JPS6375030A - Production of polycarbonate polyol - Google Patents

Abstract

PURPOSE:To obtain the titled colorless polymer having excellent heat-resistance and hydrolysis resistance and suitable as a raw material for polyurethane, by carrying out ester-interchange reaction of a carbonate with a hydroxyl compound in the presence of an alkylene carbonate. CONSTITUTION:(A) A dialkyl carbonate (e.g. dimethyl carbonate) or a diaryl carbonate (e.g. diphenyl carbonate) is mixed with (B) a hydroxyl compound (e.g. 1,3-propanediol) and (C) an alkylene carbonate (e.g. ethylene carbonate) and the mixture is subjected to ester-interchange reaction in the presence of a catalyst comprising (D) a titanium compound (e.g. titanium trichloride) or (E) a tin compound (e.g. stannous acetate) to obtain the objective polymer. The amount of the component C is 0.05-50mol% based on the component A and that of the catalyst is preferably 0.00001-0.5wt% based on the obtained polymer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a polyurethane with a hydroxyl group at the end, which is suitable for economically producing high-quality polyurethane with excellent heat resistance and hydrolysis resistance, and with little coloring. The present invention relates to a method for producing a polycarbonate polyol having the following properties.

(Prior art and its problems) Conventionally, carnate compounds used in the production of polycarbonate polyols include dimethycargonate, diethyl carbonate, di-n-butyl cargonate, ethylene cargonate, and 1,2-f propylene. carcanate,
Diphenyl carbonate, etc. These cargoate compounds are usually produced by reacting alcohols or phenols with phosdanes, but due to the halodane compounds produced as by-products in this phosdanization reaction, especially the alkyl or aryl chloroformates remaining due to incomplete reaction, Problems arise in that the polycargonate polyol or polyurethane is colored and other side reactions that are undesirable for production are caused, and the production of high-quality 4-licargonate polyol or polyurethane is hindered due to non-uniform reaction. be. However, in these production methods, if an alkali or alkaline earth metal or its metal compound is used as a transesterification catalyst, the influence of halogens can be reduced, but the reaction rate of these catalysts is higher than that of desorption. In order to promote the decomposition of carbonic acid and the like and to cause an abnormal reaction with isocyanate during the production of I-urethane, post-treatment such as neutralization is required.

(Problems to be Solved by the Invention) In order to solve these problems, the present inventors have conducted intensive research and have developed a method for rapidly producing high-grade monocargonate triol with little coloring. This heading led to the present invention.

(Means for Solving the Problems) That is, the present invention provides a method for producing a polycargonate polyol by transesterifying a dialkyl carbonate or a diaryl carbonate and a hydroxy compound in the presence of a titanium compound or a tin compound. , 0.05 to 50 mol % alkylene carton based on dialkyl carbonate or diaryl carbonate? The present invention provides a method for producing a polycargonate polyol, characterized in that the transesterification reaction is carried out in the presence of a polycarbonate.

The dialkyl cargoonate compounds used in the production of monocargonates are normally required to be purified by high-level washing and distillation, but according to the production method of the present invention, they can be purified by washing with an ordinary alkaline aqueous solution and distillation. Since the obtained quality dicarbonate compound is sufficient, there is no need for advanced purification of the raw material, and considering the steps required for this and the reduction in yield, it is an energy-saving and economical method. I understand that.

(Structure) As the dialkyl carbonate or diaryl carbonate used in the present invention, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, di-1go-butyl carbonate, diphenyl carbonate, etc. are preferable. .

Hydroxy compounds used in the method of the invention include 1,3-propanediol, 1,4-1 tanediol, 1,5-(ntandiol, 1,6-hexanediol, 1,7-hebutanediol, 1 .8-octanediol, 2-ethyl-1,6-hexanediol, 2
-Methyl-1,3-f lonomandiol, neopentyl glycol, l,3-cyclohexanediol, 1.4
-cyclohexanediol, 2,2'-bis-(4-hydroxycyclohexyl)-telonone, p-xylene diol, cytetrachloroxylene diol, 1,4
-dimethylolcyclohexane, bis-droxymethyltetrahydride o7ran, di(2-hydroxyethyl)dimethylhydantoin, diethylene glycol, triethylene glycol s' diethylene glycol, diethylene glycol, polypropylene glycol, 21? These include ritetramethylene glycol, thioglycol, trimethylolethane, trimethylolpropane, hexanetriol, and pentaerythritol. These droxy compounds can be used alone or in combination in the transesterification reaction.

The titanium compounds used in the method of the present invention include organic titanium, titanium halide, titanic acid, and other inorganic titanium compounds such as tetraethylnathanate, tetra-1so
-Propyl titanate, tetra-n-titanate, titanium acetylacetone, titanylammonium oxalate, = titanium chloride, titanium tetrachloride, titanium tetrafluoride, sodium chloride titanate, ammonium chloride titanate, ammonium fluorotitanate, titanic acid ( (2), titanium sulfate, etc., but titanium tetrachloride and nato-2-n-butyl titanate or tetra-1so-propyl titanate are preferred.

The tin compounds used in the present invention include tin sulfaminate, stannous acetate, diptyltin simalate, dibutyltin dichloride, dibutyltin oxide, monobutyltin oxide, tin octenoate, tin oxide, tin oxide, and iodine. Examples include stannic oxide, tin stearate, tin sulfide, triphenyltin malate, dimethoxybutyltin, methyltin triisooctylate, tin diurate, and preferably diptyltin simarate, tin oxide, etc. Tin, dibutyltin oxide.

The amount of the titanium compound or tin compound used is usually 0.000% based on the weight of the polycargonate podiol obtained.
01-0.5 weight 5, preferably 0.0001-0.0
It is within the range of 1% by weight.

The alkylene cargoes used in the present invention include:
Ethylene Cargonate, Trimethylene Cargonate, Tetramethylene Carnate, 1,2-Globylene Car?
1,2-1 tylene carbonate, 1,3-butylene carbonate, 2.3-butylene carbonate, 1
．． 2--R ethylene cargonate, 1.3-e ethylene cargonate, 1.4-inch ethylene cargonate), 1
．． Al with 5-pentylene carbonate, 2,3-J-ethylene carbonate, 2,4-pentylene carbonate, etc.

The alkylene carbonate used in the present invention is 0.05 to 50 mol %, preferably 0.5 to 30 mol/I/%, particularly preferably 1 ~10 mol%. The amount of alkylene carbonate used is 0.0
If it is less than 5 mol%, the obtained polycargonate will be colored, and if it is more than 50 mol%, the obtained polycargonate will not be colored, but there will be many ether group structures that have a negative effect on thermal stability. A drawback arises.

The manufacturing conditions of the present invention are not particularly limited, but are usually 18
The transesterification reaction is carried out for about 1 to 4 hours at a low temperature of 0°C or lower, and further at 150 to 280°C, preferably 180°C.
The reaction is carried out at about 240° C. for several hours, and then the reaction is carried out for several hours at the same temperature and under a pressure of 20 mHg or less.

The structure of the polycargonate polyol f: produced under pressure was analyzed by C-NMRK.
Ether group structures that adversely affect thermal stability etc. caused by decarboxylation are extremely rare or are hardly observed. Furthermore, according to a thermal stability test using Gear-Olan, a product was obtained that had a very low degree of coloring and did not have a small decrease in viscosity.

Further, the transesterification reaction is usually carried out in a large stainless steel reaction vessel, but when the production method of the present invention is not used, corrosion of the reaction vessel is observed.

In contrast, according to the manufacturing method of the present invention, corrosion of mild steel and stainless steel is not observed, and damage to the reaction vessel can be reduced without using special acid-resistant materials.

By reacting the polycargonate podiol having hydroxyl group terminals produced by the present invention with a diisocyanate, it is possible to provide a polyurethane resin having extremely excellent moist heat resistance and hydrolysis resistance.

Next, examples of the present invention will be described, but the present invention is not limited to these in any way. "Parts" and "%" in the text are based on weight.

Example 1 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 715 parts of diethyl carbonate produced by reaction lIC of ethyl alcohol and phosgene, 59 parts of ethylene carbonate, 799 parts of 1,6-hexanediol, and tetra- 0.055 part of 1go-propylene titanate) was charged, heated, and held at 125° C. for 1 hour while bubbling out ethyl alcohol produced by transesterification and reaction. The temperature was further raised to 150°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 maintaining the temperature at 200°C, and finally, after reacting for 2 hours at a pressure of 10 μHg, the temperature was raised to 220°C, and a portion of the 1°6-hexanediol was bubbled out to determine the molecular weight. Approximately 1000 polycargonate polyols were obtained. The hydroxyl value of this diol is 110, and the melting color at 75°C (APHA
) was 80.

Comparative Example 1 715 parts of diethyl carbonate produced by the reaction of ethyl alcohol and phosgene, 902 parts of 1,6-hexanediol, and 1 volume of tetra-diol were placed in a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column.

- Probyl titanate o, oss metal preparation, heating,
The temperature was maintained at 125° C. for 1 hour while bubbling ethyl alcohol produced by the transesterification reaction.

The temperature was further raised to 150°C, kept at this temperature for 2 hours, and then heated to 20°C.
The temperature was raised to 0°C and maintained for 2 hours. After that, the degree of vacuum was gradually increased while keeping the temperature at 200°C, and finally, after reacting for 2 hours at a pressure of 10 mHH, the temperature was raised to 220"C and a part of 1.6-hexanediol was distilled out to determine the molecular weight. Approximately 4 out of 1000
Liquor obtained nate polyol. This polyol water R1 & 2! The lii value was 115, and the melt color at 75°C (APRA) was 400.

Corrosion was observed in the stainless steel stirring rod in this reaction. The results are shown in Table-1.

Example 2 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 782 parts of diethyl carbonate, 31 parts of ethylene cargoate, and 830 parts of 1,6-hexanediol were placed in a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column. 1 part and 0.055 part of tetra-1so-propyl titanate were charged, heated, and held at 125° C. for 1 hour while distilling off ethyl alcohol produced by the transesterification reaction.

The temperature was further raised to 150°C and kept at this temperature for 2 hours.
The temperature was raised to 00°C and maintained for 2 hours. After that, the degree of vacuum was gradually increased while keeping the temperature at 200°C, and after finally reacting at a pressure of 10 mHg for 3 hours, the temperature was raised to 220°C and a part of 1,6-hexanediol was distilled out, resulting in a molecular weight of about 2000. The monoliquor 2 nate Iliol was obtained.

The hydroxyl value of this polyol was 55.6, and the melting color (APRA) at 75° C. was 1)0. Full results table-
Shown in 1.

Example 3 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation tower, 595 parts of diethylcarnate, 65 parts of ethylene cargoate, and 949 parts of 1,6-hexanediol were prepared by the reaction of methyl alcohol and phosgene. and Tet,
0.055 part of y-1so-globil titanate) was charged, heated, and held at 125° C. for 1 hour while extruding the methyl alcohol produced by the transesterification reaction.9. The temperature was further raised to 150°C, kept at this temperature for 4 hours, and then 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-Hg, the temperature was raised to 220℃ and a part of the 1゜6-hexanediol was distilled out to determine the molecular weight. Approximately 1000 polycarnate polyols were obtained. The hydroxyl value of this polyol is 115, and the melting color at 75°C (APRA
') was 60. The results are shown in Table-1.

Example 4 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 589 parts of diethyl carbonate, 48 parts of ethylene cargoate, and 946 parts of 1,4-cyclohexane dimetatool were prepared by the reaction of ethyl alcohol and phosgene. 1 part and 0.055 part of teto 5-1ea-norobyl titanate were charged, 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 150°C and kept at this temperature for 2 hours.
The temperature was raised to 0°C and maintained for 2 hours. After that, the degree of vacuum was gradually increased while maintaining the temperature at 200℃, and after finally reacting for 2 hours at a pressure of 10 μHg, the temperature was raised to 220℃ and a part of the 1,4-cyclohexane dimetatool was distilled out. molecular weight approximately 100
A total of 0 polycarmenate boriol was obtained. The hydroxyl value of this polyol is 118, and the melting color at 75°C (AP
HA) was 160. The results are shown in Table 1 below.

Example 5 944 parts of diphenyl carbonate, 43 parts of ethylene cargo, and 1,6-hexanediol produced by the reaction of 7 enol and phosgene were placed in a glass reaction vessel equipped with a stirrer, a thermometer, a distillation column, and a nitrogen introduction tube. 673 parts of tetra-1ea-norobyl titanate and 0.055 parts of tetra-1ea-norobyl titanate were charged, heated, and the temperature was raised to 210° C. while distilling out phenol produced by the transesterification reaction. The temperature was kept at this temperature for 10 hours while passing a small amount of nitrogen to assist foaming of phenol, and then the temperature was raised to 220°C and kept for 2 hours. While maintaining the temperature, the degree of vacuum was gradually increased, and finally a portion of 1,6-hexanediol was distilled out at a pressure of 10 swmHH to obtain a precargonate polyol having a molecular weight of about 1000. The hydroxyl value of this polyol is 116
The bath melting color (APHA) at 75°C was 180. The results are shown in Table-1.

Example 6 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 541 parts of diethyl cargo, which was produced by the reaction of ethyl alcohol and phosgene, 3 parts of ethylene cargo, and 837 parts of 1,6-hexanediol were placed. and 0.055 part of tetra-1go-zorobyl titanate, heated, and held at 125° C. for 1 hour while distilling off ethyl alcohol produced by transesterification.

After increasing the temperature to 150℃ and keeping it at this temperature for 2 hours,
The temperature was raised to 00°C and maintained 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 10μHg, the temperature was raised to 220℃ to distill out a part of the 1゜6-hexanediol, and the molecular weight A polycargonate polyol of about 1000 was obtained.The hydroxyl value of this polyol was 118, and the melting color at 75°C (APRA
) was 60. The results are shown in Table-1.

Comparative Example 2 In a glass reaction vessel equipped with a stirrer, a thermometer, and a distillation column, 795 parts of ethylene cargo, 902 parts of 1,6-hexanediol, and 0.055 parts of tetra-1go-7' lobil titanium were charged and heated. The temperature was maintained at 180° C. and a vacuum degree of 150 mHg for 4 hours. The temperature was further raised to 200°C and maintained at this temperature for 2 hours.

While maintaining that temperature, gradually increase the degree of vacuum until it reaches 1
After reacting at a pressure of 0 mHg for 2 hours, the temperature was raised to 220°C and a portion of 1,6-hexanediol was distilled off to obtain a polycarbonate preol having a molecular weight of about 1000. This polyol had a hydroxyl value of 107 and a melting color (APRA) of 80 at 75°C.

3001 of each of the polycargonate polyol 'i5001nt of Examples 1 to 6 and Comparative Examples 1 and 2 obtained as described above was collected in a glass bottle, covered with a lid to allow slight ventilation, and kept open at 200°C. The samples were left for 5 days and the changes in coloring were compared. I showed the results to Ga1.

As a result, the polycargonate polyol of Comparative Example 2 showed little coloration immediately after polycargenate polyol production, but
It was found that heat resistance caused severe discoloration due to heat. This is due to the ether groups produced in the side reactions of ethylene cargo, and as shown in Table 1, it is clear that the polyol has a low melting point and is a polycargonate polyol with an extremely large number of ether groups.

Claims (1)

[Claims] A method for producing a polycarbonate polyol by transesterifying a dialkyl carbonate or diaryl carbonate with a hydroxy compound in the presence of a titanium compound or a tin compound, wherein 0.0 for the dialkyl carbonate or diaryl carbonate.
A method for producing a polycarbonate polyol, characterized in that the transesterification reaction is carried out in the presence of 5 to 50 mol% of alkylene carbonate.