CN116710502A - Polycarbonate polyol, its production method and its composition - Google Patents

Abstract

A polycarbonate polyol, which has an ester bond and a urethane bond, and an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g. In addition, it relates to a method for producing the above-mentioned polycarbonate polyol, which uses a transesterification catalyst, at least one carbonate represented by formula (3), at least one diol represented by formula (4), and formula (5) The cyclic amides shown. Thus, there is provided a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of a polyurethane resin obtained from the polycarbonate polyol.

Description

Polycarbonate polyol, its production method and its composition

technical field

The present invention relates to polycarbonate polyols, methods for their manufacture and compositions thereof.

Background technique

Like polyester polyols and polyether polyols, polycarbonate polyols are useful as raw materials when reacting with polyisocyanate compounds to produce polyurethane resins, engineering plastics, adhesives, coatings, etc., and can also be used as Used as modifier for polyester resin etc.

For the modification of polycarbonate diol, the reaction of polycarbonate diol and lactone is known (for example, patent document 1). This product has fewer carbonate bonds than polycarbonate diol and has ester bonds.

In order to modify the characteristics of polycarbonate, the following examples are known: when polyhydric alcohol and dialkyl carbonate are reacted to synthesize polycarbonate, a urethane bond is introduced by reacting with a cyclic amide compound (such as , refer to Patent Document 2).

prior art literature

patent documents

Patent Document 1: International Publication No. 2014/069563

Patent Document 2: Specification of U.S. Patent Application Publication No. 2018/0251597

Contents of the invention

The problem to be solved by the invention

The polycarbonate diol of Patent Document 1 lacks solvent resistance at the time of urethanization, and therefore it is required to further improve solvent resistance.

In addition, since the molecular weight of the polycarbonate of patent document 2 is as high as 20,000 g/mol or more, a viscosity is high and handling is difficult. Furthermore, in the polycarbonate of Patent Document 2, the presence or absence of a molecular terminal structure capable of reacting with isocyanate, such as a hydroxyl group, is not clarified, and there is no mention of derivation to polyurethane as a polycarbonate diol.

An object of the present invention is to provide a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of a polyurethane resin obtained from the polycarbonate polyol.

means to solve the problem

Specifically, the present invention is as follows.

1. A polycarbonate polyol having an ester bond and a urethane bond, and having an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g.

2. The polycarbonate polyol according to the above 1, wherein the molar ratio of the urethane bond to the ester bond (urethane/ester) is 0.8 to 1.2.

3. The polycarbonate polyol according to the above 1 or 2, wherein the carbonate bond content is 3% by mass to 35% by mass based on the total amount of the polycarbonate polyol.

4. The polycarbonate polyol as described in any one of the above 1 to 3, wherein the content of the ester bond is 1.5% by mass to 15% by mass relative to the total amount of the polycarbonate polyol, and the content of the urethane bond is Content is 2 mass % - 20 mass % with respect to the polycarbonate polyol whole quantity.

5. The polycarbonate polyol according to any one of 1 to 4 above, wherein the content of the ester bond and the urethane bond represented by the following formula (I) is 10 mol % to 90 mol % .

(E+U)/(E+U+C)×100(I)

E: Number of moles of ester bonds in polycarbonate polyol

U: Number of moles of urethane bonds in polycarbonate polyol

C: Number of moles of carbonate bonds in polycarbonate polyol

6. The polycarbonate polyol according to any one of 1 to 5 above, which has a hydroxyl value of 25 mgKOH/g to 250 mgKOH/g.

7. The polycarbonate polyol according to any one of 1 to 6 above, which has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[chemical 1]

[Chem 2]

(In the formula, R ¹ and R ² represent a hydrocarbon group with 2 to 20 carbon atoms.)

8. The polycarbonate polyol according to the above 7, wherein in the above formula (1), R ¹ is a linear or branched alkylene group having 4 to 7 carbon atoms.

9. The polycarbonate polyol according to any one of 1 to 8 above, wherein the number average molecular weight is 400 g/mol to 4500 g/mol.

10. The polycarbonate polyol according to any one of 1 to 9 above, which is liquid at room temperature (25° C.).

11. A method for producing a polycarbonate polyol having an ester bond and a urethane bond and having an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g, wherein,

A transesterification catalyst, at least one carbonate ester represented by the following formula (3), at least one diol represented by the following formula (4), and a cyclic amide represented by the following formula (5) are used.

[Chem 3]

[chemical 4]

[chemical 5]

(In the formula, R ¹ and R ² represent a hydrocarbon group with 2 to 20 carbon atoms. In the formula, R ³ represents an alkyl group with 1 to 4 carbon atoms or an aryl group with 5 to 8 carbon atoms, and 2 in the same molecule Each R ³ may be the same or different, or two R ³ may form a ring together as an alkylene group with 1 to 4 carbon atoms.)

12. The method for producing a polycarbonate polyol according to 11 above, wherein the transesterification catalyst is a titanium compound and/or an alkali metal compound.

13. A polyurethane resin-forming composition comprising the polycarbonate polyol (A) and polyisocyanate (C) according to any one of 1 to 10 above.

14. A polyurethane resin having a structure derived from the polycarbonate polyol (A) and a structure derived from the polyisocyanate (C) according to any one of 1 to 10 above.

15. An aqueous polyurethane resin dispersion comprising the polyurethane resin described in 14 above.

16. A coating composition comprising the polyurethane resin described in 14 above.

17. A coating composition comprising the polyurethane resin described in 14 above.

18. An adhesive composition comprising the polyurethane resin described in 14 above.

19. A polyurethane resin film comprising the polyurethane resin described in 14 above.

20. A synthetic leather comprising the polyurethane resin described in 14 above.

21. A thermoplastic polyurethane comprising the polyurethane resin described in 14 above.

22. A thermosetting/cast polyurethane comprising the polyurethane resin described in 14 above.

The effect of the invention

According to the present invention, it is possible to provide a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of a polyurethane resin obtained from the polycarbonate polyol.

Detailed ways

[Polycarbonate polyol]

The polycarbonate polyol of the present invention has an ester bond and a urethane bond, and has an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g. Accordingly, it is possible to provide a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of a polyurethane resin obtained from the polycarbonate polyol. The polycarbonate polyol of the present invention is preferably a polycarbonate diol having hydroxyl groups at both molecular terminals.

It should be noted that "easy to handle" in the present invention means that at least any one of the following 1) and 2) is satisfied.

1) The viscosity at 75°C is 3000 cP or less. 2) It is liquid at room temperature (25°C).

Since handling is easy, polycarbonate polyols can be easily used as raw materials for polyurethane resins and the like.

＜Ester bond＞

The content of ester bonds is preferably 1.5% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and still more preferably 8% by mass or more, based on the total amount of the polycarbonate polyol. In addition, the content of ester bonds is preferably 15% by mass or less, more preferably 14% by mass or less, and still more preferably 12% by mass or less, based on the total amount of the polycarbonate polyol. The content of ester bonds is preferably 1.5% by mass to 15% by mass, more preferably 3% by mass to 14% by mass, and still more preferably 5% by mass to 12% by mass, based on the total amount of the polycarbonate polyol. By setting it as this range, handling is easy, and the polycarbonate polyol which can improve the mechanical performance of a polyurethane resin, and chemical resistance can be obtained.

＜Urethane bond＞

The urethane bond content is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 9% by mass or more, and still more preferably 13% by mass or more, based on the total amount of the polycarbonate polyol. In addition, the content of urethane bonds is preferably 20% by mass or less, more preferably 19% by mass or less, and still more preferably 16% by mass or less, based on the total amount of the polycarbonate polyol. The content of urethane bonds is preferably 2% by mass to 20% by mass, more preferably 4% by mass to 19% by mass, and still more preferably 9% by mass to 16% by mass, based on the total amount of the polycarbonate polyol. By setting it as this range, handling is easy, and the polycarbonate polyol which can improve the mechanical performance of a polyurethane resin, and chemical resistance can be obtained.

＜Carbonate bond＞

The content of carbonate bonds is preferably 3% by mass or more, more preferably 6% by mass or more, still more preferably 11% by mass or more, and still more preferably 14% by mass or more, based on the total amount of polycarbonate polyol. In addition, the carbonate bond content is preferably 35% by mass or less, more preferably 32% by mass or less, and still more preferably 23% by mass or less, based on the total amount of the polycarbonate polyol. The content of carbonate bonds is preferably 3% by mass to 35% by mass, more preferably 6% by mass to 32% by mass, and still more preferably 11% by mass to 23% by mass, based on the total amount of polycarbonate polyol. By setting it as this range, handling is easy, and the polycarbonate polyol which can improve the mechanical performance of a polyurethane resin, and chemical resistance can be obtained. The polycarbonate polyol of the present invention has an ester bond, a urethane bond, and a carbonate bond, and when the contents of each bond are within the above range, the general characteristics of polycarbonate can be fully exerted, and chemical resistance can be obtained. A polycarbonate polyol which is more excellent in drug properties and handleability is particularly preferable.

<Scale of each key>

The molar ratio (urethane/ester) of the said urethane bond and ester bond is preferably 0.8-1.2, More preferably, it is 0.9-1.1, More preferably, it is 0.95-1.05. By setting it as this range, the polycarbonate polyol which handles easily and can improve the mechanical performance of a polyurethane resin, and solvent resistance can be obtained.

Moreover, it is preferable that the content rate of the ester bond represented by following formula (I) and a urethane bond is 10 mol% - 90 mol%. By setting it as this range, the polycarbonate polyol which handles easily and can improve the mechanical performance of a polyurethane resin, and solvent resistance can be obtained.

(E+U)/(E+U+C)×100(I)

E: Number of moles of ester bonds in polycarbonate polyol

U: Number of moles of urethane bonds in polycarbonate polyol

C: Number of moles of carbonate bonds in polycarbonate polyol

<Measurement of content of ester bond, urethane bond and carbonate bond>

It is also possible to measure ¹ HNMR of the polycarbonate polyol, and quantify the contents of ester bonds, urethane bonds, and carbonate bonds contained in the polycarbonate polyol from integral values.

In addition, the contents of the ester bond, the urethane bond, and the carbonate bond contained in the polycarbonate polyol can also be calculated from the charged amount of the raw material of the polycarbonate polyol.

＜Acid value＞

In the polycarbonate polyol of the present invention, the acid value is 0.01 mgKOH/g to 5.0 mgKOH/g. If it is within this range, a polyurethane resin with particularly favorable physical properties can be obtained by using this as a raw material. The acid value is preferably 0.01KOH/g to 1.0 mgKOH/g, more preferably 0.01KOH/g to 0.5 mgKOH/g. By setting it as this range, the polycarbonate polyol which handles easily and can improve the mechanical performance of a polyurethane resin, and solvent resistance can be obtained.

In this specification, an acid value is the value measured based on the indicator titration method of JISK1557.

＜Hydroxy value＞

In the polycarbonate polyol of the present invention, the hydroxyl value may be 25 mgKOH/g to 250 mgKOH/g. If it is within this range, a polyurethane resin with particularly favorable physical properties can be obtained by using this as a raw material.

＜Repeating unit＞

The polycarbonate polyol preferably has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[chemical 6]

[chemical 7]

In the formula, R ¹ and R ² represent divalent hydrocarbon groups with 2 to 20 carbon atoms.

^R1 is preferably a straight-chain, branched or cyclic aliphatic hydrocarbon group with 4 to 8 carbon atoms or an aromatic hydrocarbon group with 8 to 12 carbon atoms, more preferably a straight chain with 4 to 8 carbon atoms , a branched or cyclic alkylene group, more preferably a linear or branched alkylene group having 4 to 7 carbon atoms, more preferably a linear alkylene group having 5 or 6 carbon atoms alkyl.

^R2 is preferably an aliphatic or aromatic hydrocarbon group having 5 to 12 carbon atoms, more preferably a linear or branched alkylene group having 6 to 12 carbon atoms, and even more preferably a straight chain or branched alkylene group having 6 carbon atoms. chained alkylene.

R ¹ and R ² may be various hydrocarbon groups as described above. For example, the above polycarbonate polyol may have a repeating unit in which R ¹ is an alkylene group having 5 carbon atoms, and a repeating unit in which R ¹ is an alkylene group having 6 carbon atoms.

By making ^R1 and ^R2 the above-mentioned divalent hydrocarbon groups, it is possible to obtain a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of polyurethane resins.

Examples of the above-mentioned hydrocarbon group include linear or branched alkylene groups having 2 to 20 carbon atoms, such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, Heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, Isononamethylene, 2-methylnonamethylene, etc.; substituted or unsubstituted cycloalkylenes with 3 to 20 carbon atoms, such as cyclopentylene, cyclohexylene, 1,2-dimethylene Cyclopentyl, 1,3-dimethylcyclopentyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-di Methylenecyclohexyl, 4,4'-methylenedicyclohexylene, 2,2-dicyclohexylenepropanyl, etc.; substituted or unsubstituted arylene groups with 6 to 20 carbon atoms, such as Phenylene, 1,2-dimethylenephenyl, 1,3-dimethylenephenyl, 1,4-dimethylenephenyl, naphthylene, 4,4'-methylenebis Repeating units such as phenylene and 2,2-diphenylenepropanyl.

＜Average molecular weight＞

In the polycarbonate polyol of the present invention, the number average molecular weight Mn is preferably 400 g/mol to 4500 g/mol. If it is this range, fluidity|fluidity (for example, viscosity 500cP - 10000cP) can be acquired easily under heating (for example, 75 degreeC), and it is excellent in handleability. The number average molecular weight Mn is more preferably 500 g/mol to 3500 g/mol, still more preferably 500 to 3000. In this specification, the number average molecular weight Mn is the number average molecular weight calculated based on the hydroxyl value measured based on JISK1577. Specifically, the hydroxyl value was measured and calculated using (56.1×1000×valence)/hydroxyl value (in this formula, the unit of hydroxyl value is [mgKOH/g]) by the terminal group quantification method. In the above formula, the valence number is the number of hydroxyl groups in one molecule.

In the polycarbonate polyol of the present invention, the weight average molecular weight Mw is preferably 500 g/mol to 30000 g/mol. The weight average molecular weight Mw is more preferably 1000 g/mol to 13000 g/mol. In this specification, the weight average molecular weight Mw is the value measured by GPC.

In the polycarbonate polyol of the present invention, the degree of dispersion Mw/Mn is preferably 1.0 to 3.0. The degree of dispersion Mw/Mn is preferably 2.0 to 2.3. If the degree of dispersion is greater than 3.0, the size of the hard segment and the soft segment in the obtained polyurethane may vary greatly, and the mechanical properties of the polyurethane may decrease.

＜Physical properties＞

The water content of the polycarbonate polyol of the present invention is preferably 1 ppm to 10000 ppm. If the water content exceeds 10000 ppm, the urea groups by-produced by the reaction of water and isocyanate increase during the synthesis of polyurethane, which may impair the flexibility of polyurethane.

The glass transition temperature of the polycarbonate polyol of the present invention is preferably -80°C to +50°C. If the glass transition temperature is lower than -80°C, the resulting polyurethane may have insufficient strength, and if higher than 50°C, it may become brittle near room temperature.

The viscosity of the polycarbonate polyol of the present invention is preferably 10 cP to 90,000 cP (75°C), more preferably 50 cP to 10,000 cP (75°C), and still more preferably 100 cP to 3,000 cP (75°C). When the viscosity is higher than 3,000 cP (75° C.), the handleability at the time of synthesizing polyurethane may be deteriorated.

In order to modify the properties of polycarbonate polyols, modification of raw material diols and modification of synthesized polycarbonate polyols are known. When a diol compound with a small number of carbon atoms is used as a raw material of polycarbonate polyol, the concentration of carbonate bonds in polycarbonate polyol increases, and the high cohesion of carbonate bonds improves the solvent resistance of polyurethane. On the other hand, it is known that a polycarbonate polyol composed of a structure derived from a diol with a small number of carbon atoms and a carbonate bond has a high viscosity. In the present invention, such a problem can also be solved by a polycarbonate polyol having an ester bond and a urethane bond and having a certain acid value.

[Manufacturing method]

The production method of the present invention is a production method of polycarbonate polyol, which is a production method of polycarbonate polyol having an ester bond and a urethane bond and an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g, wherein , using a transesterification catalyst, at least one carbonate ester represented by the following formula (3), at least one diol represented by the following formula (4), and a cyclic amide represented by the following formula (5).

Preferably, it is a method for producing polycarbonate polyols as follows: in the presence of a transesterification catalyst, at least one carbonate represented by the following formula (3) and at least one dicarbonate represented by the following formula (4) The alcohol is reacted, and the obtained product is reacted with a cyclic amide represented by the following formula (5). Alternatively, it is preferable to simultaneously react the carbonate ester represented by (3), at least one diol represented by the following formula (4), and the cyclic amide represented by the following formula (5).

[chemical 8]

[chemical 9]

[chemical 10]

In the formula, R ¹ and R ² have the same meaning as above.

In the formula, ^R3 represents an alkyl group with 1 to 4 carbon atoms, or an aryl group with 5 to 8 carbon atoms, and the two ^R3s in the same molecule can be the same or different, or the two ^R3s can be used together as carbon The alkylene group having 1 to 4 atoms forms a ring. R ³ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.

＜Diol＞

Examples of diols include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 - Linear chains with 2 to 2 carbon atoms such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. 20 diols of alkanes.

In addition, as other examples, 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl -1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl -1,3-propanediol, 2,2-dimethyl-1,3-propanediol and other branched diols of alkanes with 2 to 20 carbon atoms; 1,4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,7-nor Bornanediol and other diols with an alicyclic structure with 6 to 20 carbon atoms; 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 2,7- Diols having an aromatic ring structure having 6 to 20 carbon atoms, such as naphthalene dimethanol, and the like.

＜Carbonate＞

Examples of carbonates (hereinafter also referred to as carbonates) include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate; aromatic carbonates such as diphenyl carbonate; and cyclic carbonates such as ethylene carbonate. , from the viewpoint of easy removal of unnecessary by-products, preferably aliphatic carbonate or cyclic carbonate, particularly preferably dimethyl carbonate or ethylene carbonate.

＜Cyclic Amide＞

Examples of cyclic amides include aliphatic cyclic amides having 5 to 12 carbon atoms; 2-pyrrolidone, piperidone, N-methylpyrrolidone, ε-caprolactam, N-methylcaprolactam, laurolactam isocyclic amides, etc., preferably ε-caprolactam.

In addition, instead of the above-mentioned cyclic amide, a compound containing 5 to 12 aliphatic or aromatic hydrocarbon groups, amino groups, and carboxyl groups in the same molecule may be used.

＜Catalyst＞

In the case of producing the polycarbonate polyol of the present invention, a catalyst can be used. As the above-mentioned catalyst, those generally used as transesterification catalysts can be used. As the above-mentioned transesterification catalyst, for example, alkali metal compounds, alkaline earth metal compounds, aluminum compounds, zinc compounds, manganese compounds, nickel compounds, antimony compounds, zirconium compounds, titanium compounds, organotin compounds are preferable, and titanium compounds and/or alkali metal compounds are more preferable. compound. These catalysts may be used in combination.

Examples of alkali metal compounds include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal Carboxylates (lithium acetate, sodium acetate, potassium acetate, etc.), alkali metal alkoxides (lithium methoxide, sodium methoxide, potassium tert-butoxide, etc.), etc., as alkaline earth metal compounds, alkaline earth metal hydroxides (hydrogen magnesium oxide, etc.), alkaline earth metal alkoxides (magnesium methoxide, etc.), and the like.

Examples of the aluminum compound include aluminum alkoxides (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.), aluminum compounds such as aluminum acetylacetonate, and the like.

Examples of the zinc compound include zinc carboxylate (zinc acetate, etc.), zinc acetylacetonate, and the like.

Examples of manganese compounds include manganese carboxylates (manganese acetate, etc.), manganese acetylacetonate, and the like.

Examples of the nickel compound include nickel carboxylate (nickel acetate, etc.), nickel acetylacetonate, and the like.

Examples of antimony compounds include antimony carboxylates (antimony acetate, etc.), antimony alkoxides, and the like.

Examples of the zirconium compound include zirconium alkoxides (zirconium propoxide, zirconium butoxide, etc.), zirconium acetylacetonate, and the like.

Examples of titanium compounds include titanium alkoxides (titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, etc.), titanium acylate (tri butoxytitanium stearate, isopropoxystearate, etc.), titanium chelates (titanium diisopropoxybisacetylacetonate, titanium dihydroxy·bislactate, etc.), etc.

Examples of the organotin compound include dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, and the like.

It should be noted that each carboxylate is preferably a carboxylate with 2 to 30 carbon atoms, more preferably a carboxylate with 2 to 18 carbon atoms, and each alkoxide preferably has an alkoxy group with 1 to 30 carbon atoms. 30, more preferably an alkoxide having 2 to 18 carbon atoms.

Among the above catalysts, titanium compounds, organotin compounds, and alkali metal compounds are preferred, titanium compounds and/or alkali metal compounds are more preferred, titanium alkoxides, alkali metal hydroxides and/or alkali metal carbonates are further preferred. These catalysts may be used in combination.

Among titanium alkoxides, tetraalkoxytitanium such as tetraethoxytitanium, tetrapropoxytitanium, and tetrabutoxytitanium is more preferred, and tetrabutoxytitanium is still more preferred.

In addition, the said diol, carbonate, cyclic amide, and catalyst can be used individually by 1 type or in combination of 2 or more types.

<Method>

As a method for producing the polycarbonate polyol of the present invention, the following methods can be employed.

1. There is a diol compound represented by the formula (4), a cyclic amide represented by the formula (5), and a carbonate represented by the formula (3), which are produced by transesterification while extracting alcohol and the like. method.

2. After making the diol compound shown in formula (4) and the carbonate shown in formula (3) carry out transesterification reaction, add the cyclic amide shown in formula (5), and then add formula (4) The indicated diol compounds are reacted.

3. After polymerizing the cyclic amide shown in formula (5) and the diol compound shown in formula (4), add the diol compound shown in formula (4) and the carbonic acid ester shown in formula (3) to make the way it responds.

Wherein, from a kind of polycarbonate polyol obtained by transesterification reaction of diol compound represented by formula (4) and carbonate represented by formula (3) as a common raw material, by formula (5) The method shown in the above 2 is preferable from the viewpoint that a variety of products can be synthesized by changing the amount of the cyclic amide added.

The method for producing the polycarbonate polyol of the above-mentioned 2 will be described. This production method consists of two-stage reactions.

The first stage: the diol compound represented by the formula (4) and the carbonate represented by the formula (3) are subjected to a transesterification reaction.

The second stage: the cyclic amide represented by the formula (5) is added to the obtained reaction liquid, and the diol compound represented by the formula (4) is further added as needed to make it react.

(first stage response)

The diol compound represented by formula (4) and the carbonate represented by formula (3) are preferably subjected to transesterification reaction while distilling off alcohol or the like derived from the carbonate in the presence of a catalyst.

Although the reaction temperature varies depending on the type of diol compound and carbonate to be used, it is preferably 90°C to 230°C.

The pressure in the reaction system is not particularly limited, but it is preferably a reduced pressure of 30 mmHg to 500 mmHg. It should be noted that the reaction can be carried out under an atmosphere of air, carbon dioxide gas or an inert gas (nitrogen, argon, helium, etc.) or in a stream, preferably under an inert gas atmosphere or in an inert gas stream.

Moreover, when adding a catalyst, it is preferable that the addition amount of a catalyst is 1 ppm - 20000 ppm with respect to the total charging amount.

(Second Stage Response)

The polycarbonate polyol of the present invention is by adding the cyclic amide shown in formula (5) in the above-mentioned obtained product (polycarbonate polyol), and then adding the diol compound shown in formula (4) as required, according to It needs to be obtained by reacting while distilling off by-product alcohol etc.

The reaction temperature is preferably a condition under which the cyclic amide represented by the formula (5) does not distill off substantially, and is more preferably 90°C to 230°C.

The pressure in the reaction system of this reaction is not particularly limited, but it is preferably a reduced pressure of 30 mmHg to 500 mmHg. It should be noted that the reaction can be carried out under an atmosphere of air, carbon dioxide gas or an inert gas (nitrogen, argon, helium, etc.) or in a stream, preferably under an inert gas atmosphere or in an inert gas stream.

In addition, the above-mentioned catalyst may be newly added to the catalyst, or the catalyst used in the first-stage reaction may be used as it is. In addition, a compound containing 5 to 12 aliphatic or aromatic hydrocarbon groups, amino groups, and carboxyl groups in the same molecule may be used instead of the above-mentioned cyclic amide.

[Polyurethane resin-forming composition]

The above-mentioned polycarbonate polyol (A) is used as a raw material for forming a polyurethane resin, and therefore can be blended into a composition for forming a polyurethane resin. The polyurethane resin-forming composition of the present invention contains polycarbonate polyol (A) and polyisocyanate (C), preferably contains polycarbonate polyol (A), polyol (B) (wherein, the above-mentioned polycarbonate polyol (A)) and polyisocyanate (C).

The above polyurethane resin-forming composition has a one-component type and a two-component type.

The one-component type contains the polycarbonate polyol (A), polyol (B) and polyisocyanate (C) of the present invention.

In the polyurethane resin-forming composition, the polycarbonate polyol (A) relative to the total amount of polycarbonate polyol (A) and polyol (B) from the viewpoint of mechanical properties during urethanization The ratio of α is preferably more than 0 and 95% by mass or less, more preferably 1% by mass to 90% by mass, even more preferably 2% by mass to 85% by mass.

The two-component type is composed of a first liquid containing the above-mentioned polycarbonate polyol (A) and the above-mentioned polyol (B) and a second liquid containing a polyisocyanate (C), for example, they are composed of the first liquid and the second liquid kit sales.

Here, the polyol (B) is a polyol other than the above-mentioned polycarbonate polyol (A). As the polyol (B), for example, high-molecular-weight polyols and low-molecular-weight polyols can be used. From the viewpoint of ease of production, it is preferable to use high-molecular-weight diols and low-molecular-weight diols.

The high molecular weight diol is not particularly limited, and preferably has a number average molecular weight of 400 g/mol to 8000 g/mol. When the number average molecular weight is within this range, it is easy to obtain an appropriate viscosity and good handleability. It is easy to ensure the performance as a soft segment, and when the obtained composition containing a polyurethane resin is used to form a coating film, it is easy to suppress the generation of cracks, and furthermore, the reactivity with polyisocyanate (C) is sufficient, and it can also be effectively processed. Manufacture of polyurethane resins. The number average molecular weight of the polyol (B) is more preferably 400 g/mol to 4000 g/mol. In addition, the number average molecular weight is the value measured by the method described in an Example.

As a high molecular weight diol, polycarbonate polyol other than the said polycarbonate polyol (A), polyester polyol, polyether polyol etc. are mentioned, for example. From the viewpoint of light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the resulting polyurethane resin-containing composition and the coating film obtained therefrom, polycarbonate polyols other than the above-mentioned polycarbonate polyol (A) are preferred. of polycarbonate polyols.

Examples of low-molecular-weight diols include the same diols as those represented by the above formula (4), preferably 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol.

It does not specifically limit as polyisocyanate (C), For example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned.

As the aromatic polyisocyanate, specifically, 1,3-phenylene diisocyanate, 1,4-benzene diisocyanate, 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, 4, 4'-Diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4' -Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthalene diisocyanate, 4,4',4"-tri Phenylmethane triisocyanate, m-isocyanatobenzenesulfonyl isocyanate, p-isocyanatobenzenesulfonyl isocyanate, and the like.

Specific examples of aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11- Undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylhexanoate, bis(2-isocyanate ethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.

Specific examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylidene diisocyanate, methylcycloethylene Hexyl diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6- Norbornane diisocyanate, etc.

Polyisocyanate generally has two isocyanate groups per molecule, but triphenylmethane triisocyanate, isocyanurate derivatives, and the like can also be used as long as the polyurethane resin in the present invention does not gel. Polyisocyanates having 3 or more isocyanate groups.

A polyisocyanate may be used individually by 1 type, and may use it in combination of 2 or more types. The above composition for forming a polyurethane resin may contain a blocking agent, a wetting agent, a heat stabilizer, a light stabilizer, a plasticizer, an inorganic filler, a lubricant, a colorant, silicone oil, a foaming agent, and a flame retardant depending on the purpose. wait.

＜Polyurethane resin＞

The polyurethane resin-forming composition of the present invention contains polycarbonate polyol (A) and polyisocyanate (C), preferably contains polycarbonate polyol (A), polyol (B) (wherein, the above-mentioned polycarbonate polyol (A)) and polyisocyanate (C).

A polyurethane resin is obtained by at least reacting the polycarbonate polyol (A) and the polyisocyanate (C) described above. Therefore, the polyurethane resin of the present invention has a structure derived from polycarbonate polyol (A) and a structure derived from polyisocyanate (C), preferably has a structure derived from polycarbonate polyol (A), derived from polyol (B) ( However, the structure derived from the polycarbonate polyol (A)) mentioned above and the structure derived from a polyisocyanate (C) are not included.

During the reaction, a catalyst can also be used. The catalyst is not particularly limited, and examples thereof include salts of metals such as tin (tin) catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), lead catalysts (lead octoate, etc.) and organic and inorganic acids, and Organometallic derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, etc. Among them, dibutyltin dilaurate and dioctyltin dilaurate are preferable from the viewpoint of reactivity.

The reaction temperature during the reaction is not particularly limited, but is preferably 40°C to 120°C, more preferably 60°C to 100°C.

[use]

By using the polyurethane resin-forming composition, aqueous polyurethane resin dispersions, coating compositions, coating agent compositions, polyurethane resin films, adhesive compositions, synthetic leather, thermoplastic polyurethane (TPU), Heat curing · cast polyurethane (TSU). Namely, aqueous polyurethane resin dispersions, coating compositions, coating agent compositions, ink compositions, polyurethane resin films, adhesive compositions, synthetic leather, thermoplastic polyurethane (TPU), thermosetting and cast polyurethane (TSU) The above-mentioned polyurethane resin is included.

Example

Hereinafter, the content of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples. In addition, room temperature is 25 degreeC.

＜Measurement method＞

[acid value]

What dissolved 10 g of samples in the 50/50 (mass ratio) solution of toluene/ethanol was prepared, and it titrated with the 0.1N KOH ethanol solution. The acid value is obtained by the following formula: 5.61×(CB ¹ )×f/s. Here, B is the amount (mL) of the ^0.1N KOH ethanol standard solution required for neutralizing the blank control, and C is the amount (mL) of the 0.1N KOH ethanol standard solution required for neutralizing the sample, and f is Factor of 0.1N KOH ethanol standard solution, s is the mass (g) of the sample.

[Contents of ester bond, urethane bond and carbonate bond]

The contents of the ester bond, the urethane bond, and the carbonate bond contained in the polycarbonate polyol were calculated from the input amount of the raw material of the polycarbonate polyol.

[Viscosity of polycarbonate polyol]

Viscosity was measured by using LVDV II+Pro cone and Brookfield plate viscometer together with spindle cone model CPE-41 under the condition of melting at 75°C.

(Properties at room temperature)

Regarding the properties of the polycarbonate polyol at room temperature, the state of the sample heated at 80° C. for 3 hours was left to stand at 25° C. for 24 hours was visually confirmed. A state in which the solid was not visually seen but was not clouded was judged to be transparent.

Whether it is liquid or not is determined by heating the polycarbonate polyol at 80° C. for 3 hours, leaving it at 25° C. for 24 hours, and checking whether it is transparent and fluid at this time.

[Polyurethane Molecular Weight]

The polystyrene-equivalent molecular weight (number average molecular weight and weight average molecular weight) was measured by GPC under the following conditions.

Column: TSKgel HZ1000+Hz 3000 (manufactured by Tosoh) (40°C)

Mobile phase: THF, flow rate 0.6ml/min

Detector: RI (40°C)

[Hydroxy value]

According to JIS K 1557, it calculated|required by titration. Here, the unit of the hydroxyl value is mgKOH/g.

[Elastic modulus, stress at break and elongation at break]

According to ISO 527, it was carried out in an environment with a temperature of 23°C and a humidity of 50%. Specifically, elastic modulus, tensile strength, and elongation at break were measured for a test piece of a polyurethane resin film having a thickness of 0.05 mm to 0.10 mm at a width of 5 mm, a test length of 20 mm, and a test speed of 100 mm/min.

[Chemical Resistance Test]

Cotton impregnated with chemicals was placed on the polyurethane resin film obtained in each of Examples and Comparative Examples, and the lid was put on and left to stand at room temperature. After 24 hours, the polyurethane resin film was visually checked for any change, and evaluated according to the following criteria.

Excellent: no change

Good: Slightly whitened polyurethane resin film

Fair: Polyurethane resin film is obviously whitened

Poor: The color of the urethane resin film is white and the urethane resin film peels off

[Swelling test, dissolution resistance test]

The polyurethane resin film whose initial mass was measured was immersed in a solvent at 25° C. for 10 minutes, and after taking it out, the solvent was quickly wiped off to measure the mass after immersion. The swelling rate was evaluated by the following formula.

Swelling rate = 100 x (mass after immersion - initial mass) / initial mass (%)

The closer the swelling rate is to 0%, the better the solvent resistance is.

[Pendulum hardness]

Measurement was performed using the ISO 1522 Persoz pendulum method.

In this example, the abbreviations refer to the following compounds and the like.

TBT: Tetrabutoxytitanium

KOH: potassium hydroxide

NaOH: sodium hydroxide

K ₂ CO ₃ : potassium carbonate

LiOH: lithium hydroxide

(Example 1: Synthesis of polycarbonate polyol (1))

Polycarbonate diol (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200N) 170 g (hydroxyl value: 57.6 mgKOH/g), 1,6-hexanediol (manufactured by Ube Industries, Ltd.) 6.07 g, ε-caprolactam (manufactured by Ube Industries, Ltd.) 94.02g, and 0.4991g of tetrabutoxytitanium (manufactured by TCI) as a catalyst were mixed, and reacted at 190°C for 8 hours under normal pressure to obtain a solid at room temperature. Polycarbonate polyol (1).

In addition, by NMR, the peak of ε-caprolactam of a raw material disappeared, and the peak derived from the ester bond and a urethane bond newly appeared, and it confirmed that the target compound was obtained.

The hydroxyl value of the obtained polycarbonate polyol (1) was 64.5 mgKOH/g, and the acid value was 0.17 mgKOH/g.

(Example 2～11; Synthesis of polycarbonate polyol)

Except that the quality of the raw material, the type and amount of the catalyst, and the temperature and time of the reaction are changed as described in Table 1, the same method as in Example 1 is used to react to obtain a polycarbonate polycarbonate that is solid at room temperature. alcohol. The polycarbonate polyol obtained in Example 11 was liquid at room temperature.

In addition, for the polycarbonate polyol obtained in Example 11, ¹ H NMR was measured, and the contents of ester bonds, urethane bonds, and carbonate bonds contained in the polycarbonate polyol were respectively quantified from the integral values. As a result, ester The bond was 9.5 wt%, the urethane bond was 12.9 wt%, the carbonate bond was 17.5 wt%, and the molar ratio of the urethane bond to the ester bond (urethane/ester) was 1.0.

[Table 1]

(Example 12; Synthesis of single-liquid type polyurethane resin and film thereof)

30.0 g of polycarbonate polyol (1) synthesized in Example 1, 2.89 g of 1,4-butanediol (manufactured by Merck), 108.45 g of dimethylformamide (manufactured by Merck), dibutyltin dilaurate ( Merck) 0.023 g (500 ppm relative to the solid content) and 4,4'-diphenylmethane diisocyanate (Merck) 13.59 g (isocyanate group/hydroxyl = 0.99 (molar ratio)) were mixed and reacted at 80°C for 4 hours, a solution of polyurethane resin was obtained.

The obtained polyurethane resin solution (solid content: 30% by mass) was applied on a glass plate, dried at 60° C. for 1 hour and 120° C. for 4 hours, and peeled off from the glass plate to obtain a polyurethane resin film.

(Examples 13-15, Comparative Examples 1-3: Synthesis of one-component polyurethane resin and its film)

Except having changed the kind of polycarbonate polyol and the quality of a raw material as shown in Table 2, it reacted by the method similar to Example 12, and obtained the solution of a polyurethane resin.

The obtained polyurethane resin solution (solid content: 30% by mass) was applied on a glass plate, dried at 60° C. for 1 hour and 120° C. for 4 hours, and peeled off from the glass plate to obtain a polyurethane resin film.

Table 2 shows the evaluation results of the polyurethane resin films obtained in the respective Examples and Comparative Examples. Moreover, other evaluation results of the polyurethane resin film obtained in each Example are shown in Table 3.

[Table 2]

In the above table, the abbreviations represent the following compounds and the like.

HDL: 1,6-Hexanediol

PDL: 1,5-pentanediol

UH-200: (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200, polycarbonate diol made of HDL and dimethyl carbonate) number average molecular weight 2000g/mol viscosity 2300cP (75°C)

UH-200N: (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200N, polycarbonate diol made of HDL and dimethyl carbonate) number average molecular weight 2000g/mol viscosity 2300cP (75°C)

PH-200N: (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) PH-200N, polycarbonate diol made of HDL, PDL (HDL:PDL = 1:1 (molar ratio)) and dimethyl carbonate ) number average molecular weight 2000g/mol viscosity 2800cP (75 ℃)

UHC50-200: (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UHC50-200, polycarbonate diol produced from 1,6-hexanediol, dimethyl carbonate and caprolactone) number average molecular weight 2000g/ mol

PCLO-2000: (manufactured by Sigma-Aldrich, polycaprolactone diol) number average molecular weight 2000 g/mol

[table 3]

From the comparison of Examples 12 to 15 and Comparative Examples 1 to 3, it can be seen that by using polycarbonate polyols having ester bonds and urethane bonds, high modulus of elasticity, low swelling rate of hexane and toluene, That is, polyurethane with high solvent resistance.

From the comparison of Examples 12 to 15, it can be seen that by increasing the content of ester bonds and urethane bonds, polyurethane with a low swelling rate of toluene can be obtained.

As can be seen from the results in Table 3, the polyurethane obtained from the polycarbonate polyol of the present invention also exhibits practical effects in the breaking strength, elongation at breaking point, and chemical resistance tests.

Industrial Applicability

According to the present invention, it is possible to provide a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of a polyurethane resin obtained from the polycarbonate polyol.

Claims (22)

1. A polycarbonate polyol having an ester bond and a urethane bond, and having an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g. 2 . The polycarbonate polyol according to claim 1 , wherein the molar ratio of the urethane bond to the ester bond (urethane/ester) is 0.8 to 1.2. 3. The polycarbonate polyol according to claim 1 or 2, wherein the carbonate bond content is 3% by mass to 35% by mass based on the total amount of the polycarbonate polyol. 4. The polycarbonate polyol according to any one of claims 1 to 3, wherein the content of the ester bond is 1.5% by mass to 15% by mass relative to the polycarbonate polyol total amount, and the urethane bond The content of polycarbonate polyol is 2 mass % - 20 mass % with respect to the polycarbonate polyol whole quantity. 5. The polycarbonate polyol according to any one of claims 1 to 4, wherein the content of the ester bond and the urethane bond represented by the following formula (I) is 10 mol % to 90 mol %, (E+U)/(E+U+C)×100(I) In the formula, E is the number of moles of ester bonds in the polycarbonate polyol, U is the mole number of the urethane bond in the polycarbonate polyol, C is the number of moles of carbonate bonds in the polycarbonate polyol. 6. The polycarbonate polyol according to any one of claims 1 to 5, wherein the hydroxyl value is 25 mgKOH/g to 250 mgKOH/g. 7. The polycarbonate polyol according to any one of claims 1 to 6, which has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), [chemical 11] [chemical 12] In the formula, R ¹ and R ² represent a hydrocarbon group having 2 to 20 carbon atoms. 8. The polycarbonate polyol according to claim 7, wherein, in the above formula, R ¹ is a linear or branched alkylene group having 4 to 7 carbon atoms. 9. The polycarbonate polyol according to any one of claims 1 to 8, whose number average molecular weight is 400 g/mol to 4500 g/mol. 10. The polycarbonate polyol according to any one of claims 1 to 9, which is a liquid at a room temperature of 25°C. 11. A method for producing a polycarbonate polyol having an ester bond and a urethane bond and having an acid value of 0.01 mgKOH/g to 5.0 mgKOH/g, wherein, Using a transesterification catalyst, at least one carbonate represented by the following formula (3), at least one diol represented by the following formula (4), and a cyclic amide represented by the following formula (5), [chemical 13] [chemical 14] [chemical 15] In the formula, R ¹ and R ² represent a hydrocarbon group with 2 to 20 carbon atoms; in the formula, R ³ represents an alkyl group with 1 to 4 carbon atoms or an aryl group with 5 to 8 carbon atoms, two in the same molecule R ³ may be the same or different, or two R ³ may form a ring together as an alkylene group having 1 to 4 carbon atoms. 12. The method for producing polycarbonate polyol according to claim 11, wherein the transesterification catalyst is a titanium compound and/or an alkali metal compound. The composition for polyurethane resin formation containing polycarbonate polyol (A) and polyisocyanate (C) in any one of Claims 1-10. The polyurethane resin which has the structure derived from the polycarbonate polyol (A) in any one of Claims 1-10, and the structure derived from polyisocyanate (C). 15. An aqueous polyurethane resin dispersion comprising the polyurethane resin according to claim 14. 16. A coating composition comprising the polyurethane resin of claim 14. 17. A coating agent composition comprising the polyurethane resin according to claim 14. 18. An adhesive composition comprising the polyurethane resin according to claim 14. 19. A polyurethane resin film comprising the polyurethane resin according to claim 14. 20. A synthetic leather comprising the polyurethane resin according to claim 14. 21. A thermoplastic polyurethane comprising the polyurethane resin of claim 14. 22. A thermosetting/cast polyurethane comprising the polyurethane resin according to claim 14.