JP4529676B2 - Process for producing reactive stabilized polycarbonate polyol and polyurethane resin using reactive stabilized polycarbonate polyol - Google Patents

Description

  The present invention relates to a method for producing a reactive stabilized polycarbonate polyol and a polyurethane resin produced using the reactive stabilized polycarbonate polyol.

  Polycarbonate polyol is a polyurethane resin used in rigid foams, flexible foams, paints, adhesives, coating agents, elastomers, fibers, synthetic leather, ink binders, etc., by reaction with isocyanate compounds, like polyester polyols and polyether polyols. It is a useful compound used as a raw material for manufacturing.

Polycarbonate polyols are produced in the presence of relatively strong catalytic activity, such as the use of a highly active transesterification catalyst or a large amount of added catalyst because the transesterification reaction is slower than conventional polyester polyols. Has been done. However, since this transesterification reaction catalyst maintains its activity unless it is subjected to a deactivation treatment, when it is used in a polyurethane resin, it has a high reactivity with an isocyanate compound and has problems such as gelation. As these measures, for example, describes a technique of performing inactivation treatment by reaction modifiers such as Patent Document 1 and Patent Document 2 water or phosphite triester.

  Also, in the conventional method, if the reaction modifier to be added is excessive, it acts as an accelerator on the contrary, and if the amount of the reaction modifier is increased, the durability of the polyurethane resin is lowered, or the resin There are problems such as easy to color. As these measures, for example, in Patent Document 3 below, an invention is found that exhibits the delay effect of a polyol containing a high proportion of 1,4-butanediol units without adding a reaction modifier to the adjustment of urethanization reactivity. Has been proposed.

Japanese Patent Publication No. 8-26140 JP 2002-69166 A JP-A-5-25264

  However, when the deactivation treatment is performed with water (used in Patent Document 1), there is a problem that turbidity is generated due to generation of a metal oxide or the like, which is not useful. On the other hand, the deactivation treatment was performed by adding inorganic acids such as hydrochloric acid and sulfuric acid, organic salts such as p-toluenesulfonic acid, esters such as phosphoric acid esters and phosphorous acid esters (used in Patent Document 2) as reaction modifiers. In such a case, the reactivity with the isocyanate compound varies from lot to lot, causing an abnormal reaction and causing gelation or the like. In addition, in order to produce a stable polyurethane resin, it is necessary to adjust the amount of reaction modifier used for each lot, and there are problems in the global environment such as the utility load associated with the production of polycarbonate polyol. .

  Further, in the method of Patent Document 3, about 60% or more of the diol component requires 1,4-butanediol, so that the application or adaptation range is very narrow, and it is effective in a state where the catalytic activity is low. In the state where catalyst activity is high, the reactivity at the time of urethanation has changed, so the fundamental solution has not yet been reached. Polycarbonate polyol with reduced reaction adjustment work for each lot and stable reactivity The offer of was desired.

  The present invention has not been obtained in the past by solving these problems, which are problems in producing a reactive stabilized polycarbonate polyol, and by using a polyurethane resin using the reactive stabilized polycarbonate polyol. A method for producing an excellent reactive stabilized polycarbonate polyol such as stable productivity and stable resin performance in terms of quality, and a polyurethane resin using the reactive stabilized polycarbonate polyol produced by this production method The purpose is to provide.

Means and effects for solving the problems

The method for producing the reactive stabilized polycarbonate polyol of the present invention is selected from glycol having 4 to 20 carbon atoms or aliphatic linear or branched linear chain, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. was to comprise a single type and step of reacting the dialkyl carbonate, said Jiariruka Bo sulfonate, or the alkylene carbonate, a tosyl isocyanate were dehydrated, are the following moisture content 15ppm Features . Also, the production method of the reactive stabilizing polycarbonate polyols of the present invention is preferably one further comprising the step of embedding processing heat in the presence of phosphoric esters.
Conventionally, the adjustment amount of the reaction modifier was adjusted for each lot until the desired reactivity was obtained. With the above configuration, a stable urethanization reactivity was obtained by adding a certain amount of the reaction modifier. Therefore, the reaction adjustment work can be reduced.

Here, the moisture content of 15ppm or less of the dialkyl carbonate, Jiariruka Bo sulfonates, or reason for using alkylene carbonate will be described.
Conventionally used polycarbonate polyols cause an abnormal reaction in the urethanization reaction with an isocyanate compound during the urethanization reaction, causing problems such as gelation. Although the cause of this is not clear, since the reaction rate of the polyol during the urethanization reaction is high, it is conceivable that the reaction is accelerated by crosslinking due to the heat generation. In order to suppress this reaction promotion, reaction modifiers that have a reaction delay effect have been studied and are still in use, but it takes a long time to reach the desired viscosity and gelation due to abnormal phenomena that occur occasionally. The problem was not solved.

  In the study by the present inventors, the cause of the reactivity that differs for each lot of polycarbonate polyol lies in the quality of the raw material used, and in particular, in the carbonating agent such as dialkyl carbonate, diaryl carbonate, alkylene carbonate, etc. whose water content and variation are large. Was also found to be caused. The transesterification reaction catalyst is partially deactivated by the moisture, and the variation in moisture content varies the deactivation amount of the transesterification catalyst. It is thought that the reactivity varied and sometimes gelation occurred due to an abnormal phenomenon. That is, conventionally, a distillation method having a high number of theoretical plates or an adsorption method using activated carbon or the like has been mainly used, but there is a limit to processing a very small amount of water. It has been found that stable reactivity can be obtained by using the above carbonating agent having a water content of 15 ppm or less, which is obtained by treating the water with a chemical reaction.

Hereinafter, embodiments of the present invention will be described in detail. The method for producing the reactive stabilized polycarbonate polyol of the present embodiment is selected from glycol having 4 to 20 carbon atoms or aliphatic linear or branched linear chain, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. it is those containing one and the step of reactions, the dialkyl carbonate, the Jiariruka ball sulfonate, or the alkylene carbonate, and characterized in that it is of less water content 15 ppm, of phosphoric esters It is preferable that the method further includes a step of heat-embedding in the presence. In addition, the dialkyl carbonate, the Jiariruka ball sulfonate, or the alkylene carbonate used those dehydrated by tosyl isocyanate.

  Examples of glycols composed of alicyclic or aliphatic straight chain or branched chain having 4 to 20 carbon atoms used in the present embodiment include 1,4-butanediol, diethylene glycol, 1,5-pentanediol, and 1,6-hexane. Diol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 2-ethyl-1,6-hexane Diol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedi Methanol, 2,2'-bis (4-hydroxycyclohexyl) -propane, 1,4-cyclohexanedimethano Rudipropylene glycol, polytetramethylene glycol, 2,6′-dihydroxyethylhexyl ether, 2,4′-dihydroxyethyl butyl ether, 2,5′-dihydroxyethyl pentyl ether, 2,3′-dihydroxy-2,2′-dimethyl Although propyl ether etc. are mentioned, Preferably it is glycol which consists of C4-C9 alicyclic or aliphatic linear or branched chain, for example, 1, 4- butanediol, diethylene glycol, 1,5 -Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,7-pentane Diol, 1,8-octanediol, 2-methyl-1,8-octanedio Le, can be used to select one or two or more of the 1,9 and these diols.

  Examples of the dialkyl carbonate as a carbonating agent having a water content of 15 ppm or less used in the present embodiment include asymmetric dialkyl carbonates such as methyl ethyl carbonate in addition to symmetric dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, and butylene carbonate. Examples of the diaryl carbonate include symmetric diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate, and asymmetric diaryl carbonates such as phenyl naphthyl carbonate. Of these, dialkyl carbonate is preferred as the carbonating agent, but diethyl carbonate is particularly preferred.

  Impurities and moisture contained in carbonating agents such as dialkyl carbonate, diaryl carbonate, or alkylene carbonate have been conventionally removed using distillation, activated carbon, etc., but such facilities and physical methods can remove the impurities and moisture. Therefore, a method of chemically removing water by addition of tosyl isocyanate or the like is preferable because the water content is also limited. The water content in these carbonating agents is preferably 15 ppm or less, particularly preferably 10 ppm or less.

  Examples of the phosphoric acid ester used in this embodiment include ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, olein acid phosphate, tetracosyl acid phosphate , Dibutyl phosphate, bis (2-ethylhexyl) phosphate, and the like.

  The range of the number average molecular weight of the polycarbonate polyol of this embodiment varies depending on the application, but is usually 300 to 10,000, preferably 500 to 8,000.

  Subsequently, a specific reaction will be described. The reaction in this embodiment has the same reaction mechanism as a known transesterification reaction.

  In the present embodiment, it is preferable to use a catalyst used in the transesterification reaction during the reaction. As this catalyst, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, cerium and other metals, metal alkoxides, metal salts, A metal oxide etc. are mentioned. In this embodiment, carbonates, carboxylates, borates, silicates, oxides, and organometallic compounds of alkali metals, argali earth metals, zinc, titanium, and lead are used as catalysts. Of these, organic titanium compounds are preferred.

  The amount of catalyst used is 0.0001 to 1%, preferably 0.001 to 0.1% of the total mass of the starting materials. When the amount of the catalyst is too small, the reaction time becomes long, so that the production efficiency is deteriorated and the obtained polycarbonate polyol is also easily colored, which is not preferable. Moreover, when there is too much catalyst amount, since the water resistance of the polycarbonate polyol obtained may fall, it is unpreferable.

  The polycarbonate polyol in the present embodiment can proceed under milder conditions than known transesterification reactions. Specifically, in the process of proceeding the reaction, it is possible to proceed the reaction in a temperature range of 90 to 200 ° C. under normal pressure (that is, without reducing pressure). The reaction is preferably allowed to proceed in a temperature range of 100 to 195 ° C, more preferably in a temperature range of 110 to 190 ° C.

  Although the reaction can be carried out at normal pressure, it is also possible in this embodiment to accelerate the reaction by carrying out the reaction in the latter half of the reaction under reduced pressure, for example, at 0.13 kPa to 26.6 kPa. Further, during the known dealcoholization treatment after the transesterification reaction, it is also possible to promote this by reducing the pressure similarly.

  The initial stage of the reaction is carried out in the vicinity of the boiling point of the carbonating agent, specifically in the temperature range of 90 to 150 ° C., and the reaction is further advanced by gradually raising the temperature as the reaction proceeds.

  An apparatus capable of separating the produced polycarbonate polyol and the carbonating agent is usually a reactor equipped with a distillation tower, which reacts while refluxing the carbonating agent, and generates a low molecular hydroxyl group as the reaction proceeds. An apparatus for distilling the contained compound is preferred.

Polycarbonate polyol used in the polyurethane resin of the present embodiment has a molecular weight of Ru it used those 400 to 10000, preferably one in particular of 500 to 5000. Examples of the organic diisocyanate used in the polyurethane resin of the present embodiment include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-. Diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethylxylylene Range isocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-di Aromatic diisocyanates such as isocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, aliphatic diisocyanates such as lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, Aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and cyclohexyl diisocyanate, and these Mixtures of two or more, urethane-modified products of these organic diisocyanates, allophanate modified product, a urea modified product, a biuret modified product, uretdione modified product, uretonimine modified products, isocyanurate modified products, carbodiimide-modified products, etc., all known organic diisocyanates It may be.

  The chain extender used in this embodiment is preferably a low molecular weight compound having two or more active hydrogen groups. Examples of such a low molecular weight compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3. -Butanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,9-nonanediol and the like. These compounds may be used alone or in combination of two or more.

  In this reaction, as a matter of course, known catalysts such as metal salts and amines can be used in combination as necessary. In addition, these reactions are obtained by reacting in a solvent, and preferred solvents are one of isocyanate inert solvents such as dimethylformamide, diethylformamide, dimethylacetamide, cyclohexanone, methyl ethyl ketone, ethyl acetate, and toluene. Or the mixture of 2 or more types is mentioned.

  The molecular weight of the polyurethane resin of this embodiment is preferably 20,000 to 100,000, more preferably 30,000 to 80,000. When the molecular weight is 20,000 or less, the mechanical strength of the obtained polyurethane resin is not sufficient, and when the molecular weight exceeds 100,000, the solution viscosity is high and handling properties are lowered, which is not practical.

  In addition, in order to improve the heat resistance, weather resistance, workability, and the like of the polyurethane resin of this embodiment, various generally known additives can be used for the polyurethane resin of this embodiment. For example, these additives include antioxidants, UV absorbers, UV stabilizers, reinforcing fibers, fillers, mold release agents, and colorants.

  The polyurethane resin of this embodiment is used for rigid foams, flexible foams, paints, adhesives, coating agents, elastomers, fibers, synthetic leather, ink binders, etc., because of the small variation in reactivity, especially the properties of polyurethane resins. Is a compound useful for synthetic leather, artificial leather, coating composition, and thermoplastic resin that require a delicate touch feeling.

  According to this embodiment, the glycol consisting of an alicyclic or aliphatic straight chain or branched chain having 4 to 20 carbon atoms is reacted with one kind selected from dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Since the dialkyl carbonate, the diaryl carbonate, or the alkylene carbonate uses a water content of 10 ppm or less in the production process of the reactive stabilized polycarbonate polyol including a step, a stable urethanization reaction can be obtained, Furthermore, since the urethanization reaction has been stabilized, the partially gelled product that has sometimes occurred in the past can be suppressed, and a stable urethane resin can be produced.

  Moreover, the polycarbonate polyol obtained in the present embodiment can provide a polyurethane resin with little variation in quality.

  Furthermore, the polycarbonate polyol obtained in the present embodiment is useful in that, for example, a polyurethane resin reacted with an isocyanate compound using this as a raw material has a small variation in characteristics between lots, and is thus stable in obtaining characteristics. is there. Therefore, it can be widely used in various industrial applications such as rigid foams, flexible foams, paints, adhesives, coating agents, elastomers, fibers, binders for magnetic tapes, various sealing materials, which are main uses of polyurethane resins. In particular, for synthetic leather, artificial leather, and coating agents as a direct touch application, variation in characteristics among lots is a fatal problem, so the polycarbonate polyol obtained in this embodiment can be used as a raw material. Useful. It is also useful as a modifier or a raw material for urethane acrylate resin for imparting toughness and workability to polyester resin, polycarbonate resin, polyvinyl chloride resin, acrylonitrile-styrene resin, epoxy resin and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In the examples, “part” means part by mass, and “%” means mass%.

The moisture in the examples was measured using a trace moisture measuring device CA-100 manufactured by Mitsubishi Chemical Corporation. The hydroxyl value in the examples was measured by an acetylation method. Moreover, the number average molecular weight in an Example was measured by the method described below. The terminals of the polycarbonate polyol of the present invention were substantially all hydroxyl groups by NMR measurement. Furthermore, the acid value in the polymer was measured by titration with KOH, and all of the polymers were 0.01 or less. Therefore, the number average molecular weight of the polymer is obtained by the following formula (1).
Number average molecular weight = (56.11 × 2 × 1000) / hydroxyl value (1)

Diethyl carbonate used in the examples was procured by the following method.
(Example of dehydration of diethyl carbonate)
Although not shown in the figure, diethyl with a water content of 200 ppm was added to a reaction apparatus in which a stirrer, a thermometer, a heating device, and a distillation column (a short tube (column) was set with a Toh tube, a Riich condenser tube, and an eggplant type flask set). 9000 parts of carbonate and 74 parts of tosyl isocyanate were collected and stirred at room temperature for 15 minutes. Next, the temperature was raised to 120 to 130 ° C., and distillation was stopped when 8820 parts of diethyl carbonate in the reactor was recovered in the eggplant type flask. When the moisture was measured using a trace moisture measuring device CA-100 manufactured by Mitsubishi Chemical Corporation, the moisture content was 4 ppm. The purity was 99.96% when the distillate was measured using a capillary column with Shimadzu Corporation gas chromatography GC-14A.
Diethyl carbonate DEC-1 prepared in this manner and DEC-2 to 9 prepared by adding purified water to DEC-1 so as to have the water content shown in Table 1 were obtained.

The dimethyl carbonate used in the examples was procured by the method shown below.
(Example of dehydration of dimethyl carbonate)
Although not shown in the figure, a reactor equipped with a stirrer, a thermometer, a heating device, and a distillation column (a short tube (column) is set with a Toh tube, a Riipich cooling tube, and an eggplant type flask) is combined with dimethyl having a water content of 235 ppm. 9000 parts of carbonate (DMC-A) and 74 parts of tosyl isocyanate were collected and stirred at room temperature for 15 minutes. Next, the temperature was raised to 90 to 100 ° C., and distillation was stopped when 8790 parts of dimethyl carbonate in the reactor was recovered in the eggplant type flask. When the moisture content was measured using a trace moisture measuring device CA-100 manufactured by Mitsubishi Chemical Corporation, the moisture content was 5 ppm. The purity was 99.92% when the distillate was measured using a capillary column with Shimadzu Gas Chromatography GC-14A.
Purified water was added to the thus obtained diethyl carbonate DMC-1 to obtain DMC-2 having a water content of 9 ppm.

Example 1
In a reaction apparatus including a stirrer, a thermometer, a heating device, and a distillation tower, 830 parts of 1,6-hexanediol (hereinafter abbreviated as 1,6HG), 771 parts of diethyl carbonate DEC-1 (water content 4 pppm), As a reaction catalyst, 0.05 part of tetrabutyl titanate is charged, and the reaction product is maintained at a temperature of about 125 ° C. to 135 ° C. under a nitrogen stream to distill the produced ethyl alcohol. When the distillation of ethyl alcohol reaches 30% to 40% (mass) of the theoretical production amount, the temperature is raised to 190 ° C. at a rate of 4 to 10 ° C./hour. The reaction was carried out at a reaction temperature of 190 ° C. until no distillation of ethanol occurred. Furthermore, the reaction was carried out under reduced pressure in order to remove low boiling substances. In the reduced pressure reaction, while maintaining the reaction temperature at 190 ° C., the degree of vacuum is reduced from normal pressure at a reduced pressure rate of 6.6 to 13.2 kPa / hr, and finally at a pressure of 1.3 kPa for 2 to 5 hours. The reaction was continued under the same temperature and reduced pressure, and the reaction was terminated when the end of the polycarbonate polyol was replaced with a hydroxyl group by NMR measurement, and a colorless transparent liquid (polycarbonate) having a hydroxyl value of 56.2 KOHmg / g and a number average molecular weight of 1997. Polyol) 980 parts were obtained.
500 parts of the obtained polycarbonate polyol and 0.05 part of 2-ethylhexyl acid phosphate as a reaction adjusting agent were mixed at 120 ° C. for 4 hours in the same reaction apparatus as described above, and the reactive stabilized polycarbonate polyol PCD-1 About 500 parts were obtained.

(Examples 2 to 4)
The reactivity shown in Table 1 was the same as in Example 1 except that DEC-2 to 4 having different water contents were prepared in the same reactor as in Example 1 and the moisture content shown in Table 1 was used. Stabilized polycarbonate polyols PCD-2 to 4 were obtained.

(Example 5)
In the same reactor as in Example 1, DEC-10 to 14 having a water content of 15 ppm or less with tosyl isocyanate was used for diethyl carbonate having a different water content by the same method as in the above-mentioned diethyl carbonate dehydration example. The reactive stabilized polycarbonate polyols PCD-EX1 to 5 shown in Table 2 were obtained in the same manner as in Example 1 except that.

(Example 6)
The same method as in Example 1 except that 1,5 pentanediol (hereinafter abbreviated as 1,5PD) was reacted in the same reaction apparatus as in Example 1 with 811 parts and DEC-10 shown in Table 2 as 860 parts. Thus, a reactive stabilized polycarbonate polyol PCD-5 having a hydroxyl number of 55.6 KOHmg / g and a number average molecular weight of 2018 was obtained.

(Example 7)
A reaction apparatus similar to that of Example 1 was reacted in the same manner as in Example 1 except that 1,5PD was reacted at 811 parts and DEC-14 shown in Table 2 at 860 parts, and a hydroxyl value of 56.5 KOHmg / g. A reactive stabilized polycarbonate polyol PCD-6 having a number average molecular weight of 1986 was obtained.

(Example 8)
In the same manner as in Example 1, except that 385 parts of 1,5PD, 436 parts of 1,6HG, and 813 parts of DEC-11 shown in Table 2 were reacted in the same reaction apparatus as in Example 1. A reactive stabilized polycarbonate polyol PCD-7 having a hydroxyl number of 55.3 KOHmg / g and a number average molecular weight of 2029 was obtained.

Example 9
In the same manner as in Example 1, except that 385 parts of 1,5PD, 436 parts of 1,6HG, and 813 parts of DEC-12 shown in Table 2 were reacted in the same reaction apparatus as in Example 1. A reactive stabilized polycarbonate polyol PCD-8 having a number average molecular weight of 2000 having a hydroxyl value of 56.1 KOHmg / g was obtained.

(Example 10)
In the same reactor as in Example 1, 513 parts of 1,4-butanediol (hereinafter abbreviated as 1,4BG), 288 parts of 1,6HG, and 902 parts of DEC-12 shown in Table 2 were reacted. A reactive stabilized polycarbonate polyol PCD-9 having a number average molecular weight of 1979 having a hydroxyl value of 56.7 KOHmg / g was obtained in the same manner as in Example 1 except that.

(Example 11)
In the same manner as in Example 1, except that 513 parts of 1,4BG, 288 parts of 1,6HG, and 902 parts of DEC-13 shown in Table 2 were reacted in the same reactor as in Example 1. A reactive stabilized polycarbonate polyol PCD-10 having a number average molecular weight of 2037 having a hydroxyl value of 55.1 KOHmg / g was obtained.

(Example 12)
Example 1 except that 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM) was reacted in the same reaction apparatus as in Example 1 using 869 parts and DEC-13 shown in Table 2 as 594 parts. In the same manner, a reactive stabilized polycarbonate polyol PCD-11 having a number average molecular weight of 2018 having a hydroxyl value of 55.6 KOHmg / g was obtained.

(Example 13)
The number of hydroxyl values of 54.9 KOHmg / g was the same as in Example 1 except that 869 parts of CHDM and 594 parts of DEC-14 shown in Table 2 were reacted in the same reactor as in Example 1. A reactive stabilized polycarbonate polyol PCD-12 having an average molecular weight of 2044 was obtained.

(Example 14)
In the same reaction apparatus as in Example 1, 436 parts of 1,9 nonanediol (hereinafter abbreviated as 1,9ND), 436 parts of 2-methyl-1,8-octanediol (hereinafter abbreviated as 2MOD), A reactive stabilized polycarbonate polyol PCD-13 having a hydroxyl number of 56.8 KOHmg / g and a number average molecular weight of 1976 was obtained in the same manner as in Example 1, except that 583 parts of DEC-11 shown in 2 was reacted.

(Example 15)
The hydroxyl group was reacted in the same manner as in Example 1 except that 1,9ND, 436 parts, 2MOD, 436 parts, and DEC-13 shown in Table 2 were reacted in the same reaction apparatus as in Example 1. A reactive stabilized polycarbonate polyol PCD-14 having a number average molecular weight of 1993 with a value of 56.3 KOHmg / g was obtained.

(Example 16)
In the same reaction apparatus as in Example 1, except that 830 parts of 1,6HG and 587 parts of DMC-1 shown in the dehydration example of dimethyl carbonate were reacted, the hydroxyl value of 55 was obtained. A reactive stabilized polycarbonate polyol PCD-15 having a number average molecular weight of 2008 of .9 KOHmg / g was obtained.

(Example 17)
In the same reaction apparatus as in Example 1, except that 830 parts of 1,6HG and 587 parts of DMC-2 shown in the dehydration example of dimethyl carbonate were reacted, the hydroxyl value of 56 was obtained. A reactive stabilized polycarbonate polyol PCD-16 having a number average molecular weight of 1986 of 5 KOH mg / g was obtained.

(Comparative Examples 1-5)
Comparative Example shown in Table 1 in the same manner as in Example 1 except that DEC-5 to 9 having different water contents were prepared in the same reactor as in Example 1. 1 to 5 polycarbonate polyols PCD-A to E were obtained.

(Comparative Example 6)
Reactivity stabilization shown in Table 2 in the same manner as in Example 1 except that diethyl carbonate DEC-15-19 having different water contents shown in Table 2 was used in the same reactor as in Example 1. Polycarbonate polyol PCD-EX6-10 was obtained.

(Comparative Example 7)
A hydroxyl value of 54.7 KOHmg / g was obtained in the same manner as in Example 1, except that 1,11 PD was reacted with 811 parts and DEC-15 shown in Table 2 was reacted with 860 parts in the same reaction apparatus as in Example 1. The polycarbonate polyol PCD-F having a number average molecular weight of 2052 was obtained.

(Comparative Example 8)
A hydroxyl value of 55.5 KOHmg / g was obtained in the same manner as in Example 1, except that 1,11 PD was reacted with 811 parts and DEC-19 shown in Table 2 was reacted with 860 parts in the same reaction apparatus as in Example 1. The polycarbonate polyol PCD-G having a number average molecular weight of 2022 was obtained.

(Comparative Example 9)
In the same manner as in Example 1, except that 1,5 PD, 385 parts, 1,6HG, 436 parts, and DEC-16 shown in Table 2 as 813 parts were reacted in the same reaction apparatus as in Example 1. A polycarbonate polyol PCD-H having a number average molecular weight of 1993 having a hydroxyl value of 56.3 KOHmg / g was obtained.

(Comparative Example 10)
In the same manner as in Example 1, except that 385 parts of 1,5PD, 436 parts of 1,6HG, and 813 parts of DEC-19 shown in Table 2 were reacted in the same reaction apparatus as in Example 1. A polycarbonate polyol PCD-I having a number average molecular weight of 2018 having a hydroxyl value of 55.6 KOHmg / g was obtained.

(Comparative Example 11)
In the same manner as in Example 1, except that 513 parts of 1,4BG, 288 parts of 1,6HG, and 902 parts of DEC-17 shown in Table 2 were reacted in the same reaction apparatus as in Example 1. A polycarbonate polyol PCD-J having a number average molecular weight of 2000 having a hydroxyl value of 56.1 KOHmg / g was obtained.

(Comparative Example 12)
In the same manner as in Example 1, except that 513 parts of 1,4BG, 288 parts of 1,6HG, and 902 parts of DEC-18 shown in Table 2 were reacted in the same reactor as in Example 1. A polycarbonate polyol PCD-K having a number average molecular weight of 1965 having a hydroxyl value of 57.1 KOHmg / g was obtained.

(Comparative Example 13)
The number of hydroxyl values of 56.7 KOHmg / g was the same as in Example 1 except that 869 parts of CHDM and 594 parts of DEC-15 shown in Table 2 were reacted in the same reactor as in Example 1. A polycarbonate polyol PCD-L having an average molecular weight of 1979 was obtained.

(Comparative Example 14)
The number of hydroxyl values of 56.3 KOHmg / g was the same as in Example 1 except that 869 parts of CHDM and 594 parts of DEC-18 shown in Table 2 were reacted in the same reactor as in Example 1. A polycarbonate polyol PCD-M having an average molecular weight of 1993 was obtained.

(Comparative Example 15)
In the same manner as in Example 1, except that 1,9ND, 436 parts, 2MOD, 436 parts, and DEC-16 shown in Table 2 were reacted in the same reaction apparatus as in Example 1, were reacted in the same manner as in Example 1. A polycarbonate polyol PCD-N having a number average molecular weight of 2026 having a value of 55.4 KOHmg / g was obtained.

(Comparative Example 16)
In the same manner as in Example 1, except that 1,9ND was 436 parts, 2MOD was 436 parts, and DEC-19 shown in Table 2 was 583 parts in the same reaction apparatus as in Example 1, A polycarbonate polyol PCD-O having a number average molecular weight of 1976 having a value of 56.8 KOHmg / g was obtained.

(Comparative Example 17)
In the same reaction apparatus as in Example 1, except that 830 parts of 1,6HG and 587 parts of DMC-1 shown in the dehydration example of dimethyl carbonate were reacted, the hydroxyl value of 54 was obtained. A reactive stabilized polycarbonate polyol PCD-P having a number average molecular weight of 2044 of 9.9 KOH mg / g was obtained.

  Next, a reference example in which whether the variation in the water content in diethyl carbonate contributes to the urethanization reaction using the polycarbonate polyol obtained in each example and comparative example will be described.

(Reference Example 1)
100 parts of PCD-1 obtained in Examples and 300 parts of dimethylformamide were charged into a reactor equipped with a stirrer, thermometer, and cooling tube, and heated and bonded to 60 ° C. When the internal temperature reached 60 ° C., 12.3 parts corresponding to isocyanate group / hydroxyl molar ratio (R value) = 0.98 was added to diphenylmethane diisocyanate, and 2250 cm ⁻¹ ˜ The time until the NCO detection peak detected at 2270 cm ⁻¹ disappeared was measured. The time required for PCD-1 was 47 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Example 2)
The required time was measured in the same manner as in Reference Example 1 except that PCD-2 was used as the polycarbonate polyol. The required time was 49 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Example 3)
The required time was measured in the same manner as in Reference Example 1 except that PCD-3 was used as the polycarbonate polyol. The required time was 49 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Example 4)
The required time was measured in the same manner as in Reference Example 1 except that PCD-4 was used as the polycarbonate polyol. The required time was 51 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Example 5)
Polycarbonate polyols were prepared in the same manner as in Example 1 using diethyl carbonate having a water content of 15 ppm or less adjusted with tosyl isocyanate in the same manner as in the dehydration example of diethyl carbonate. Synthesized. The obtained polycarbonate polyols PCD-EX1 to 5 were measured for the required time in the same manner as in Reference Example 1, and were found to have stable reactivity with an average of 48.2 minutes and a standard deviation of 2 minutes.

(Reference Examples 6-17)
Polycarbonate polyols PCD-5 to 16 obtained in Examples 6 to 17 were evaluated in the same manner as in Reference Example 1 for reactivity (minutes) and molecular weight peaks around 1,000,000 in molecular weight. The evaluation results are shown in Table 3 as Reference Examples 6 to 17.

(Reference Comparative Example 1)
The required time was measured in the same manner as in Reference Example 1 except that PCD-A was used as the polycarbonate polyol. The required time was 62 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Comparative Example 2)
The required time was measured in the same manner as in Reference Example 1 except that PCD-B was used as the polycarbonate polyol. The required time was 45 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Comparative Example 3)
The required time was measured in the same manner as in Reference Example 1 except that PCD-C was used as the polycarbonate polyol. The required time was 38 minutes. Further, when the molecular weight was measured in terms of polystyrene using GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of a molecular weight of 1,000,000.

(Reference Comparative Example 4)
The required time was measured in the same manner as in Reference Example 1 except that PCD-D was used as the polycarbonate polyol. The required time was 21 minutes. Further, when the molecular weight was measured in terms of polystyrene by GPC manufactured by Tosoh Corporation, a high molecular weight peak was detected at 1% of the total area in the vicinity of a molecular weight of 1,000,000. The sample after the disappearance of the NCO peak was diluted with methyl ethyl ketone (MEK) and filtered through a 200 mesh filter to trap the gelled product.

(Reference Comparative Example 5)
The required time was measured in the same manner as in Reference Example 1 except that PCD-9 was used as the polycarbonate polyol. The required time was 16 minutes. Further, when the molecular weight was measured in terms of polystyrene by GPC manufactured by Tosoh Corporation, a high molecular weight peak was detected in the vicinity of 1 million in molecular weight of 4% of the total area. The sample after the disappearance of the NCO peak was diluted with MEK and filtered through a 200 mesh filter to trap the gelled product.

(Reference Comparative Example 6)
Polycarbonate polyols were synthesized in the same manner as in Example 1 using diethyl carbonate DEC-15 to 19 having different water contents shown in Table 2. The obtained polycarbonate polyols PCD-EX6 to 10 were measured for the required time in the same manner as in Reference Example 1. As a result, the average variation of 34 minutes and the standard deviation of 15 minutes were large.

(Reference Comparative Examples 7 to 17)
The polycarbonate polyols PCD-F to P obtained in Comparative Examples 7 to 17 were evaluated in the same manner as in Reference Example 1 for reactivity (minutes) and molecular weight peaks around 1 million molecular weight. The evaluation results are shown in Table 4 as Reference Comparative Examples 6 to 17.

  As can be seen from the above Reference Examples 1 to 5 and Reference Comparative Examples 1 to 17, it is clear that the variation in water content in diethyl carbonate, which is a carbonating agent, greatly contributes to the urethanization reaction. .

(Example 18)
Mix 717 parts of reaction stabilized polycarbonate polyol PCD-1 and 18.5 parts of 1,4-BD, add 231 parts of diphenylmethane diisocyanate I prepared at 60 ° C. after adjusting the liquid temperature to 70 ° C. The mixture was stirred and mixed at high speed until the temperature reached 100 ° C., and after the liquid temperature reached 100 ° C., it was cast into a vat and reacted at 80 ° C. for 12 hours. Next, this reaction product was pulverized and then pelletized by an extruder to obtain a thermoplastic polyurethane resin. When the molecular weight of the obtained thermoplastic polyurethane resin was measured in terms of polystyrene by GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of 1,000,000, the number average molecular weight was 55,000, and JIS A hardness. Was 85, and the tensile strength was 42 MPa.

  In order to verify the variation in product quality, samples (10 samples) of the thermoplastic polyurethane resin of Example 18 were further produced. When the molecular weight of these thermoplastic polyurethane resins was measured in terms of polystyrene by GPC manufactured by Tosoh Corporation, no high molecular weight peak was detected in the vicinity of 1 million from any sample. In addition, these samples have a number average molecular weight of 50,000 to 60,000 (average number average molecular weight 55,200, standard deviation 1,900), and a JIS A hardness of 84 to 86 (average 85.1, The physical properties were within a range of standard deviation 0.7) and tensile strength 40 MPa to 44 MPa (average value 41.7, standard deviation 1.2). Therefore, it can be seen that a thermoplastic polyurethane resin with very little quality variation was obtained.

  The present invention can be changed in design without departing from the scope of the claims, and is not limited to the above-described embodiments and examples.

Claims (2)

Reactivity stabilization including a step of reacting a glycol having 4 to 20 carbon atoms or an alicyclic or aliphatic linear or branched chain with one kind selected from dialkyl carbonate, diaryl carbonate, and alkylene carbonate A method for producing a polycarbonate polyol, comprising:
The dialkyl carbonate, the Jiariruka ball sulfonate, or the alkylene carbonate, a tosyl isocyanate were dehydrated, production method of the reactive stabilizing polycarbonate polyol, characterized in that the following water content 15 ppm. The method for producing a reactive stabilized polycarbonate polyol according to claim 1, further comprising a step of heat-embedding in the presence of a phosphate ester.