JP4665449B2 - Diaminopolycarbonate and process for producing the same - Google Patents

Description

  The present invention relates to a diaminopolycarbonate having amino groups at both ends useful as a flexibility-imparting component for polymers such as polyimide, polyamide, polyamideimide, and polyetherimide, and a method for producing the same.

  As a polycarbonate having an amino group at the terminal, an aliphatic amino polycarbonate obtained by synthesizing an aliphatic nitropolycarbonate by ring-opening polymerization of a cyclic carbonate using nitroalcohol as a polymerization initiator and reducing the nitro group is known. (Non-Patent Document 1). However, since this amino polycarbonate is derived from ring-opening polymerization of a cyclic carbonate, an amino group is introduced only at one end and cannot be introduced as a flexibility-imparting component into the main chain of a polymer such as polyimide or polyamide. Is.

  On the other hand, an aromatic diamino polycarbonate having both amino groups as amino groups is also known (Patent Document 1). However, this cannot be used for applications where the glass transition temperature is as high as 150 ° C. and flexibility is required. Furthermore, the introduction ratio of the amino group to the terminal is only about 60%, and a polycarbonate having a high introduction ratio of the terminal amino group has not been obtained.

Macromolecules, 1997, 30, 6074-6076. Japanese Patent Laid-Open No. 2-107633

  The present invention provides a diaminopolycarbonate having an amino group at both ends having a low glass transition temperature and a high introduction ratio of amino groups at both ends to such an extent that it can be used for applications requiring flexibility, and a method for producing the same. The task is to do.

The problems of the present invention are solved by the following invention.
1. A diamino polycarbonate represented by the general formula (1). (In the formula, R ¹ represents a divalent aliphatic hydrocarbon group having 2 to 25 carbon atoms, R ² represents a divalent organic group having 2 to 25 carbon atoms, and n is a positive integer representing the degree of polymerization. A part of the carbon chain of the aliphatic hydrocarbon group may form a branched chain structure or a cyclic structure, and the carbon atom inside the carbon chain may be substituted with an oxygen atom.)

2. 2. The diamino polycarbonate according to 1 above, wherein the “—R ² — group” in the general formula (1) is an organic group represented by the general formula (2). (In the formula, R ³ represents a divalent organic group having 1 to 19 carbon atoms. The phenyl group portion of the organic group is bonded to the terminal amino group in the general formula (1).)

3. 3. The diamino polycarbonate according to 1 or 2 above, wherein the number average molecular weight is 500 to 20000.
4). 4. The diamino polycarbonate according to any one of 1 to 3 above, wherein the amino group introduction ratio at the terminal is 90% or more.
5. 2. The method for producing a diamino polycarbonate according to the above 1, wherein the nitro group of the dinitropolycarbonate represented by the general formula (3) is reduced. (Wherein R ¹ , R ² and n are the same as described above.)

6). The diamino polycarbonate according to the above item 5, wherein the dinitropolycarbonate is obtained by reacting a carbonate ester, an aliphatic dihydric alcohol and nitroalcohol, or obtained by reacting a polycarbonate diol and a nitro group-containing carbonate ester. A method for producing polycarbonate.
7). A dinitropolycarbonate represented by the general formula (3).

  By this invention, the diamino polycarbonate which can be usefully used as a softness | flexibility provision component of polymers, such as a polyimide, polyamide, polyamideimide, and polyetherimide, can be obtained. That is, the diamino polycarbonate of the present invention has a very high introduction ratio of amino groups at the terminals and a glass transition temperature that is low enough to be used for applications requiring flexibility. It can often give flexibility to the polymer. Furthermore, since the diamino polycarbonate of the present invention is obtained by reducing a dinitropolycarbonate obtained by reacting a carbonate ester, an aliphatic dihydric alcohol and a nitroalcohol, or reacting a polycarbonate diol and a nitro group-containing carbonate ester, Residual chlorine content is low, suitable for electronic materials, and does not adversely affect the environment.

The diamino polycarbonate of the present invention is represented by the above general formula (1), and its number average molecular weight is preferably about 500 to 20000, more preferably about 500 to 10,000 when used as a polymer softening component. When the number average molecular weight exceeds 20000, the reactivity when diamino polycarbonate is used as a flexibility-imparting component is lowered. That is, in the diamino polycarbonate of the present invention, the repeating unit is —CO—O—R ¹ —O—, both ends are amino groups, and the number average molecular weight is preferably within the above range. The repeating unit is —CO—O—R ¹ —O—, and the terminal group bonded to the terminal part on the carbonyl group side of the repeating unit is an H ₂ N—R ² —O— group, and the other ether group The terminal group bonded to the terminal portion on the side is a —CO—O—R ² —NH ₂ group, and the number average molecular weight is preferably within the above range. The diamino polycarbonate of the present invention has a very high amino group introduction ratio (amination fraction) of 90% or more, further 95% or more. In the general formula (1), n is a positive integer representing the degree of polymerization and is a numerical value satisfying the number average molecular weight.

In the general formula (I), R ¹ is a divalent aliphatic hydrocarbon group having 2 to 25 (preferably 3 to 20) carbon atoms, and a part of the carbon chain of the aliphatic hydrocarbon group is a branched chain structure. Alternatively, a cyclic structure may be formed, and carbon atoms in the carbon chain may be substituted with oxygen atoms. Specific examples of the divalent aliphatic hydrocarbon group include an alkylene group having 2 to 25 (preferably 3 to 20) carbon atoms. For example, an aliphatic group represented by the following general formula (4): A residue of a dihydric alcohol (corresponding to R ¹ ) is preferably mentioned. In the general formula (4), R ¹ is the same as in the general formula (1).

R ¹ is a trimethylene group: 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2 -Butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-heptanediol, etc. Residues.

-R ¹ is a tetramethylene group: a residue such as 1,4-butanediol.
-R ¹ is a pentamethylene group: residues such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol and the like.
-R ¹ is a hexamethylene group: residues such as 1,6-hexanediol and 2-ethyl-1,6-hexanediol.

-R ¹ is a heptamethylene group: a residue such as 1,7-heptanediol.
-Those in which R ¹ is an octamethylene group: residues such as 1,8-octanediol and 2-methyl-1,8-octanediol.
-R ¹ is a nonamethylene group: a residue such as 1,9-nonanediol.

-R ¹ is a decamethylene group: a residue such as 1,10-decanediol.
-R ¹ is an undecamethylene group: a residue such as 1,11-undecanediol.
-R ¹ is a dodecamethylene group: a residue such as 1,12-dodecanediol.
-R ¹ is an eicosamethylene group: a residue such as 1,20-eicosandiol.

A part of the carbon chain of R ¹ forms a cyclic structure: 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, cyclohexane-1,4-diethanol , 2,2-bis (4-hydroxycyclohexyl) propane, 2,7-norbornanediol and the like.

A carbon atom inside R ^{1 having} a carbon atom substituted with an oxygen atom: residues such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
A part of the carbon chain of R ¹ forms a cyclic structure, and the carbon atom inside the carbon chain is substituted with an oxygen atom: 2,5-tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane Etc. residues.

In the general formula (1), R ² is a divalent organic group having 2 to 25 carbon atoms (preferably 3 to 20 carbon atoms), and the divalent organic group has 2 to 25 carbon atoms (preferably 3 to 20 carbon atoms). And a divalent aromatic hydrocarbon group having 6 to 25 carbon atoms (preferably 6 to 20 carbon atoms). The number of carbon atoms in the case of an aromatic hydrocarbon group indicates the total number of carbon atoms including the substituent on the aromatic ring, and the carbon chain of this substituent may form a branched chain structure or a cyclic structure. The carbon atom in the carbon chain may be substituted with an oxygen atom.

  Among the divalent organic groups, examples of the divalent aliphatic hydrocarbon group having 2 to 25 carbon atoms include alkylene groups such as ethylene group, trimethylene group, and tetramethylene group. The carbon chain of the aliphatic hydrocarbon group may form not only a linear structure but also a branched chain structure or a cyclic structure, and carbon atoms inside these carbon chains may be substituted with oxygen atoms. Examples of the divalent aromatic hydrocarbon group having 6 to 25 carbon atoms include a phenylene group, a xylylene group, an alkyl-substituted phenylene group (such as a methylphenylene group), and an organic group represented by the general formula (2). It is done.

  Among the divalent organic groups, a diamino polycarbonate in which the terminal amino group is an aromatic amino group in the general formula (1) can be obtained, and a phenylene group or an organic group represented by the general formula (2) is preferable. Of these, the organic group represented by the latter general formula (2) is particularly preferred.

In the general formula (2), R ³ is a divalent organic group having 1 to 19 (preferably 1 to 5) carbon atoms, and a divalent aliphatic carbonization having 1 to 19 (preferably 1 to 5) carbon atoms. Preferable examples include a hydrogen group and a divalent aromatic hydrocarbon group having 6 to 19 (preferably 6 to 8) carbon atoms. Examples of the former include alkylene groups such as ethylene group, trimethylene group and tetramethylene group, but the carbon chain of the divalent aliphatic hydrocarbon group has not only a straight chain structure but also a branched chain structure or a cyclic structure. They may be formed, and the carbon atoms in these carbon chains may be substituted with oxygen atoms. Examples of the latter include phenylene group, tolylene group, xylylene group and the like. In addition, the phenyl group part of General formula (2) couple | bonds with a terminal amino group in General formula (1).

The R ^2, used in the preparation of diamino polycarbonate to be described later, the general formula (5) of the nitro alcohol represented by residues (corresponding to R ²⁾ are mentioned specifically. In the general formula (5), R ² is the same as in the general formula (1).

For example, nitroalcohol residues in which R ² is a divalent aliphatic hydrocarbon group such as 2-nitroethanol, 3-nitropropanol, 4-nitrobutanol, nitrophenol, nitrobenzyl alcohol, nitrophenethyl alcohol, etc. Specific examples include nitroalcohol residues in which R ² is a divalent aromatic hydrocarbon group. The nitroalcohol residue is preferably a nitrophenyl alcohol having a nitrophenyl group, particularly a (nitrophenyl) alkyl alcohol residue.

The diamino polycarbonate of the present invention is preferably produced by obtaining a dinitropolycarbonate represented by the general formula (3) in advance and reducing the terminal nitro group to an amino group. In this way, a diamino polycarbonate having a high amino group at both ends can be obtained. The number average molecular weight of dinitropolycarbonate is preferably about 500 to 20000, more preferably about 500 to 10,000 when diaminopolycarbonate is used as a component for imparting flexibility to a polymer. That is, in this dinitropolycarbonate, the repeating unit is —CO—O—R ¹ —O—, both ends are nitro groups, and the number average molecular weight is preferably within the above range. The unit is —CO—O—R ¹ —O—, and the terminal group bonded to the terminal part on the carbonyl group side of the repeating unit is the O ₂ N—R ² —O— group, and the other ether group side The terminal group bonded to the terminal part is a —CO—O—R ² —NO ₂ group, and the number average molecular weight is preferably within the above range.

  The reaction for reducing the nitro group of the dinitropolycarbonate to an amino group can be suitably carried out by contacting the dinitropolycarbonate with hydrogen in the presence of a reduction catalyst. In addition, dinitropolycarbonate can be produced by reducing nitro group to amino group by reacting dinitropolycarbonate with metal hydride complex compounds (lithium aluminum hydride, sodium aluminum hydride, sodium borohydride, etc.) or Benkeser reduction reaction. can do.

The reduction catalyst is not particularly limited as long as it is a compound that catalyzes the reduction of a nitro group to an amino group, and a metal such as aluminum, tin, iron, nickel, cobalt, chromium, palladium, platinum, or a compound thereof is used. be able to. When both ends of dinitropolycarbonate are nitroalkyl (for example, R ² is a divalent aliphatic hydrocarbon group), palladium carbon, Raney nickel, iron, pentacyanocobalt (II) complex, carbonyl chromium complex In the case where platinum oxide or the like is suitable as a reduction catalyst and both ends are nitrophenyl (for example, R ² is an organic group represented by the general formula (2)), palladium carbon, Raney nickel, aluminum Tin, iron, nickel, tin chloride, platinum, platinum oxide and the like are suitable as the reduction catalyst.

  The amount of the reduction catalyst used varies depending on the dinitropolycarbonate species, the catalyst species, the reaction conditions, etc., but is about 0.00001 to 0.1 times mol, especially about 0.001 to 0.01 times mol for 1 mol of dinitropolycarbonate. Preferably there is. A single catalyst or a plurality of catalysts can be used.

The reduction reaction is usually carried out in the presence of a reduction catalyst, at normal pressure or under pressure, in a hydrogen atmosphere or in a hydrogen stream, usually in the presence of a solvent. At this time, it is preferable that reaction temperature is a temperature which a raw material and a solvent do not vaporize, for example, may be 0-200 degreeC, Preferably it may be the range of 0-100 degreeC. The hydrogen pressure may be in a range from normal pressure to about 50 kg / cm ² -G (about 5 MPa-G). After completion of the reaction, the target diaminopolycarbonate can be obtained by removing the catalyst by filtration or centrifugation, and then removing the solvent by distillation or the like.

  As the solvent, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate are suitable. These solvents (first solvent) A solvent (second solvent) that dissolves polycarbonates such as ethers such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons such as hexane, toluene and xylene, and aprotic polar solvents such as dimethylformamide; It is more preferable to use a mixed solvent of The amount of the solvent used may be about 5 to 50 ml of the first solvent with respect to 1 g of dinitropolycarbonate, and the second solvent may be added to the extent that the dinitropolycarbonate is dissolved therein.

The dinitropolycarbonate used for the production of diaminopolycarbonate is preferably produced by the following method in order to increase the introduction ratio of the amino group to the terminal.
[Method 1] Reaction of carbonate ester, aliphatic dihydric alcohol represented by general formula (4) and nitroalcohol represented by general formula (5).
[Method 2] Reaction of a polycarbonate diol represented by the following general formula (6) and a nitro group-containing carbonate represented by the following general formula (7).

In general formulas (6) and (7), R ¹ is the same as in general formula (1). R ⁴ represents a hydrocarbon group having 1 to 15 carbon atoms (preferably 1 to 6), n-1 represents the degree of polymerization of polycarbonate carbonate, and n is the same as described above.

  Method 1 can be performed according to a known method. For example, in the reaction (transesterification reaction) in Method 1, in the presence of a transesterification catalyst, aliphatic dihydric alcohol and nitro alcohol are reacted with carbonate ester while extracting by-produced aliphatic or aromatic alcohol out of the system. Can be done.

  In Method 1, examples of the carbonic acid ester include aliphatic or aromatic carbonic acid esters such as dialkyl carbonate, diaryl carbonate, alkylene carbonate, and alkylaryl carbonate, and a plurality of them may be used in combination. Specific examples include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methylphenyl carbonate, ethylene carbonate, propylene carbonate, and the like.

  The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, metal compounds such as zinc, titanium, tin, aluminum, copper, nickel, iron, etc., proton acids such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, cationic ion exchange resin, potassium carbonate, carbonic acid Examples thereof include inorganic bases such as sodium, potassium hydroxide and sodium hydroxide, and organic bases such as sodium methoxide, sodium ethoxide and potassium t-butoxide.

  Examples of the metal compound include organic acid salts or inorganic acid salts of zinc such as zinc acetate and zinc chloride, and alkoxy having 4 to 40 carbon atoms such as tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and tetraphenoxy titanium. Having an alkyl group having 2 to 40 carbon atoms such as dibutyltin oxide, diphenyltin oxide, dibutyltin acetate, dibutyltin laurate and tin 2-ethylhexanoate, an aryl group, or an acyloxy group Organotin compounds, organoaluminum compounds having a C3-C30 alkoxy group such as triisopropoxyaluminum, inorganic or organic acid salts of copper such as cupric chloride and copper acetate, nickel chloride, acetic acid Nickel inorganic or organic acid salts such as nickel, Such as an inorganic acid salt of iron such as ferric chloride. Among these transesterification catalysts, organic acid salts of zinc, organic titanium compounds, organic tin compounds, and organic aluminum compounds are preferable.

  The conditions for the transesterification reaction in Method 1 are not particularly limited as long as a dinitropolycarbonate can be produced. For example, using a reaction vessel that can be used under reduced pressure, the above-mentioned aliphatic dihydric alcohol, nitroalcohol, carbonate ester The transesterification catalyst is mixed, and the temperature is 20 to 150 ° C. under a nitrogen stream for about 0.5 to 10 hours, and then gradually heated, and at the same time increasing the degree of vacuum, 110 ° C. to 250 ° C., particularly 140 ° C. to What is necessary is just to make it reduce to 3-20 mmHg at 240 degreeC, and to make it react for about 0.5 to 24 hours.

  In the transesterification reaction, the amount of aliphatic dihydric alcohol and nitroalcohol used is not particularly limited as long as dinitrocarbonate can be produced, but carbonic acid is used so that both ends of the obtained polycarbonate are substantially nitro groups. Aliphatic dihydric alcohol 0.8-3 times mole, nitroalcohol 0.001-2 times mole, and aliphatic dihydric alcohol 0.9-1.5 times mole, nitroalcohol 0.001 with respect to ester. It is preferable that it is about -0.5 times mole. The amount of the catalyst used varies depending on the catalyst type, reaction conditions, and the like, but the catalyst is preferably in a ratio of 0.00001 to 0.3 mol, particularly 0.001 to 0.1 mol, with respect to 1 mol of the carbonic ester. A single catalyst or a plurality of catalysts can be used.

According to the method 2, the aliphatic or aromatic alcohol (alcohol having R ⁴ as a residue) and an aliphatic dihydric alcohol that are by-produced in the presence of a transesterification catalyst are removed from the system in the presence of a transesterification catalyst. While removing, polycarbonate diol and nitro group-containing carbonate can be reacted. For example, under a nitrogen stream at about 20 to 150 ° C. for about 0.5 to 10 hours, then gradually heating and simultaneously increasing the degree of vacuum while reducing the pressure to 110 to 250 ° C., particularly 140 to 240 ° C. and 3 to 20 mmHg. The reaction can be carried out for about 0.5 to 24 hours.

  In the reaction (transesterification reaction) in Method 2, the amount of polycarbonate diol and nitroalcohol used is not particularly limited as long as dinitrocarbonate can be produced, but the both ends of the obtained polycarbonate are substantially nitro groups. The amount of nitroalcohol is preferably 0.5 to 60 mol, more preferably 1.5 to 30 mol, relative to 1 mol of polycarbonate. The type and amount used of the transesterification catalyst are the same as in Method 1.

  In addition, as the polycarbonate diol represented by the general formula (6), a commercially available product can be suitably used. When diamino polycarbonate is used as a component for imparting flexibility to a polymer, the number average molecular weight of the polycarbonate diol is preferably about 500 to 10,000. Further, the nitro group-containing carbonate represented by the general formula (7) includes the nitro alcohol and the chloro carbonate represented by the general formula (5) (methyl chlorocarbonate, ethyl chlorocarbonate, butyl chlorocarbonate, phenyl chlorocarbonate). Etc.) or a carbonate ester (dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, etc.).

  When reacting nitroalcohol with chlorocarbonic acid ester, 1 to 2 moles of tertiary amines such as triethylamine are dissolved in halogenated hydrocarbon solvent (dichloroethane etc.) or ether solvent (diethyl ether etc.) per 1 mole of nitroalcohol. Then, it is cooled to a temperature of −5 to 5 ° C. in a nitrogen stream, and 1 to 2 mol of chlorocarbonate is dropped and reacted to suitably produce a nitro group-containing carbonate. After completion of the reaction, washing with dilute hydrochloric acid, washing with water (several times) and evaporation of the solvent yield the desired product, and if necessary, recrystallization may be performed with alcohols (methanol, ethanol, etc.).

  Next, the present invention will be specifically described with reference to examples and comparative examples. The evaluation methods are as follows.

1) ¹ H-NMR spectrum: A sample was dissolved in deuterated chloroform and measured using a nuclear magnetic spectrometer (AL-300 manufactured by JEOL Ltd.).
2) Infrared absorption spectrum: Measured by KBr tablet method using Fourier transform infrared absorption spectrometer (MAGNA-IR manufactured by Nicolet).

3) Amine equivalent: Diamino polycarbonate was dissolved in benzyl alcohol or a mixed solvent of benzyl alcohol and THF and titrated with 0.05N hydrochloric acid ethanol solution using phenolphthalein as an indicator.

4) Amination fraction: The introduction ratio of amino groups to the terminal (amination fraction) was determined from the ¹ H-NMR spectrum according to the following formula.
Amination fraction (α) = S1 / (S1 + S2 + S3 + S4)

S1, S2, S3, and S4 are as follows.
S1 (amino terminal amount): a value obtained by dividing the integrated intensity attributed to the 3- and 5-position protons of the 4-aminophenethyl group appearing in the vicinity of 6.5 to 6.7 ppm by 4 which is the number of protons.
S2 (nitro end amount): a value obtained by dividing the integrated intensity attributed to the 3- and 5-position protons of the 4-nitrophenethyl group appearing in the vicinity of 8.2 to 8.0 ppm by 4 which is the number of protons.
S3 (hydroxyl terminal amount): a value obtained by dividing the integral intensity attributed to methylene protons of hydroxymethylene appearing in the vicinity of 3.8 to 4.0 ppm by 4 which is the number of protons.
S4 (phenyl end amount): a value obtained by dividing the integral intensity attributed to the phenyl proton of the phenyl carbonate group appearing in the vicinity of 7.3 to 7.5 ppm by 10 which is the number of protons.

5) Number average molecular weight: Determined by ¹ H-NMR spectrum.
6) Glass transition temperature (Tg): Measured using a differential scanning calorimeter DSC (Diamond DSC manufactured by PerkinElmer) in a helium atmosphere at a heating rate of 10 ° C./min.

[Example 1]
In a glass reaction container having an internal volume of 300 ml, 6.67 g (0.04 mol) of 4-nitrophenethyl alcohol, 14.77 g (0.125 mol) of 1,6-hexanediol, 31.06 g (0.145 mol) of diphenyl carbonate, Zinc acetate 0.26g was added, and it stirred at 120 degreeC under nitrogen for 2 hours. Subsequently, the pressure was reduced to 10 mmHg, and the mixture was stirred at 180 ° C. for 2 hours and 200 ° C. for 2 hours while removing phenol, and then cooled to room temperature to obtain an oily dinitropolycarbonate (di-4-nitrophenethylpolycarbonate). The infrared absorption spectrum of this dinitropolycarbonate is shown in FIG. 1, and the ¹ H-NMR spectrum is shown in FIG. The number average molecular weight was 1400.

  27.8 g of the obtained dinitropolycarbonate, 200 ml of tetrahydrofuran, 200 ml of methanol, and 0.28 g of palladium activated carbon are added to a glass reaction vessel with an internal volume of 1 L, and the mixture is stirred for 18 hours at 25 ° C. in a hydrogen atmosphere (normal pressure). did. After the catalyst was filtered off, the solvent was distilled off to obtain 26.5 g of a waxy diamino polycarbonate (di-4-aminophenethyl polycarbonate).

From the infrared spectrum of this diamino polycarbonate (FIG. 3), the peak derived from the symmetrical stretching vibration of the nitro group (near 1340 cm ⁻¹ ) has disappeared, and the reduction reaction from the nitro group to the amino group has proceeded sufficiently. confirmed. From ¹ H-NMR spectrum (FIG. 4), S1 = 3.99 / 4 = 0.998, S2 = 0, S3 = 0.09 / 4 = 0.023, S4 = 0.31 / 10 = 0. The amination fraction (α) was 0.949, which was high. The amine equivalent was 618, the number average molecular weight was 1300, and the glass transition temperature was -37 ° C.

[Reference Example 1] Production of 4-nitrophenethyl phenyl carbonate In a 1 L glass reaction vessel, 50.7 g (0.30 mol) of 4-nitrophenethyl alcohol, 42.7 ml (0.30 mol) of triethylamine, 500 ml of dehydrated dichloroethane And stirred while cooling in an ice bath under a nitrogen stream. To this, 57.0 ml (0.45 mol) of phenyl chloroformate was added dropwise over 0.5 hour, followed by stirring for 1 hour and further stirring at room temperature for 4 hours. The obtained reaction solution was washed with dilute hydrochloric acid and distilled water, the solvent was distilled off, and then recrystallized with methanol to obtain 45.0 g of 4-nitrophenethylphenyl carbonate (yield 51%). The ¹ H-NMR spectrum of this compound is shown in FIG.

[Example 2]
In a glass reaction vessel having an internal volume of 300 ml, polycarbonate diol 30.0 g (29.9 mol; UH-CARB100 manufactured by Ube Industries), 17.2 g (59.8 mol) of 4-nitrophenethylphenyl carbonate obtained in Reference Example 1, Zinc acetate 150 mg (0.027 mol) was added, and the mixture was stirred at 150 ° C. for 2 hours under nitrogen. Subsequently, the pressure was reduced to 10 mmHg, and the mixture was stirred at 180 ° C. for 2 hours and 200 ° C. for 2 hours while removing phenol, and then cooled to room temperature to obtain an oily dinitropolycarbonate (di-4-nitrophenethylpolycarbonate). The number average molecular weight was 1700.

  41.0 g of the obtained dinitropolycarbonate, 200 ml of tetrahydrofuran, 200 ml of methanol, and 0.41 g of palladium activated carbon were placed in a glass reaction container having an internal volume of 1 L, and stirred at a temperature of 25 ° C. for 18 hours under a hydrogen atmosphere (normal pressure). After the catalyst was filtered off, the solvent was distilled off to obtain 39.9 g of a waxy diamino polycarbonate (di-4-aminophenethyl polycarbonate).

From the infrared spectrum of this diaminopolycarbonate (FIG. 6), it was confirmed that the reduction reaction from the nitro group to the amino group proceeded sufficiently. From the ¹ H-NMR spectrum (FIG. 7), S1 = 4.00 / 4 = 1.00, S2 = 0, S3 = 0.13 / 4 = 0.033, S4 = 0, and the amination fraction (Α) was 0.968, which was high. The amine equivalent was 668, the number average molecular weight was 1600, and the glass transition temperature was -38 ° C.

  The diamino polycarbonate of the present invention is a compound useful as a flexible component such as polyimide, polyamide, and other resins, and is also useful as an additive such as an epoxy curing material and a polyurethane chain extender. Furthermore, it can also be used as an ink, a paint, a coating material, an adhesive, or an electronic material.

2 is an infrared absorption spectrum of the dinitropolycarbonate obtained in Example 1. 1 is ¹ H-NMR of dinitropolycarbonate obtained in Example 1. FIG. 2 is an infrared absorption spectrum of the diamino polycarbonate obtained in Example 1. 2 is ¹ H-NMR of the diamino polycarbonate obtained in Example 1. FIG. 1 is ¹ H-NMR of a nitro group-containing carbonate obtained in Reference Example 1. 2 is an infrared absorption spectrum of the diamino polycarbonate obtained in Example 2. 2 is ¹ H-NMR of the diamino polycarbonate obtained in Example 2.

Claims (7)

A diamino polycarbonate represented by the general formula (1).

(Wherein R ¹ represents a divalent aliphatic hydrocarbon group having 2 to 25 carbon atoms, and a part of the carbon chain of the aliphatic hydrocarbon group may form a branched chain structure or a cyclic structure. The carbon atom in the carbon chain may be substituted with an oxygen atom, and R ² is a divalent aliphatic hydrocarbon group having 2 to 25 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 25 carbon atoms. The aromatic hydrocarbon group represents the total number of carbon atoms including the substituent on the aromatic ring, and the carbon chain of this substituent may form a branched chain structure or a cyclic structure. The carbon atom in the carbon chain may be substituted with an oxygen atom, and n is a positive integer representing the degree of polymerization.) Formula (1) in ^- an organic group "-R 2 group" is represented by the general formula (2), diamino polycarbonate according to claim 1, wherein.

(In the formula, R ³ represents a divalent aliphatic hydrocarbon group having 1 to 19 carbon atoms. The carbon chain of the aliphatic hydrocarbon group may form a branched chain structure or a cyclic structure. The carbon atom in the chain may be substituted with an oxygen atom, and the phenyl group portion of this organic group is bonded to the terminal amino group in the general formula (1). The diamino polycarbonate according to claim 1 or 2, having a number average molecular weight of 500 to 20,000. The diamino polycarbonate according to any one of claims 1 to 3, wherein the introduction ratio of the amino group to the terminal is 90% or more. The method for producing a diamino polycarbonate according to claim 1, wherein the nitro group of the dinitropolycarbonate represented by the general formula (3) is reduced.

(Wherein R ¹ , R ² and n are the same as described above.) 6. The diamino polycarbonate according to claim 5, wherein the dinitropolycarbonate is obtained by reacting a carbonate ester, an aliphatic dihydric alcohol and nitroalcohol, or obtained by reacting a polycarbonate diol and a nitro group-containing carbonate ester. A method for producing polycarbonate.   A dinitropolycarbonate represented by the general formula (3).

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