JP2010280770A - Polycarbonate polyol and manufacturing method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate polyol excellent in handleability. <P>SOLUTION: The polycarbonate polyol includes a diol residue originated from tricyclodecane dimethanol, and a diol residue originated from an aliphatic diol. The molar ratio of the diol residue originated from tricyclodecane dimethanol and the diol residue originated from an aliphatic diol is 80/20 to 20/80. The number-average molecular weight of the polycarbonate polyol is 540 to 1,600. The aliphatic diol is preferably a diol having a 4-7C straight-chain hydrocarbon as a main chain. In the molar ratio of the diol residue originated from tricyclodecane dimethanol and the diol residue originated from an aliphatic diol, one of the diol residues is preferably larger in number than the other diol residues. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polycarbonate polyol having at least a diol residue derived from tricyclodecane dimethanol and a diol residue derived from an aliphatic diol, and a method for producing the same.

Polycarbonate polyol is useful as a raw material for polycarbonate resin, polyurethane resin, and polyester resin. It is also widely used as a raw material for reactive coating agents.
Polyurethane resins and polyester resins using polycarbonate polyol as a raw material have high hydrolysis resistance compared to those using polyester polyol as a raw material, and weather resistance compared to those using polyether polyol as a raw material. It has high added value in the fields of resins and coating agents.

  It is known that a polycarbonate polyol using a chain aliphatic diol as a diol compound as a raw material of the polycarbonate polyol gives a relatively soft property to a polyurethane resin obtained by reacting with an isocyanate compound. On the other hand, it is known that a polycarbonate polyol using a diol having an alicyclic structure as a diol compound as a raw material for a polycarbonate polyol imparts heat resistance to a polyurethane resin obtained by reacting with an isocyanate compound.

In view of these, Patent Document 1 proposes a polycarbonate diol using tricyclodecane dimethanol as a raw material and a polycarbonate diol using tricyclodecane dimethanol and an aliphatic diol as raw materials.
However, since these polycarbonate diols become solid at 25 ° C., there are problems that they must be heated at the time of use, and a crushing step is required at the time of production.

JP 2006-31729 A

  An object of the present invention is to obtain a polycarbonate polyol which is liquid at 25 ° C. and has heat resistance and flexibility in order to improve handling at the time of use and to reduce the number of steps during production.

The present invention has been made to solve the above problems, and specifically has the following configuration.
(1) At least a tricyclodecane dimethanol residue derived from tricyclodecane dimethanol represented by the general formula (1) and an aliphatic diol residue in an average molar ratio of 80/20 to 20/80 And a polycarbonate polyol having a number average molecular weight of 540 to 1600.

(2) The polycarbonate polyol according to (1), wherein the aliphatic diol is a diol having a main chain of a linear hydrocarbon having 4 to 7 carbon atoms.
(3) In the molar ratio of the diol residue derived from tricyclodecane dimethanol and the diol residue derived from the aliphatic diol, one diol residue is larger than the other diol residue (1) or ( It is a polycarbonate polyol as described in 2).
(4) The method for producing a polycarbonate polyol according to the above (1) to (3), wherein at least tricyclodecane dimethanol represented by the general formula (1), an aliphatic diol, and a carbonate ester are subjected to a transesterification reaction.

  According to the polycarbonate polyol of the present invention, a polycarbonate polyol that is liquid at 25 ° C., can be improved in handling at the time of use, can be reduced in the number of steps during production, and has heat resistance and flexibility. be able to.

  The polycarbonate polyol of the present invention is a polycarbonate polyol having at least a diol residue derived from tricyclodecane dimethanol represented by the general formula (1) and a diol residue derived from an aliphatic diol, A polycarbonate polyol having a molar ratio of a diol residue derived from tricyclodecane dimethanol to a diol residue derived from the aliphatic diol of 80/20 to 20/80 and a number average molecular weight of 540 to 1600. is there.

(Tricyclodecane dimethanol residue)
The tricyclodecane dimethanol residue in the present invention is represented by the above general formula (1) and is represented by tricyclodecanediethanol represented by tricyclo [5.2.1.0 ^2,6 ] decandimethanol. This refers to the portion of each structural isomer of methanol or a mixture thereof excluding the hydrogen atoms of the two hydroxyl groups.

(Aliphatic diol residue)
Examples of the aliphatic diol residue in the present invention include a linear aliphatic diol residue, a branched aliphatic diol residue, an aliphatic diol residue having an alicyclic structure in the main chain, and an alicyclic structure in a side chain. And an aliphatic diol residue having an alicyclic structure such as an aliphatic diol residue having an alicyclic structure in the main chain and side chain. Only one of these aliphatic diol residues may be present in the polycarbonate polyol, or a plurality of these may be present in the polycarbonate polyol.
Moreover, the aliphatic diol residue in the present invention refers to a portion excluding hydrogen atoms of two hydroxyl groups of the aliphatic diol.

Examples of the linear aliphatic diol residue include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Diol residues based on 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like. Only one of these aliphatic diol residues may be present in the polycarbonate polyol, or a plurality of these may be present in the polycarbonate polyol.
Examples of the branched aliphatic diol residue include 1,3-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,6-diol, neopentyl glycol, and 2-methyl. Examples include diol residues based on -1,8-octanediol. Only one of these aliphatic diol residues may be present in the polycarbonate polyol, or a plurality of these may be present in the polycarbonate polyol.
Examples of the aliphatic diol residue having an alicyclic structure in the main chain include 1,2-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Diol residues based on 1,2-cyclohexanediethanol, 1,4-cyclohexanediethanol and the like. Only one of these aliphatic diol residues may be present in the polycarbonate polyol, or a plurality of these may be present in the polycarbonate polyol.

  As the aliphatic diol residue, a linear aliphatic diol residue is preferable because the viscosity of the obtained polycarbonate polyol tends to be low. Moreover, when the obtained polycarbonate polyol is used as a raw material for the urethane resin, among the straight-chain aliphatic diol residues, from the point that the high heat resistance and weather resistance of the urethane resin can be expressed. 7 linear aliphatic diol residues are more preferred.

(Polycarbonate polyol)
The polycarbonate polyol of the present invention is a polycarbonate polyol having an average molar ratio of tricyclodecane dimethanol residue and aliphatic diol residue of 80/20 to 20/80. The average molar ratio of tricyclodecane dimethanol residue and aliphatic diol residue is preferably 75/25 to 25/75.
The average ratio of the number of moles of tricyclodecane dimethanol residue (average ratio of the number of residues) to the total number of moles (total number) of tricyclodecane dimethanol residues and aliphatic diol residues is 20 to 80%. Yes, it is preferably 25 to 75%.
If the proportion of the tricyclodecane dimethanol residue is too small, the polycarbonate polyol having no tricyclodecane dimethanol residue is present in the obtained polycarbonate polyol, so that the glass transition point (Tg) is lowered. Thus, the hardness of the urethane resin or the like using the polycarbonate polyol becomes low. When the ratio of the tricyclodecane dimethanol residue is too large, the glass transition point (Tg) of the obtained polycarbonate polyol becomes too high or the viscosity becomes too high, resulting in poor handling of the polycarbonate polyol.

The polycarbonate polyol of the present invention may have other polyol residues in addition to the tricyclodecane dimethanol residue and the aliphatic diol residue.
Examples of the other polyol residues include polyvalent polyol residues and aromatic diol residues.

  The number average molecular weight of the polycarbonate polyol of the present invention is 540 to 1600. If the number average molecular weight is too small, the performance of the polycarbonate diol cannot be expressed for the use of a polymer raw material such as polyurethane, and if it is too large, the viscosity of the polycarbonate polyol becomes high and the handling becomes difficult. The number average molecular weight in the present invention is a number average molecular weight in terms of polystyrene.

  The hydroxyl value of the polycarbonate polyol of the present invention is preferably 40 to 200 mgKOH / g, and more preferably 50 to 130 mgKOH / g. If the hydroxyl value is too small or too large, the performance of polycarbonate diol may be difficult to express for the use of polymer raw materials such as polyurethane.

  The acid value of the polycarbonate polyol of the present invention is preferably 0.2 or less, and more preferably 0.1 or less. If the acid value of the polycarbonate polyol is too high, the storage stability of the polycarbonate polyol may deteriorate.

  The moisture contained in the polycarbonate polyol of the present invention is preferably 100 ppm or less. If the moisture is too much, the storage stability of the polycarbonate polyol may deteriorate.

  The glass transition point (Tg) of the polycarbonate polyol of the present invention is preferably −60 to 40 ° C., and more preferably −40 to 20 ° C. If the glass transition point is too low, the effect of heat resistance due to the introduction of the tricyclodecane dimethanol residue is reduced, and if it is too high, the viscosity of the polycarbonate polyol may be increased and it may be difficult to handle.

  The viscosity of the polycarbonate polyol of the present invention at 75 ° C. is preferably 500 to 80,000 cp, and more preferably 500 to 75,000 cp. When the said viscosity is too high, there exists a tendency for the viscosity of polycarbonate polyol to become high and to become difficult to handle.

The method for producing the polycarbonate polyol of the present invention is not particularly limited. For example, a method for producing by transesterification of tricyclodecane dimethanol, an aliphatic diol, a carbonate ester and an arbitrary polyol, a high molecular weight aliphatic polycarbonate. Examples include a method of producing by a transesterification reaction between a polyol and tricyclodecane dimethanol. In the transesterification reaction, a transesterification catalyst may be used as necessary.
Among the above production methods, tricyclodecane dimethanol, aliphatic diol, carbonate and any polyol are used from the viewpoint that tricyclodecane dimethanol residues can be dispersed as uniformly as possible in the polycarbonate polyol molecule. A production method in which a transesterification reaction is performed is preferable.

(Carbonate ester)
Although it does not restrict | limit especially as said carbonate ester, It is desirable to select suitably what can extract byproduct alcohol derived from carbonate ester efficiently. Examples thereof include dialkyl carbonate, diaryl carbonate, and alkylene carbonate.
The dialkyl carbonate is preferably a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include dimethyl carbonate and diethyl carbonate.
Examples of the diaryl carbonate include diphenyl carbonate.
As the alkylene carbonate, alkylene carbonate having an alkanediyl group having 2 to 4 carbon atoms is preferable, and specific examples include ethylene carbonate, propylene carbonate, butylene carbonate and the like. Among these, from the viewpoint of easy extraction of by-product alcohols, dialkyl carbonates having an alkyl group having 1 to 4 carbon atoms are preferred, and dimethyl carbonate is particularly preferred.

(Transesterification catalyst)
The transesterification catalyst is not particularly limited, and a catalyst used in a normal transesterification reaction can be used. Specific examples of the transesterification catalyst include alkali metal compounds, alkaline earth metal compounds, aluminum compounds, zinc compounds, manganese compounds, nickel compounds, antimony compounds, zirconium compounds, titanium compounds, and organic tin compounds.
Examples of the alkali metal compound include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), and alkali metal compounds. Examples thereof include carboxylates (lithium acetate, sodium acetate, potassium acetate, etc.), alkali metal alkoxides (lithium methoxide, netrium methoxide, potassium t-butoxide, etc.) and the like.
Examples of the alkaline earth metal compound include alkaline earth metal hydroxides (magnesium hydroxide and the like), alkaline earth metal alkoxides (magnesium methoxide and the like), and the like.

Examples of the aluminum compound include aluminum compounds such as aluminum alkoxide (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.), aluminum acetylacetonate, and the like.
Examples of the zinc compound include zinc carboxylates (such as zinc acetate) and zinc acetylacetonate. Examples of manganese compounds include manganese carboxylates (such as manganese acetate) and manganese acetylacetonate. Examples of the nickel compound include nickel carboxylates (such as nickel acetate) and nickel acetylacetonate.
Examples of the antimony compounds include antimony carboxylates (antimony acetate, etc.), antimony alkoxides, and the like. Examples of zirconium compounds include zirconium alkoxides (zirconium propoxide, zirconium butoxide, etc.), zirconium acetylacetonate, and the like. It is done.

Examples of the titanium compound include titanium alkoxide (titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, etc.), titanium acylate (tributoxy titanium stearate, isopropoxy systemate, etc.). ), Titanium chelates (diisopropoxytitanium bisacetylacetonate, dihydroxy bislactotitanium, etc.).
Examples of the organotin compound include dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, and the like.
Each carboxylate preferably has 2 to 30 carbon atoms, more preferably 2 to 18 carbon atoms, and each alkoxide preferably has 1 to 30 carbon atoms in the alkoxy group. 18 is more preferable.
In said catalyst, a titanium compound and an organotin compound are preferable, a titanium compound is more preferable, and a titanium alkoxide is still more preferable. Among the titanium alkoxides, titanium tetraethoxide, titanium tetrapropoxide, and titanium tetrabutoxide are more preferable, and titanium tetrabutoxide is particularly preferable.
In addition, said transesterification catalyst may be used independently and may use multiple types together.

  Next, the present invention will be specifically described with reference to examples and comparative examples. The APHA, hydroxyl value, and acid value of polycarbonate diol and polycarbonate diol copolymer were measured by a method based on JIS-K1557. The moisture was measured by a coulometric titration method using a Karl Fischer moisture meter. The melting point and glass transition temperature were measured by differential scanning calorimetry (measurement temperature range: −100 to 150 ° C.). The viscosity was measured with an E-type viscometer.

[Example 1]
In a 500 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introduction tube, 194.8 g (2.16 mol) of dimethyl carbonate, 101.3 g (0.52 mol) of tricyclodecane dimethanol, 1 , 6-hexanediol 183.0 g (1.55 mol) and titanium tetrabutoxide 0.03 g were charged, and the ester exchange reaction was carried out for 10 hours while distilling off the mixture of methanol and dimethyl carbonate under normal pressure and stirring. . During this time, the reaction temperature was gradually raised from 98 ° C. to 190 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.

  Thereafter, the pressure was gradually reduced to 50 mmHg, and a transesterification reaction was further carried out at 190 to 195 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 312 g of a polycarbonate diol copolymer. The resulting polycarbonate diol copolymer has a number average molecular weight of 617, APHA of 60, hydroxyl value of 181.8 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 36 ppm, glass transition point of -46 ° C, The viscosity was 515 cp / 75 ° C.

[Example 2]
In a 500 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introduction tube, 189.1 g (2.10 mol) of dimethyl carbonate, 99.1 g (0.50 mol) of tricyclodecane dimethanol, 1 , 4-Butanediol 139.5 g (1.51 mol) and titanium tetrabutoxide 0.03 g were charged, and a transesterification reaction was carried out for 10 hours while distilling off a mixture of methanol and dimethyl carbonate under normal pressure and stirring. . During this time, the reaction temperature was gradually raised from 98 ° C. to 170 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.

  Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further performed at 170 to 175 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 276 g of a polycarbonate diol copolymer. The transesterification reaction was performed in a nitrogen stream. The resulting polycarbonate diol copolymer has a number average molecular weight of 546, APHA of 50, hydroxyl value of 205.5 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 48 ppm, glass transition point of −43 ° C., The viscosity was 716 cp / 75 ° C.

[Example 3]
Dimethyl carbonate 212.4 g (2.36 mol), tricyclodecane dimethanol 91.1 g (0.46 mol), 1,6-hexanediol 164.6 g (1.39 mol), and titanium tetrabutoxide 0.03 g were charged. Except for the above, the same method as in Example 1 was used to obtain 320 g of a polycarbonate diol copolymer. To the obtained polycarbonate diol copolymer, 2.9 g (0.015 mol) of tricyclodecane dimethanol and 5.2 g (0.044 mol) of 1,6-hexanediol were further added, and transesterification was performed at 30 mmHg and 190 ° C. The reaction was conducted to obtain 328 g of a polycarbonate diol copolymer. The resulting polycarbonate diol copolymer has a number average molecular weight of 1480, APHA of 60, hydroxyl value of 75.8 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 52 ppm, glass transition point of −32 ° C., The viscosity was 4660 cp / 75 ° C.

[Example 4]
Dimethyl carbonate 171.8 g (1.91 mol), tricyclodecane dimethanol 164.9 g (0.84 mol), 1,6-hexanediol 99.3 g (0.84 mol), and titanium tetrabutoxide 0.03 g were charged. The procedure was the same as in Example 1, except that 310 g of a polycarbonate diol copolymer was obtained. The resulting polycarbonate diol copolymer has a number average molecular weight of 963, APHA of 80, hydroxyl value of 116.5 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 73 ppm, glass transition point of −14 ° C., The viscosity was 7042 cp / 75 ° C.

[Example 5]
Dimethyl carbonate 218.5 g (2.43 mol), tricyclodecane dimethanol 98.4 g (0.50 mol), 1,6-hexanediol 177.1 g (1.50 mol), and titanium tetrabutoxide 0.03 g were charged. Otherwise, the same procedure as in Example 1 was followed to obtain 322 g of a polycarbonate diol copolymer. The obtained polycarbonate diol copolymer has a number average molecular weight of 1590, APHA of 60, hydroxyl value of 70.6 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 45 ppm, glass transition point of −30 ° C., The viscosity was 8505 cp / 75 ° C.

[Example 6]
157.1 g (1.74 mol) of dimethyl carbonate, 222.6 g (1.13 mol) of tricyclodecane dimethanol, 44.7 g (0.38 mol) of 1,6-hexanediol, and 0.03 g of titanium tetrabutoxide were charged. The procedure was the same as in Example 1 except that 318 g of a polycarbonate diol copolymer was obtained. 9.7 g (0.049 mol) of tricyclodecane dimethanol and 2.0 g (0.017 mol) of 1,6-hexanediol were further added to the obtained polycarbonate diol copolymer, and the ester exchange was performed at 50 mmHg and 190 ° C. Reaction was performed to obtain 330 g of a polycarbonate diol copolymer. The resulting polycarbonate diol copolymer has a number average molecular weight of 1017, APHA of 80, hydroxyl value of 110.4 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 83 ppm, glass transition point of 12 ° C., viscosity Was 74045 cp / 75 ° C.

[Comparative Example 1]
179.7 g (1.99 mol) of dimethyl carbonate, 75.7 g (0.39 mol) of tricyclodecane dimethanol, 136.8 g (1.16 mol) of 1,6-hexanediol, and 0.03 g of titanium tetrabutoxide were charged. The procedure was the same as in Example 1, except that 262 g of a polycarbonate diol copolymer was obtained. To the obtained polycarbonate diol copolymer, 1.1 g (0.006 mol) of tricyclodecane dimethanol and 2.1 g (0.018 mol) of 1,6-hexanediol were further added, and transesterification was performed at 30 mmHg and 190 ° C. Reaction was performed to obtain 265 g of a polycarbonate diol copolymer. The resulting polycarbonate diol copolymer has a number average molecular weight of 2026, APHA of 60, hydroxyl value of 55.4 mgKOH / g, acid value of 0.03 mgKOH / g, moisture of 77 ppm, glass transition point of −28 ° C., The viscosity was 11288 cp / 75 ° C.

[Comparative Example 2]
173.7 g (1.93 mol) of dimethyl carbonate, 49.2 g (0.25 mol) of tricyclodecane dimethanol, 167.8 g (1.42 mol) of 1,6-hexanediol, and 0.03 g of titanium tetrabutoxide were charged. Except for the above, the same operation as in Example 1 was carried out to obtain 255 g of a polycarbonate diol copolymer. The resulting polycarbonate diol copolymer has a number average molecular weight of 1010, APHA of 50, hydroxyl value of 111.1 mgKOH / g, acid value of 0.02 mgKOH / g, moisture of 32 ppm, glass transition point of −52 ° C., The viscosity was 652 cp / 75 ° C.

[Comparative Example 3]
167.9 g (1.86 mol) of dimethyl carbonate, 257.7 g (1.31 mol) of tricyclodecane dimethanol, 27.4 g (0.23 mol) of 1,6-hexanediol, and 0.03 g of titanium tetrabutoxide were charged. Except for the above, the same procedure as in Example 1 was followed to obtain 323 g of a polycarbonate diol copolymer. The obtained polycarbonate diol copolymer has a number average molecular weight of 1620, APHA of 70, hydroxyl value of 69.3 mgKOH / g, acid value of 0.03 mgKOH / g, moisture of 88 ppm, glass transition point of 21 ° C., viscosity Was 173,000 or more and could not be measured.

[Comparative Example 4]
160.7 g (1.78 mol) of dimethyl carbonate, 209.2 g (1.07 mol) of tricyclodecane dimethanol, 27.2 g (0.23 mol) of 1,6-hexanediol, and 0.03 g of titanium tetrabutoxide were charged. The procedure was the same as in Example 1, except that 275 g of a polycarbonate diol copolymer was obtained. The resulting polycarbonate diol copolymer has a number average molecular weight of 1800, APHA of 60, hydroxyl value of 62.3 mgKOH / g, acid value of 0.03 mgKOH / g, moisture of 92 ppm, glass transition point of 19 ° C., viscosity Was 173,000 or more and could not be measured.

Claims (4)

The tricyclodecane dimethanol residue derived from at least tricyclodecane dimethanol represented by the general formula (1) and the aliphatic diol residue in an average molar ratio of 80/20 to 20/80 Polycarbonate polyol having an average molecular weight of 540 to 1600.

  The polycarbonate polyol according to claim 1, wherein the aliphatic diol is a diol having a main chain of a linear hydrocarbon having 4 to 7 carbon atoms.   The polycarbonate according to claim 1 or 2, wherein one diol residue is larger than the other diol residue in a molar ratio of a diol residue derived from tricyclodecane dimethanol and a diol residue derived from an aliphatic diol. Polyol.   The method for producing a polycarbonate polyol according to claim 1, wherein at least tricyclodecane dimethanol represented by the general formula (1), an aliphatic diol, and a carbonate ester are subjected to an ester exchange reaction.