours. After that, the degree of vacuum was gradually increased while maintaining the temperature at 200°C, and finally, after reacting at a pressure of 1OxmHg for 3 hours, the temperature was raised to 220°C, and a part of 1,6-hexanediol was distilled out. 2000 polycarbonate polyol was obtained. Hydroxyl value Fi of this polyol
58.4, and the melting color (Gardner) at 75°C is 3
It was ~4. The results are shown in Table-1.

Procedural amendment (voluntary) June 1986, 2nd day

Claims (1)

[Claims] 1. In a method for producing a polycarbonate polyol by transesterifying a dialkyl carbonate or diaryl carbonate and a polyhydroxy compound in the presence of a titanium catalyst, the ratio of the polyhydroxy compound to the dialkyl carbonate or diaryl carbonate is a stoichiometric amount. 1.01 to 1.30
The titanium-based catalyst amount is 0.0 times that of the dialkyl carbonate or diaryl carbonate as titanium.
0005 to 0.05% by weight of a polycarbonate polyol.