HK1163650A

HK1163650A - Cyclic carbodiimide compounds

Info

Publication number: HK1163650A
Application number: HK12103971.3A
Authority: HK
Inventors: Shoji Shinichiro; Suzuki Hirotaka
Original assignee: Teijin Limited
Priority date: 2008-12-15
Filing date: 2012-04-20
Publication date: 2012-09-14

Description

Cyclic carbodiimide compound

The present application is a divisional application of an invention patent application having an application date of 2009, 12/15, application No. 200980151338.4, entitled "cyclic carbodiimide compound".

Technical Field

The present invention relates to an intermediate of a cyclic carbodiimide compound.

Background

Polyesters, polyamides, polyimides, polycarbonates, polyurethanes, and the like are suitable for a wide range of applications because of their excellent mechanical properties. Since the above-mentioned polymer has a hydrolyzable ester bond, amide bond, imide bond, carbonate bond, or urethane bond in its molecule, there is a case where a problem arises in reliability when used under a more severe environment, and a countermeasure therefor has been desired as early as possible.

Since the presence of a polar group such as a carboxyl group in a molecule promotes hydrolysis of a catalyst, a method of reducing the carboxyl group concentration by applying a carboxyl group capping agent to suppress the above-mentioned disadvantages has been proposed (patent documents 1 and 2).

As the blocking agent for the acidic group such as a carboxyl group, a mono-or polycarbodiimide compound is used to obtain a certain degree of effect in consideration of stability and reactivity of the blocking agent and color tone of the product to be obtained. However, since the mono-or polycarbodiimide compounds are linear carbodiimide compounds, volatile isocyanate compounds are generated during use, and odor is emitted, thereby incorporating the essential defect of deteriorating the working environment. It is desired to develop a blocking agent which does not have the above-mentioned drawbacks and has higher reactivity.

Patent document 3 describes a macrocyclic carbodiimide compound having a urethane bond and a polymer chain having a molecular weight of 100 to 7,000. The macrocyclic carbodiimide compound has a high molecular weight, and therefore is not effective as a blocking agent for an acidic group. In addition, in patent document 3, prevention of generation of malodor is not studied.

(patent document 1) Japanese patent application laid-open No. 2004-

(patent document 2) Japanese 2005-350829

(patent document 3) pamphlet of International patent No. 2008/081230

Disclosure of Invention

The invention aims to: disclosed is an intermediate of a cyclic carbodiimide compound which is useful as a stabilizer for a polymer having a hydrolyzable functional group such as a polyester. In addition, the present invention aims to: a process for producing an intermediate of the cyclic carbodiimide compound is provided.

The present inventors have conducted intensive studies on a blocking agent which does not release an isocyanate compound even when it reacts with an acidic group such as a carboxyl group. As a result, they have found that a cyclic carbodiimide compound having a cyclic structure does not release an isocyanate compound, does not generate an offensive odor, and does not deteriorate the working environment even when it reacts with an acidic group, and have conducted intensive studies on an intermediate of the compound, thereby completing the present invention.

That is, the present invention includes the following inventions.

1. A compound represented by the following formula (S),

wherein X is a 4-valent group represented by the following formula (i-4),

Ar¹～Ar⁴each independently an aromatic group which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group,

alpha is-NO₂、-NH₂、-N＝PAr^a ₃N ═ C ═ O or two α may be combined to form a bonding group represented by the following formula (i-5), wherein said Ar is^aIs a phenyl group, and the phenyl group,

wherein Z is an oxygen atom or a sulfur atom.

2. The compound of the above 1, wherein, Ar¹～Ar⁴Each independently an o-phenylene group or a 1, 2-naphthalenediyl group which may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

3. The compound of the above 1 represented by the following formula (C),

in the formula, X, Ar¹～Ar⁴The same as the above formula (S).

4. The compound of the above 1 represented by the following formula (D),

in the formula, X, Ar¹～Ar⁴The same as the above formula (S).

5. The compound of the above 1 represented by the following formula (E-1),

in the formula, X, Ar¹～Ar⁴、Ar^aThe same as the above formula (S).

6. The compound of the above 1 represented by the following formula (E-2),

in the formula, X, Ar¹～Ar⁴And Z is the same as the above formula (S).

7. The compound of the above 1 represented by the following formula (G),

in the formula, X, Ar¹～Ar⁴The same as the above formula (S).

Best Mode for Carrying Out The Invention

< Cyclic carbodiimide Compound >

The present invention is an intermediate of a cyclic carbodiimide compound represented by the following formula (i).

In the formula Ar¹～Ar⁴Each independently is an aryl group. The aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. Examples of the aryl group include aryl groups having 5 to 15 carbon atoms such as a phenylene group and a naphthalenediyl group.

Examples of the alkyl group having 1 to 6 carbon atoms as a substituent include a methyl group, an ethyl group, a n-propyl group, a sec-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, a n-pentyl group, a sec-pentyl group, an isopentyl group, a n-hexyl group, a sec-hexyl group, and an isohexyl group. The presence of the alkyl group having 1 to 6 carbon atoms or the phenyl group increases compatibility with a polymer such as a polyester, and the effect of improving the action of the cyclic carbodiimide compound of the invention can be expected. In addition, an effect of suppressing the volatility of the cyclic carbodiimide compound can be expected.

X is a group having a valence of 4.

X is preferably a 4-valent group of the following formula (i-4).

The cyclic carbodiimide compound may contain a monocyclic compound of the following formula (F) and a 2-ring compound of the following formula (F), but the compound of the present invention is an intermediate of the 2-ring compound of the formula (F).

In the formula Ar¹～Ar²And X is the same as formula (i). Ar (Ar)¹～Ar²Preferred is an o-phenylene group which may be substituted. The substituent is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. X is a 2-valent group.

In the formula Ar¹～Ar⁴And X is the same as formula (i). Ar (Ar)¹～Ar⁴Preferred is an o-phenylene group which may be substituted. The substituent is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. X is a 4-valent group.

The cyclic carbodiimide compound of the present invention preferably has 2 o-phenylene groups bonded to each other through the 1, 3-positions of the carbodiimide groups, and the o-phenylene groups each have an ether oxygen atom at the ortho-position of the carbodiimide group, and the ether oxygen atoms are bonded to each other through X to form a cyclic structure.

That is, a compound represented by the following formula is preferable.

The molecular weight of the cyclic carbodiimide compound is preferably 100 to 1,000. If the amount is less than 100, the structural stability and volatility of the cyclic carbodiimide compound may be problematic. If the amount is more than 1,000, the cyclic carbodiimide may be synthesized in a diluted system or the yield may be lowered in the production of the cyclic carbodiimide, which may cause a problem in terms of cost. From this viewpoint, the content is more preferably 100 to 750, and still more preferably 250 to 750. The cyclic carbodiimide compound has 1 carbodiimide group in 1 ring. When 1 ring has 2 or more carbodiimide groups, an isocyanate compound is generated by a blocking reaction, which causes an offensive odor.

< preparation of monocyclic carbodiimide Compound (f) >

For reference purposes, the preparation of the monocyclic carbodiimide compound (f) is described. The monocyclic carbodiimide compound (f) can be produced by the following steps (1) to (4).

The step (1) is a step of producing a nitro compound (c). The step (1) includes 2 modes of the step (1a) and the step (1 b). The step (2) is a step of obtaining an amine compound (d) from the nitro compound (c). The steps (3) and (4) are steps for producing the monocyclic carbodiimide compound (f) from the amine compound (d). The steps (3) to (4) include a mode in which the step (3a) and the step (4a) are passed through and a mode in which the step (3b) and the step (4b) are passed through.

Specifically, the carbodiimide compound (f) can be prepared by the following route.

(embodiment 1) Process (1a) -Process (2a) -Process (3a) -Process (4a)

(scheme 2) step (1a) -step (2a) -step (3b) -step (4b)

(scheme 3) step (1b) -step (2a) -step (3b) -step (4b)

(scheme 4) step (1b) -step (2a) -step (3a) -step (4a)

(step (1a))

The step (1a) is a step of reacting a compound of the following formula (a-1), a compound of the following formula (a-2) and a compound of the following formula (b-1) to obtain a nitro compound (c) of the following formula.

HO——Ar¹——NO₂ (a-1)

HO——Ar²——NO₂ (a-2)

E¹——X——E² (b-1)

In the formula, X, Ar¹、Ar²The same as the above formula (i). X is a 2-valent group.

E¹And E²Each independently a group selected from a halogen atom, a methylbenzenesulfonyloxy group, a methylsulfonyloxy group, a phenylsulfonyloxy group and a p-bromobenzenesulfonyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

As the reaction, a conventionally known ether synthesis method can be used, and for example, a Williamson reaction in which a compound represented by the formula (a-1), a compound represented by the formula (a-2) and a compound represented by the formula (b-1) are reacted in a solvent in the presence of a basic compound, or the like can be used.

As the basic compound, sodium hydride, metallic sodium, sodium hydroxide, potassium carbonate, or the like can be used. As the solvent, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, or the like can be used. The reaction temperature is preferably in the range of 25 ℃ to 150 ℃. In addition, although the reaction proceeds very rapidly under the above conditions, a phase transfer catalyst may be added in order to promote the reaction.

(step (1b))

The step (1b) is a step of reacting a compound of the following formula (a-i), a compound of the following formula (a-ii) and a compound of the following formula (b-i) to obtain a nitro compound of the following formula (c).

E³——Ar¹——NO₂ (a-i)

E⁴——Ar²——NO₂ (a-ii)

HO——X——OH (b-i)

In the formula, Ar¹、Ar²And X is the same as formula (i). X is a 2-valent group. E³、E⁴Each independently a group selected from a halogen atom, a methylbenzenesulfonyloxy group, a methylsulfonyloxy group, a phenylsulfonyloxy group and a p-bromobenzenesulfonyloxy group.

The reaction can be carried out by a conventionally known ether synthesis method, and for example, a Williamson reaction in which a compound represented by the formula (a-i), a compound represented by the formula (a-ii) and a compound represented by the formula (b-i) are reacted in a solvent in the presence of a basic compound can be used.

As the basic compound, sodium hydride, metallic sodium, sodium hydroxide, potassium carbonate, or the like can be used. As the solvent, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, or the like can be used. The reaction temperature is preferably in the range of 25 ℃ to 150 ℃. In addition, although the reaction is carried out under the above conditions, it is preferable to add a phase transfer catalyst in order to promote the reaction. As the phase transfer catalyst, tetrabutylammonium salts, trioctylmethylammonium salts, benzyldimethyloctadecylammonium salts, crown ethers, etc. can be used.

(step (2))

The step (2) is a step of reducing the obtained nitro compound (c) to obtain an amine compound (d) of the following formula.

Ar¹、Ar²And X is the same as formula (i). X is a 2-valent group.

The reaction may be carried out by a conventionally known method, for example, a method of reducing the nitro compound (c) by contacting it with a solvent in the presence of hydrogen and a catalyst.

As the catalyst, palladium carbon-ethylenediamine complex, palladium-fibroin, palladium-polyethyleneimine, nickel, copper, or the like can be used. As the solvent, methanol, ethanol, isopropanol, or isopropanol can be usedAlkane, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, N-dimethylformamide, and the like. The reaction temperature is selected from the range of 25-100 ℃. Although the reaction is carried out under normal pressure, it is preferable to apply pressure to promote the reaction.

As another reaction for producing the amine compound (d), a method of reacting the nitro compound (c) with an acid and a metal, a method of reacting the nitro compound (c) with hydrazine and a catalyst, or the like can be used.

(step (3a))

The step (3a) is a step of reacting the obtained amine compound (d) with triphenylphosphine dibromide to obtain a triphenylphosphine compound (e-1) of the following formula.

In the formula Ar¹、Ar²X and formula (A)i) Same as Ar^aIs phenyl.

The reaction can be carried out by a conventionally known method, for example, a method of reacting an amine compound represented by the formula (d) with triphenylphosphine dibromide in a solvent in the presence of a basic compound, and the like. As the basic compound, triethylamine, pyridine, or the like can be used. As the solvent, dichloroethane, chloroform, benzene, or the like can be used. The reaction temperature is preferably from 0 ℃ to 80 ℃.

(step (4a))

The step (4a) is a step of isocyanating the triphenylphosphine compound obtained in the reaction system and then decarbonylating the product directly to obtain a cyclic carbodiimide compound (f).

The reaction can be carried out by a conventionally known method, for example, a method of reacting the triphenylphosphine compound of the formula (e-1) in a solvent in the presence of di-tert-butyl diisocyanate and N, N-dimethyl-4-aminopyridine, or the like. As the solvent, dichlorohexane, chloroform or the like can be used. The reaction temperature is preferably from 10 ℃ to 40 ℃.

(step (3b))

The step (3b) is a step of reacting the amine compound (d) with carbon dioxide or carbon disulfide to obtain a urea compound or a thiourea compound represented by the following formula (e-2).

In the formula Ar¹、Ar²X is the same as formula (i), and Z is an oxygen atom or a sulfur atom.

The reaction for producing the urea compound (e-2) can be carried out by a conventionally known method, and for example, a method of reacting the amine compound (d) in a solvent in the presence of carbon dioxide, a phosphorus compound and a basic compound can be used.

As the phosphorus compound, phosphite, phosphate, or the like can be used. As the basic compound, triethylamine, pyridine, imidazole, picoline, or the like can be used. As the solvent, pyridine, N-dimethylformamide, acetonitrile, chlorobenzene, toluene, or the like can be used. The reaction temperature is preferably in the range of 0 ℃ to 80 ℃.

As another reaction for producing the urea compound (e-2), a method of reacting the amine compound (d) with carbon monoxide, a method of reacting the amine compound (d) with phosgene, or the like can be used.

The reaction for producing the thiourea compound (e-2) may be carried out by a conventionally known method, for example, a method of reacting the amine compound (d) in a solvent in the presence of carbon disulfide and a basic compound.

As the basic compound, triethylamine, pyridine, imidazole, picoline, or the like can be used. As the solvent, acetone, methanol, ethanol, isopropanol, 2-butanone, pyridine, N-dimethylformamide, acetonitrile, or the like can be used. The reaction temperature is preferably in the range of 25 ℃ to 90 ℃. In addition, although the reaction proceeds very rapidly under the above conditions, carbon tetrabromide or the like may be combined in order to accelerate the reaction.

(step (4b))

The step (4b) is a step of dehydrating the obtained urea compound (e-2) or desulfurizing the thiourea compound (e-2) to obtain a cyclic carbodiimide compound (f).

The reaction can be carried out by a conventionally known method, for example, a method of reacting a urea compound or a thiourea compound (e-2) in a solvent in the presence of methylbenzenesulfonyl chloride or methanesulfonyl chloride, dehydrating the urea compound (e-2), and desulfurizing the thiourea compound (e-2).

As the solvent, dichloromethane, chloroform, pyridine, or the like can be used. The reaction temperature is preferably in the range of 0 ℃ to 80 ℃.

As another reaction for obtaining the cyclic carbodiimide compound (f), a method of reacting the urea compound (e-2) with mercury oxide, a method of reacting the thiourea compound (e-2) with sodium hypochlorite, or the like can be used.

<2 preparation of Cyclic carbodiimide Compound (F) >

The compound of the present invention is an intermediate of the 2-ring carbodiimide compound (F). The 2-ring carbodiimide compound (F) can be produced by the following steps (1) to (4).

The step (1) is a step of producing a nitro compound (C). The step (1) includes 2 modes of the step (1A) and the step (1B). The step (2) is a step of producing an amide compound (D) from the nitro compound (C). The steps (3) and (4) are steps for producing the 2-ring carbodiimide compound (F) from the amide compound (D). The steps (3) to (4) include a mode in which the step (3A) and the step (4A) are passed through and a mode in which the step (3B) and the step (4B) are passed through.

The carbodiimide compound (F) can be prepared by the following route.

(embodiment 1) Process (1A) -Process (2A) -Process (3A) -Process (4A)

(embodiment 2) step (1A) -step (2A) -step (3B) -step (4B)

(embodiment 3) step (1B) -step (2A) -step (3B) -step (4B)

(scheme 4) Process (1B) -Process (2A) -Process (3A) -Process (4A)

(step (1A))

The step (1A) is a step of reacting the compounds represented by the following formulas (A-1) to (A-4) with the compound represented by the following formula (B-1) to obtain a nitro compound represented by the following formula (C).

HO——Ar¹——NO₂ (A-1)

HO——Ar²——NO₂ (A-2)

HO——Ar³——NO₂ (A-3)

HO——Ar⁴——NO₂ (A-4)

(wherein X₁Is composed of)

In the formula, Ar¹～Ar⁴And X is the same as formula (i). X is a 4-valent group. E¹～E⁴Each independently a group selected from a halogen atom, a methylbenzenesulfonyloxy group, a methylsulfonyloxy group, a phenylsulfonyloxy group and a p-bromobenzenesulfonyloxy group.

The reaction conditions are the same as in the step (1 a).

(step (1B))

The step (1B) is a step of reacting the compounds represented by the following formulas (A-i) to (A-iv) with the compound represented by the following formula (B-1) to obtain a nitro compound represented by the following formula (C).

E⁵——Ar¹——NO₂ (A-i)

E⁶——Ar²——NO₂ (A-ii)

E⁷——Ar³——NO₂ (A-iii)

E⁸——Ar⁴——NO₂ (A-iv)

(wherein X₁Is composed of)

In the formula, Ar¹～Ar⁴And X is the same as formula (i). E⁵～E⁸Each independently a group selected from a halogen atom, a methylbenzenesulfonyloxy group, a methylsulfonyloxy group, a phenylsulfonyloxy group and a p-bromobenzenesulfonyloxy group.

The reaction conditions are the same as in the step (1 b).

(step (2A))

The step (2A) is a step of reducing the obtained nitro compound to obtain an amine compound (D) of the following formula.

Ar¹～Ar⁴And X is the same as formula (i).

The reaction conditions are the same as in the step (2 a).

(step (3A))

In the formula Ar¹～Ar⁴X is the same as formula (i), Ar^aIs phenyl.

The reaction conditions are the same as in the step (3 a).

(step (4A))

The step (4A) is a step of isocyanating the obtained triphenylphosphine compound in the reaction system and then decarbonylating the product directly to obtain a compound (F) of the following formula.

In the formula, Ar¹～Ar⁴And X is the same as formula (i).

The reaction conditions are the same as in the step (4 a).

(step (3B))

The step (3B) is a step of reacting the amine compound with carbon dioxide or carbon disulfide to obtain a urea compound or thiourea compound (E-2) of the following formula.

In the formula Ar¹～Ar⁴X is the same as formula (i), and Z is an oxygen atom or a sulfur atom.

The reaction conditions are the same as in the step (3 b).

(step (4B))

The step (4B) is a step of dehydrating the obtained urea compound or desulfurizing the thiourea compound to obtain a compound (F) of the following formula.

In the formula, Ar¹～Ar⁴X and formula(i) The same is true.

The reaction conditions are the same as in the step (4 b).

< Polymer Compound >

The polymer compound to which the cyclic carbodiimide compound obtained from the intermediate of the present invention is applied has an acidic group. Examples of the acidic group include at least one selected from the group consisting of a carboxyl group, a sulfonic group, a sulfinic group, a phosphonic group and a phosphinic group. The polymer compound may be at least one selected from the group consisting of polyesters, polyamides, polyamideimides, polyimides, and polyesteramides.

Examples of the polyester include polymers or copolymers obtained by polycondensation of 1 or more members selected from the group consisting of dicarboxylic acids or ester-forming derivatives thereof and diols or ester-forming derivatives thereof, hydroxycarboxylic acids or ester-forming derivatives thereof, and lactones, and thermoplastic polyester resins are preferably used. Such a thermoplastic polyester resin may contain a crosslinked structure obtained by treatment with a radical generating source (e.g., an active energy ray, an oxidizing agent, etc.) for reasons such as moldability.

Examples of the dicarboxylic acid or ester-forming derivative include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4' -diphenyletherdicarboxylic acid, 5-tetrabutylphosphonium isophthalate (5- テトラブチルスルホニウムイソフタル acid) and 5-sodium sulfoisophthalate (5- ナトリウムスルホイソフタル acid), and ester-forming derivatives thereof. Further, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, and dimer acid, and ester-forming derivatives thereof are exemplified. Examples thereof include alicyclic dicarboxylic acids such as 1, 3-cyclohexanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

Examples of the diol or its ester-forming derivative include aliphatic diols having 2 to 20 carbon atoms, i.e., ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, and polyglycols. Examples of the diol include long-chain diols having a molecular weight of 200 to 100,000, such as polyethylene glycol, polypropylene glycol, poly-1, 2-propanediol, and polybutylene glycol. Further, aromatic dioxy compounds, i.e., 4' -dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol a, bisphenol S, bisphenol F, and the like, and ester-forming derivatives thereof, and the like can be mentioned.

Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and ester-forming derivatives thereof. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecanolactone, and 1, 5-oxepan-2-one.

Examples of the aromatic polyester obtained by polycondensation of an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof as main components include a polymer obtained by polycondensation of an aromatic carboxylic acid or an ester-forming derivative thereof, preferably terephthalic acid, naphthalene 2, 6-dicarboxylic acid or an ester-forming derivative thereof, and an aliphatic diol or an ester-forming derivative thereof selected from ethylene glycol, 1, 3-propanediol and butanediol as main components.

Specifically, preferred examples thereof include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, poly (ethylene terephthalate/isophthalate), poly (trimethylene terephthalate/isophthalate) trimethylene terephthalate, poly (butylene terephthalate/isophthalate) butylene terephthalate, polyethylene terephthalate/polyethylene glycol, polybutylene naphthalate/polyethylene glycol, polyethylene terephthalate/polytetrahydrofuran glycol (ポリエチレンテレフタ - ト. ポリ (テトラメチレンオキシド) グリコ - ル polyethylene terephthalate/polyethylene oxide) glycol, Polytrimethylene terephthalate polytetrahydrofuran diol, polybutylene naphthalate polytetrahydrofuran diol, poly (ethylene terephthalate/isophthalate) polytetrahydrofuran diol, poly (trimethylene terephthalate/isophthalate) polytrimethylene terephthalate polytetrahydrofuran diol, poly (butylene terephthalate/isophthalate) butanediol polytetrahydrofuran diol, poly (butylene terephthalate/succinate), poly (ethylene terephthalate/succinate), poly (butylene terephthalate/adipate), poly (ethylene terephthalate/adipate) and the like.

Examples of the aliphatic polyester include a polymer mainly composed of an aliphatic hydroxycarboxylic acid, a polymer mainly composed of an aliphatic polycarboxylic acid or an ester-forming derivative thereof and an aliphatic polyhydric alcohol, and a copolymer thereof.

Examples of the polymer containing an aliphatic hydroxycarboxylic acid as a main component include a polycondensate or copolymer of glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, and hydroxycaproic acid. Examples thereof include polyglycolic acid, polylactic acid, ポリ 3- ヒドロキシカルボン butyric acid, poly-4-hydroxybutyric acid, poly-3-hydroxycaproic acid, polycaprolactone and copolymers thereof. In particular, poly L-lactic acid, poly D-lactic acid, and poly (lactic acid) stereocomplex (ステレオコンプレツクスポリ poly lactic acid stereocomplex) and racemic poly (lactic acid) can be preferably used.

The polyester may be a polymer mainly composed of an aliphatic polycarboxylic acid and an aliphatic polyol. Examples of the polycarboxylic acid include aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, and dimer acid. Examples thereof include alicyclic dicarboxylic acid units such as 1, 3-cyclohexanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

Examples of the diol component include aliphatic diols having 2 to 20 carbon atoms, that is, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, decanediol, cyclohexanedimethanol, cyclohexanediol, and polyglycols. Or a condensate containing a long-chain diol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, polypropylene glycol, poly-1, 2-propylene glycol, or polybutylene glycol as a main component. Specific examples thereof include polyethylene adipate, polyethylene succinate, polybutylene adipate, polybutylene succinate, and copolymers thereof.

Further, the wholly aromatic polyester may be exemplified by a polymer obtained by polycondensation of an aromatic carboxylic acid or an ester-forming derivative thereof, preferably terephthalic acid or naphthalene 2, 6-dicarboxylic acid or an ester-forming derivative thereof, and an aromatic polyhydric hydroxyl compound or an ester-forming derivative thereof as main components.

Specifically, poly (4-phenylene oxide-2, 2-propylene oxide-4-phenylene oxide-terephthaloyl-co-isophthaloyl) and the like can be exemplified.

The polyester contains 1 to 50 equivalents/ton of carboxyl group andor hydroxyl group at the molecular terminal as a carbodiimide reactive component. Because of the stability of such terminal groups, particularly carboxyl-degradable polyesters, blocking by a cyclic carbodiimide compound is preferred.

When the carbodiimide compound is used for blocking a carboxyl end group, the cyclic carbodiimide compound of the present invention can block a carboxyl group without generating toxic free isocyanate, which is a great advantage.

Further, as an additional effect, when the blocking is performed with a cyclic carbodiimide compound, an increase in the molecular weight or a decrease in the molecular weight of the polyester due to chain extension action of isocyanate end groups formed in the polyester without liberating and hydroxyl end groups or carboxyl end groups present in the polyester can be more effectively suppressed than in the case of a conventional linear carbodiimide compound, and thus, the industrial significance is large.

The above polyesters can be prepared by a known method (for example, recorded in handbook of saturated polyester resins (Toxoki and Male, Nissan Industrial News Co., Ltd. (12/22/1989)), etc.).

In the present invention, examples of the polyester include, in addition to the above-mentioned polyester, an unsaturated polyester resin obtained by copolymerizing an unsaturated polycarboxylic acid or an ester-forming derivative thereof, and a polyester elastomer containing a low-melting polymer segment.

Examples of the unsaturated polycarboxylic acid include maleic anhydride, tetrahydromaleic anhydride, fumaric acid, endomethylenetetrahydromaleic anhydride, and the like. In such unsaturated polyesters, various monomers are added to control the curing properties, and the resulting products are cured and molded by heat curing, radical curing, or curing treatment with active energy rays such as light and electron beams. Although control of the carboxyl group is an important technical problem in terms of rheological properties such as thixotropy and resin durability, such unsaturated resins have a great industrial significance because the cyclic carbodiimide compound can block and control the carboxyl group without generating toxic free isocyanate and can increase the molecular weight more effectively.

In the present invention, the polyester may be a polyester elastomer obtained by copolymerizing a soft component. As disclosed in a publicly known document, for example, Japanese patent application laid-open No. 11-92636, a polyester elastomer is a copolymer containing a high-melting polyester segment and a low-melting polymer segment having a molecular weight of 400 to 6,000.

The melting point when the copolymer is formed only by the high-melting polyester segment is 150 ℃ or higher. The melting point or softening point when the copolymer is formed only by the low-melting polymer segment is 80 ℃ or lower. The low-melting polymer segment preferably contains polyalkylene glycols or aliphatic dicarboxylic acids having 2 to 12 carbon atoms and aliphatic diols having 2 to 10 carbon atoms. Such elastomers have a problem in terms of hydrolytic stability, but the cyclic carbodiimide compound has a great industrial significance in that it is free from a safety problem, and it is possible to control carboxyl groups and suppress or increase the decrease in molecular weight.

The polyamide is a thermoplastic resin having an amide bond, which is mainly composed of an amino acid, a lactam or a diamine and a dicarboxylic acid or an amide-forming derivative thereof.

In the present invention, as the polyamide, a polycondensate obtained by condensing a diamine and a dicarboxylic acid or an acyl active compound thereof, a polymer obtained by condensing an aminocarboxylic acid, a lactam or an amino acid, or a copolymer thereof can be used.

Examples of the diamine include aliphatic diamines and aromatic diamines. Examples of the aliphatic diamine include butanediamine, hexanediamine, undecanediamine, dodecanediamine, 2, 4-trimethylhexanediamine, 2, 4, 4-trimethylhexanediamine, 5-methylnonanediamine, 2, 4-dimethyloctanediamine, m-xylylenediamine, p-xylylenediamine, 1, 3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane, 3, 8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, and aminoethylpiperazine.

As the aromatic diamine, p-phenylenediamine, m-phenylenediamine, 2, 6-naphthalenediamine, 4 '-biphenyldiamine, 3, 4' -biphenyldiamine, 4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfone, 4 '-diaminobenzophenone, 3, 4' -diaminobenzophenone, 2-bis (4-aminophenyl) propane, and the like are mentioned.

Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalate, hexahydroterephthalic acid, hexahydroisophthalic acid, and glyoxylic acid. Specific examples thereof include aliphatic polyamides such as polycaproamide (nylon 6), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecanoamide (nylon 612), polyundecanoamide (nylon 116), polyundecanoamide (nylon 11), and polydodecanoamide (nylon 12).

Further, there may be mentioned aliphatic-aromatic polyamides such as poly (trimethylhexamethylene terephthalamide), poly (hexamethylene isophthalamide) (nylon 6I), poly (hexamethylene terephthalamide)/isophthalamide) (nylon 6T/6I), poly (bis (4-aminocyclohexyl) methanedodecamide (nylon PACM12), poly (3-methyl-4-aminocyclohexyl) methanedodecamide (nylon dimethyl PACM12), poly (m-xylylene adipamide) (nylon MXD6), poly (undecyl terephthalamide) (nylon 11T), poly (undecyl hexahydrophthalamide) (nylon 11T (H)), and copolyamides thereof, and copolymers or mixtures thereof. Further, poly (p-phenylene terephthalamide), poly (p-phenylene terephthalamide-co-phenylene terephthalamide), and the like can be cited.

Examples of the amino acid include omega-aminocaproic acid, omega-aminoheptanoic acid, omega-aminocaprylic acid, omega-aminononanoic acid (ペルゴン acid pelargonic acid), omega-aminocaprylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and p-aminomethylbenzoic acid, and examples of the lactam include omega-caprolactam, omega-enantholactam, omega-decanolactam, and omega-dodecanolactam.

The molecular weight of these polyamide resins is not particularly limited, but it is preferable that the relative viscosity measured at 25 ℃ in a 98% concentrated sulfuric acid solution of the polyamide resin having a concentration of 1% by weight is in the range of 2.0 to 4.0.

These amide resins can be produced by a known method, for example, "handbook of polyamide resins (manufactured by Fuben, Japan Industrial News Co., Showa, 63, 1 month and 30 days)".

The polyamide of the present invention includes known polyamides as the polyamide elastomer. Examples of such polyamides include graft or block copolymers obtained by reaction with a polyamide-forming component having 6 or more carbon atoms and a polyalkylene oxide glycol, and the bond between the polyamide-forming component having 6 or more carbon atoms and the polyalkylene oxide glycol component is usually an ester bond or an amide bond, but is not particularly limited to these chemical bonds, and a 3 rd component such as dicarboxylic acid or diamine may be used as the reaction component of the two components.

As examples of the polyalkylene oxide glycol, polyethylene oxide glycol, poly (1, 2-propylene oxide) glycol, poly (1, 3-propylene oxide) glycol, polytetrahydrofuran glycol, polyhexamethylene oxide glycol, a block or random copolymer of ethylene oxide and propylene oxide, a block or random copolymer of ethylene oxide and tetrahydrofuran, and the like can be exemplified. The number average molecular weight of the alkylene oxide glycol is preferably 200 to 6,000, more preferably 300 to 4,000, from the viewpoint of polymerizability and rigidity. The polyamide elastomer used in the present invention is preferably a polyamide elastomer obtained by polymerizing caprolactam, polyethylene glycol, and terephthalic acid.

As can be easily understood from the raw materials, such a polyamide resin contains about 30 to 100 equivalents/ton of carboxyl groups and about 30 to 100 equivalents/ton of amino groups, but it is known that carboxyl groups have an undesirable effect of stabilizing amides.

The cyclic carbodiimide compound can control the carboxyl group to 20 equivalents/ton or less, or 10 equivalents/ton or less, more preferably to less than that without safety problems, and is of great significance in a composition which can control the molecular weight reduction more effectively.

The polyamideimide resin used in the present invention has a main repeating structural unit represented by the following formula (I).

In the formula R²Represents a 3-valent organic group, R³Represents a 2-valent organic group, and n represents a positive integer.

Typical examples of the synthetic method of such a polyamideimide resin include (1) a method of reacting a diisocyanate with a triacid anhydride, (2) a method of reacting a diamine with a triacid anhydride, and (3) a method of reacting a diamine with a triacid acid chloride (water of a salt of a hydrochloric acid クロライド). However, the method for synthesizing the polyamideimide resin used in the present invention is not limited to these methods. Representative compounds used in the above synthesis method are listed below.

First, as the diisocyanate, preferable compounds include 4, 4 '-diphenylmethane diisocyanate, xylylene diisocyanate, 3' -diphenylmethane diisocyanate, 4 '-diphenylether diisocyanate, 3' -diphenylether diisocyanate, p-phenylene diisocyanate, and the like.

Preferred examples of the diamine include 4, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 3' -diaminodiphenyl methane, xylylenediamine, and phenylenediamine. Among these, more preferable examples of the compound include 4, 4 '-diphenylmethane diisocyanate, 3' -diphenylmethane diisocyanate, 4 '-diphenylether diisocyanate, 3' -diphenylether diisocyanate, 4 '-diaminodiphenylether, 3' -diaminodiphenylether, 4 '-diaminodiphenylmethane, and 3, 3' -diaminodiphenylmethane.

The preferable examples of the tribasic acid anhydride include trimellitic anhydride, and the tribasic acid anhydride chloride includes trimellitic anhydride chloride.

In the synthesis of the polyamideimide resin, a dicarboxylic acid, a tetracarboxylic dianhydride, or the like may be reacted within a range that does not impair the properties of the polyamideimide resin. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, and adipic acid, and examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, and biphenyl tetracarboxylic acid dianhydride. These compounds are preferably used in an amount of 50% equivalent or less of the total acid components.

The polyamide-imide resin preferably has a carboxyl group content of preferably 1 to 10 equivalents/ton or less because the durability of the concentration of the carboxyl group contained in the polymer is reduced. In the cyclic carbodiimide compound of the present invention, the carboxyl group concentration can be preferably set in the above range.

As the polyimide resin, a thermoplastic polyimide resin is preferably selected. Examples of the polyimide resin include polyimides formed from a diamine component described below and a tetracarboxylic acid.

H₂N-R⁴-NH₂

[ in the formula, R⁴Represents (i) a single bond,

(ii)C_2～12an aliphatic hydrocarbon group, a hydrocarbon group,

(iii)C_4～30an alicyclic group, a carboxyl group,

(iv)C_6～30an aryl group, a heteroaryl group,

(v)-Ph-O-R⁵-O-Ph-group (wherein, R⁵Represents phenylene or Ph-W¹-Ph-radical, W¹Represents a single bond, C which may be substituted by a halogen atom_1～4Alkylene, -O-Ph-O-group, -O-, -CO-, -S-, -SO-or-SO₂-radical) or

(vi)-R⁶-(SiR⁷ ₂O)_m-SiR⁷ ₂-R⁶A group (wherein R is⁶Is represented by- (CH)₂)_s-、-(CH₂)_s-Ph-、-(CH₂)_s-O-Ph-or Ph-, m is an integer of 1 to 100, s represents an integer of 1 to 4, R⁷Is represented by C_1～6Alkyl, phenyl or C_1～6An alkyl phenyl group. ).]

[ in the formula, Y represents C_2～12A tetravalent aliphatic radical of_4～8Tetravalent alicyclic group of、C_6～14Mono-or poly-condensed ring tetravalent aromatic group, > Ph-W²Ph < radical (wherein, W²Represents a single bond, C which may be substituted by a halogen atom_1～4Alkylene, -O-Ph-O-, -CO-, -S-, -SO-or-SO₂-radical).]。

Specific examples of the tetracarboxylic anhydride used for preparing the polyamic acid include pyromellitic anhydride (PMDA), 4, 4 ' -oxydiphthalic anhydride (ODPA), biphenyl-3, 3 ', 4, 4 ' -tetracarboxylic anhydride (BPDA), benzophenone-3, 3 ', 4, 4 ' -tetracarboxylic anhydride (BTDA), ethylenetetracarboxylic anhydride, butanetetracarboxylic anhydride, cyclopentanetetracarboxylic anhydride, benzophenone-2, 2 ', 3, 3 ' -tetracarboxylic anhydride, biphenyl-2, 2 ', 3, 3 ' -tetracarboxylic anhydride, 2-bis (3, 4-dicarboxyphenyl) propane anhydride, 2-bis (2, 3-dicarboxyphenyl) propane anhydride, bis (3, 4-dicarboxyphenyl) ether anhydride, bis (3, 4-dicarboxyphenyl) sulfone anhydride, and the like, 1, 1-bis (2, 3-dicarboxyphenyl) ethane anhydride, bis (2, 3-dicarboxyphenyl) methane anhydride, bis (3, 4-dicarboxyphenyl) methane anhydride, 4 '- (p-phenylenedioxy) diphthalic anhydride, 4' - (m-phenylenedioxy) diphthalic anhydride, naphthalene-2, 3, 6, 7-tetracarboxylic anhydride, naphthalene-1, 4, 5, 8-tetracarboxylic anhydride, naphthalene-1, 2, 5, 6-tetracarboxylic anhydride, benzene-1, 2, 3, 4-tetracarboxylic anhydride, perylene-3, 4, 9, 10-tetracarboxylic anhydride, anthracene-2, 3, 6, 7-tetracarboxylic anhydride, phenanthrene-1, 2, 7, 8-tetracarboxylic anhydride, and the like, but is not limited to these compounds. The dicarboxylic anhydrides may be used singly or in admixture of 2 or more. Among them, pyromellitic anhydride (PMDA), 4, 4 ' -oxydiphthalic anhydride (ODPA), biphenyl-3, 3 ', 4, 4 ' -tetracarboxylic anhydride (BPDA), benzophenone-3, 3 ', 4, 4 ' -tetracarboxylic anhydride, and diphenylsulfone-3, 3 ', 4, 4 ' -tetracarboxylic anhydride (DSDA) are preferably used.

Specific examples of the diamine used for the preparation of the polyimide include 4, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfide, 4 ' -bis (m-aminophenoxy) diphenyl sulfone, 4 ' -bis (p-aminophenoxy) diphenyl sulfone, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, 2 ' -diaminobenzophenone, 4 ' -diaminodiphenyl-2, 2 ' -propane, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, propylenediamine, butylenediamine, hexamethylenediamine, 4-dimethylheptanediamine, 2, 11-dodecanediamine, dodecylenediamine, butylenediamine, hexylenediamine, 4-dimethylheptanediamine, etc, Bis (p-aminophenoxy) dimethylsilane, 1, 4-bis (3-aminopropyl-disilazane) benzene, 1, 4-diaminocyclohexane, o-tolyldiamine, m-tolyldiamine, acetoguanamine, benzoylguanamine, 1, 3-bis (3-aminophenoxy) benzene (APB), bis [4- (3-aminophenoxy) phenyl ] methane, 1-bis [4- (3-aminophenoxy) phenyl ] ethane, 1, 2-bis [4- (3-aminophenoxy) phenyl ] ethane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] butane, 2, 2-bis [4- (3-aminophenoxy) phenyl ] -1, 1, 1, 3, 3, 3-hexafluoropropane, 4' -bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl ] methanone, bis [4- (3-aminophenoxy) phenyl ] sulfide, bis [4- (3-aminophenoxy) phenyl ] sulfoxide, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis (4- (3-aminophenoxy) phenyl) ether and the like, but are not limited to these compounds. The above diamines may be used singly or in combination of two or more.

Examples of the thermoplastic polyimide include polyimide resins containing tetracarboxylic anhydride represented by the following formula and known diamines such as p-phenylenediamine, various cyclohexane diamines, and hydrogenated bisphenol a diamines. Further, examples of the commercially available products include Ultem1000, Ultem1010, Ultem CRS5001 and Ultem XH6050 available under the trade name Ultem from general electric company (ゼネラルエレクトリツク Co., Ltd.), and オ - ラム 250AM available from Mitsui Chemicals, Inc.

[ in the formula, R⁸And R⁹Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or an aryl group. R¹⁰Represents a carbon atom number of 6 to 30Aryl or alkylene having 2 to 20 carbon atoms. m and n are integers of 0-5, and k is an integer of 1-3.]

As the polyester amide resin, conventionally known polyester amide resins obtained by copolymerization of a polyester constituent and a polyamide constituent can be exemplified, and among them, a thermoplastic polyester amide resin is suitably selected.

The polyester amide resin can be synthesized by a known method or the like. For example, the following method can be used: a method comprising first reacting the polyamide components by polycondensation to synthesize a polyamide having a functional group at the end, and then polymerizing the polyester components in the presence of the polyamide. The polycondensation reaction is generally carried out as follows: amidation reaction was performed as a first stage, and esterification reaction was performed in a second stage. As such a polyester constituent component, the polyester constituent component described above is suitably selected. The above-described polyamide component is suitably selected as such a polyamide component.

< use of carbodiimide >

The cyclic carbodiimide compound obtained from the intermediate of the present invention can block an acid group by mixing and reacting with a polymer compound having an acid group. The method for adding and mixing the cyclic carbodiimide compound to the polymer compound is not particularly limited, and a method of adding a solution, a melt, or an appropriate polymer as a master batch by a conventionally known method, a method of bringing a solid of a polymer compound into contact with a liquid in which the cyclic carbodiimide compound is dissolved, dispersed, or melted, and impregnating the cyclic carbodiimide compound with the solution, and the like can be employed.

When a method of adding a solution, a melt or a suitable polymer as a master batch is adopted, a method of adding using a conventionally known kneading apparatus can be adopted. In kneading, from the viewpoint of uniform kneading properties, a kneading method in a solution state or a kneading method in a molten state is preferable. The kneading apparatus is not particularly limited, and conventionally known vertical reaction vessels, mixing tanks, kneading tanks, or uniaxial or multiaxial horizontal kneading apparatuses (for example, a uniaxial or multiaxial extruder (ル - ダ -extruder), kneader, etc.) can be exemplified. The mixing time with the polymer compound is not particularly limited, and depends on the mixing apparatus and the mixing temperature, but is preferably selected from 0.1 minute to 2 hours, more preferably from 0.2 minute to 60 minutes, and still more preferably from 0.2 minute to 30 minutes.

As the solvent, a substance inert to the polymer compound and the cyclic carbodiimide compound can be used. Particularly preferred are solvents having affinity for both and at least partially dissolving both.

Examples of the solvent include hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, halogen solvents, and amide solvents.

Examples of the hydrocarbon solvent include hexane, cyclohexane, benzene, toluene, xylene, heptane, decane, and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isophorone, and the like. Examples of the ester solvent include ethyl acetate, methyl acetate, ethyl succinate, methyl carbonate, ethyl benzoate, diethylene glycol diacetate, and the like. As the ether solvent, diethyl ether, dibutyl ether, tetrahydrofuran, and dibutyl ether are exemplifiedAlkanes, diglyme, triglyme diethyl ether, diphenyl ether, and the like.

Examples of the halogen-based solvent include dichloromethane, chloroform, tetrachloromethane, dichloroethane, 1 ', 2, 2' -tetrachloroethane, chlorobenzene, dichlorobenzene, and the like. Examples of the amide solvent include formamide, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone. These solvents may be used alone or as a mixed solvent as required.

The solvent is preferably used in an amount of 1 to 1,000 parts by weight per 100 parts by weight of the total amount of the polymer compound and the cyclic carbodiimide compound. If it is less than 1 part by weight, a suitable solvent is not meaningful. The upper limit of the amount of the solvent used is not particularly limited, but is about 1,000 parts by weight from the viewpoint of the operability and the reaction efficiency.

When a method of contacting a solid of a polymer compound with a liquid in which a cyclic carbodiimide compound is dissolved, dispersed, or melted to impregnate the cyclic carbodiimide compound is employed, as described above, a method of contacting a solid polymer compound with a carbodiimide compound dissolved in a solvent, a method of contacting a solid polymer compound with an emulsion of a cyclic carbodiimide compound, or the like can be employed. As a method of contact, a method of impregnating a polymer compound, a method of coating on a polymer compound, a method of spreading, and the like can be preferably adopted.

The blocking reaction by the cyclic carbodiimide compound obtained from the intermediate of the present invention may be carried out at a temperature of about room temperature (25 ℃) to about 300 ℃, but from the viewpoint of reaction efficiency, the blocking reaction is further accelerated in a range of preferably 50 to 280 ℃, more preferably 100 to 280 ℃. The polymer compound is more likely to react at a melting temperature, but is preferably reacted at a temperature lower than 300 ℃ in order to suppress the increase, decomposition, and the like of the cyclic carbodiimide compound. In addition, it is effective to use a solvent in order to lower the melting temperature of the polymer and to improve the stirring efficiency.

Although the reaction proceeds very rapidly in the absence of a catalyst, catalysts which promote the reaction may also be used. As the catalyst, a catalyst which has been conventionally used for linear carbodiimide compounds can be suitably used (Japanese patent laid-open No. 2005-2174). Examples of the organic acid include alkali metal compounds, alkaline earth metal compounds, tertiary amine compounds, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium salts, phosphoric acid esters, organic acids, and Lewis acids, and 1 or 2 or more of these compounds can be used. The amount of the catalyst to be added is not particularly limited, but is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, and most preferably 0.02 to 0.1 part by weight, based on 100 parts by weight of the total amount of the polymer compound and the cyclic carbodiimide compound.

The amount of the carbodiimide compound to be used is selected from the range of 0.5 to 100 equivalents of the carbodiimide group contained in the cyclic carbodiimide compound per 1 equivalent of the acidic group. If the amount is less than 0.5 equivalent, carbodiimide may be used meaninglessly. When the amount is more than 100 equivalents, the properties of the substrate may be changed (changed). From such a viewpoint, the amount of the catalyst is preferably 0.6 to 75 equivalents, more preferably 0.65 to 50 equivalents, still more preferably 0.7 to 30 equivalents, and particularly preferably 0.7 to 20 equivalents.

Examples

The present invention is further illustrated by the following examples. Various physical properties were measured by the following methods.

(1) Identification of the Cyclic carbodiimide Structure by NMR

Synthetic cyclic carbodiimide compounds prepared by¹H-NMR、¹³C-NMR was confirmed. JNR-EX270 (manufactured by Japan Electron Ltd.) was used for NMR. Deuterated chloroform was used as a solvent.

(2) Identification of the carbodiimide skeleton of Cyclic carbodiimide by IR

The carbodiimide compound of the cyclic carbodiimide compound is one having a thickness of 2,100 to 2,200cm, which is characteristic of the carbodiimide compound produced by FT-IR^-1The confirmation of (1). As FT-IR, Magna-750, manufactured by Thermo-Nicolet (サ - モニコレ) (Inc.) was used.

(3) Concentration of carboxyl groups

The sample was dissolved in purified o-cresol, dissolved under a stream of nitrogen, and titrated with 0.05 defined ethanolic potassium hydroxide solution using bromocresol blue as indicator.

Reference example 1 Synthesis of Cyclic carbodiimide CC1 (scheme 1)

CC1：MW＝252

Step (1a)

In N₂Ortho-nitrophenol (0.11mol), 1, 2-dibromoethane (0.05mol), potassium carbonate (0.33mol), and 200ml of N, N-dimethylformamide were charged into a reaction apparatus equipped with a stirring apparatus and a heating apparatus under an atmosphere, and after 12 hours of reaction at 130 ℃, DMF was removed by reducing pressure, the resulting solid matter was dissolved in 200ml of dichloromethane, and 3 times of liquid separation was carried out with 100ml of water. The organic layer was dehydrated with 5g of sodium sulfate, and methylene chloride was removed under reduced pressure to obtain intermediate A (nitro compound).

Step (2a)

Subsequently, the intermediate product A (0.1mol), 5% palladium on carbon (Pd/C) (1g) and 200ml of ethanol/methylene chloride (70/30) were charged into a reaction apparatus equipped with a stirrer, and the reaction mixture was substituted with 5 hydrogens, reacted at 25 ℃ with hydrogen being supplied, and the reaction was terminated once hydrogen was not reduced. Pd/C was recovered, and upon removal of the mixed solvent, an intermediate product B (amine compound) was obtained.

Step (3a)

Then at N₂Triphenylphosphine dibromide (0.11mol) and 150ml 1, 2-dichloroethane were added to a reaction apparatus equipped with a stirring apparatus, a heating apparatus, and a dropping funnel under an atmosphere and stirred. A solution of intermediate B (0.05mol) and triethylamine (0.25mol) in 50ml of 1, 2-dichloroethane was slowly added dropwise thereto at 25 ℃. After completion of the dropwise addition, the reaction was carried out at 70 ℃ for 5 hours. Then, the reaction solution was filtered, and the filtrate was subjected to 5 times of liquid separation with 100ml of water. The organic layer was dehydrated with 5g of sodium sulfate, and 1, 2-dichloroethane was removed under reduced pressure to obtain intermediate C (triphenylphosphine compound).

Step (4a)

Then, atN₂Di-tert-butyl dicarbonate (0.11mol), N-dimethyl-4-aminopyridine (0.055mol) and 150ml of methylene chloride were charged into a reaction apparatus equipped with a stirring apparatus and a dropping funnel under an atmosphere and stirred. 100ml of methylene chloride in which intermediate C (0.05mol) was dissolved was slowly added dropwise thereto at 25 ℃. After the dropwise addition, the reaction was carried out for 12 hours. Thereafter, the solid obtained by removing methylene chloride was purified to obtain CC 1. The structure of CC1 was confirmed by NMR and IR.

Example 1 Synthesis of Cyclic carbodiimide CC2 (scheme 1)

CC2：MW＝516

Step (1A)

In N₂Ortho-nitrophenol (0.11mol), pentaerythritol tetrabromide (0.025mol), potassium carbonate (0.33mol), and 200ml of N, N-dimethylformamide were charged into a reaction apparatus equipped with a stirring apparatus and a heating apparatus under an atmosphere, and after 12 hours of reaction at 130 ℃, DMF was removed by reducing pressure, the resulting solid matter was dissolved in 200ml of dichloromethane, and 3 times of liquid separation was carried out with 100ml of water. The organic layer was dehydrated with 5g of sodium sulfate, and methylene chloride was removed under reduced pressure to obtain intermediate D (nitro compound).

Step (2A)

Subsequently, the intermediate product D (0.1mol), 5% palladium on carbon (Pd/C) (2g) and 400ml of ethanol/methylene chloride (70/30) were charged into a reaction apparatus equipped with a stirrer, and the reaction mixture was substituted with 5 hydrogens, reacted at 25 ℃ with hydrogen being supplied, and the reaction was terminated once hydrogen was not reduced. After recovering Pd/, the mixed solvent was removed to obtain an intermediate E (amine compound).

Step (3A)

Then at N₂A stirring device and a heating device are arranged downwards in the atmosphereTriphenylphosphine dibromide (0.11mol) and 150ml 1, 2-dichloroethane were added to the reaction apparatus of the dropping funnel and stirred. A solution of intermediate E (0.025mol) and triethylamine (0.25mol) in 50ml of 1, 2-dichloroethane was slowly added dropwise thereto at 25 ℃. After completion of the dropwise addition, the reaction was carried out at 70 ℃ for 5 hours. Then, the reaction solution was filtered, and the filtrate was subjected to 5 times of liquid separation with 100ml of water. The organic layer was dehydrated with 5g of sodium sulfate, and 1, 2-dichloroethane was removed under reduced pressure to obtain intermediate F (triphenylphosphine compound).

Step (4A)

Then, in N₂Di-tert-butyl dicarbonate (0.11mol), N-dimethyl-4-aminopyridine (0.055mol) and 150ml of methylene chloride were charged into a reaction apparatus equipped with a stirring apparatus and a dropping funnel under an atmosphere and stirred. 100ml of methylene chloride in which intermediate F (0.025mol) was dissolved was slowly added dropwise thereto at 25 ℃. After the dropwise addition, the reaction was carried out for 12 hours. Then, the solid obtained by removing methylene chloride was purified to obtain CC 2. The structure of CC2 was confirmed by NMR and IR.

Example 2 Synthesis of Cyclic carbodiimide CC2 (scheme 2)

Step (1A)

In N₂Ortho-nitrophenol (0.11mol), pentaerythritol tetrabromide (0.025mol), potassium carbonate (0.33mol), and 200ml of N, N-dimethylformamide were charged into a reaction apparatus equipped with a stirring apparatus and a heating apparatus under an atmosphere, and after 12 hours of reaction at 130 ℃, N-dimethylformamide was removed by reducing the pressure, and the resulting solid matter was dissolved in 200ml of dichloromethane and subjected to 3 times of liquid separation with 100ml of water. The organic layer was dehydrated with 5g of sodium sulfate, and methylene chloride was removed under reduced pressure to obtain intermediate D (nitro compound).

Step (2A)

Subsequently, the intermediate product D (0.1mol), 5% palladium on carbon (Pd/C) (1.25g) and 500ml of N, N-dimethylformamide were charged into a reaction apparatus equipped with a stirring apparatus, and the reaction mixture was reacted at 25 ℃ with hydrogen being supplied all the time, and the reaction was terminated once hydrogen did not decrease. Pd/C was recovered by filtration, and a solid precipitated upon addition of the filtrate to 3L of water. This solid was recovered and dried to obtain intermediate E (amine compound).

Step (3B)

Then at N₂To a reaction apparatus equipped with a stirring apparatus, a heating apparatus, and a Walter flask (ウオルタ I) to which alkaline water was added, were added under an atmosphere an intermediate product E (0.025mol), imidazole (0.2mol), carbon disulfide (0.2mol), and 150ml of 2-butanone. The temperature of the reaction solution was adjusted to 80 ℃ and the reaction was carried out for 15 hours. The solid precipitated after the reaction was collected by filtration and washed to prepare an intermediate G (thiourea compound).

Step (4B)

Then, in N₂To a reaction apparatus equipped with a stirring apparatus, intermediate G (0.025mol), p-toluenesulfonyl chloride (0.1mol), and 50ml of pyridine were added under an atmosphere and stirred. After 3 hours of reaction at 25 ℃, 150ml of methanol was added, and the mixture was further stirred at 25 ℃ for 1 hour. The precipitated solid was collected by filtration and washed to obtain CC 2. The structure of CC2 was confirmed by NMR and IR.

Example 3 Synthesis of Cyclic carbodiimide CC2 (scheme 2)

Step (1A)

Step (2A)

Step (3B)

Then at N₂To a reaction apparatus equipped with a stirring apparatus, a heating apparatus and a dropping funnel, 0.025mol of intermediate product E, 0.2mol of imidazole and 125ml of acetonitrile were charged under an atmosphere, and diphenyl phosphite (0.1mol) was charged into the dropping funnel. After 5 times of substitution with carbon dioxide, diphenyl phosphite was slowly added dropwise under stirring at 25 ℃ in a state where carbon dioxide was constantly supplied, and the reaction was carried out for 15 hours. The solid precipitated after the reaction was collected by filtration and washed to obtain an intermediate product H (urea compound).

Step (4B)

Then, in N₂To a reaction apparatus equipped with a stirring apparatus, intermediate H (0.025mol), p-toluenesulfonyl chloride (0.1mol), and 50ml of pyridine were added under an atmosphere and stirred. After 3 hours of reaction at 25 ℃, 150ml of methanol was added, and the mixture was further stirred at 25 ℃ for 1 hour. The precipitated solid was collected by filtration and washed to obtain CC 2. The structure of CC2 was confirmed by NMR and IR.

Example 4 Synthesis of Cyclic carbodiimide CC2 (scheme 3)

Step (1B)

In N₂To a reaction apparatus equipped with a stirring apparatus and a heating apparatus, o-chloronitrobenzene (0.125mol), pentaerythritol (0.025mol), potassium carbonate (0.25mol), tetrabutylammonium bromide (0.018mol), and 50ml of N, N-dimethylformamide were charged under an atmosphere, and reacted at 130 ℃ for 12 hours. After the reaction, the solution was added to 200ml of water, and the precipitated solid was collected by filtration. Washing the solid, drying to obtain intermediate productProduct D (nitro compound).

Step (2A)

Step (3B)

Step (4B)

Example 5 Synthesis of Cyclic carbodiimide CC2 (scheme 3)

Step (1B)

In N₂To a reaction apparatus equipped with a stirring apparatus and a heating apparatus, o-chloronitrobenzene (0.125mol), pentaerythritol (0.025mol), potassium carbonate (0.25mol), tetrabutylammonium bromide (0.018mol), and 50ml of N, N-dimethylformamide were added under an atmosphereAmine, at 130 ℃ for 12 hours. After the reaction, the solution was added to 200ml of water, and the precipitated solid was collected by filtration. The solid was washed and dried to obtain intermediate D (nitro compound).

Step (2A)

Step (3B)

Then at N₂To a reaction apparatus equipped with a stirring apparatus, a heating apparatus, and a Walter flask to which alkaline water was added, was added under an atmosphere an intermediate product E (0.025mol), imidazole (0.2mol), carbon disulfide (0.2mol), and 150ml of 2-butanone. The temperature of the reaction solution was adjusted to 80 ℃ and the reaction was carried out for 15 hours. The solid precipitated after the reaction was collected by filtration and washed to prepare an intermediate G (thiourea compound).

Step (4B)

Example 6 Synthesis of Cyclic carbodiimide CC2 (scheme 4)

Step (1B)

In N₂O-chloronitrobenzene (0.125mol), pentaerythritol (0.025mol) and potassium carbonate (0.25 m) were fed into a reaction apparatus equipped with a stirring apparatus and a heating apparatus under an atmosphereol), tetrabutylammonium bromide (0.018mol), 50ml of N, N-dimethylformamide, at 130 ℃ for 12 hours. After the reaction, the solution was added to 200ml of water, and the precipitated solid was collected by filtration. The solid was washed and dried to obtain intermediate D (nitro compound).

Step (2A)

Step (3A)

Then at N₂Triphenylphosphine dibromide (0.11mol) and 150ml 1, 2-dichloroethane were added to a reaction apparatus equipped with a stirring apparatus, a heating apparatus, and a dropping funnel under an atmosphere and stirred. A solution of intermediate E (0.025mol) and triethylamine (0.25mol) in 50ml of 1, 2-dichloroethane was slowly added dropwise thereto at 25 ℃. After completion of the dropwise addition, the reaction was carried out at 70 ℃ for 5 hours. Then, the reaction solution was filtered, and the filtrate was subjected to 5 times of liquid separation with 100ml of water. The organic layer was dehydrated with 5g of sodium sulfate, and 1, 2-dichloroethane was removed under reduced pressure to obtain intermediate F (triphenylphosphine compound).

Step (4A)

Then, in N₂Di-tert-butyl dicarbonate (0.11mol), N-dimethyl-4-aminopyridine (0.055mol) and 150ml of methylene chloride were charged into a reaction apparatus equipped with a stirring apparatus and a dropping funnel under an atmosphere and stirred. 100ml of methylene chloride in which intermediate F (0.025mol) was dissolved was slowly added dropwise thereto at 25 ℃. After the dropwise addition, the reaction was carried out for 12 hours. Thereafter, the solid obtained by removing methylene chloride was purified to obtain CC 2. The structure of CC2 was confirmed by NMR and IR.

Reference example 2 end-capping of polylactic acid by CC1

0.005 part by weight of tin octylate was added to 100 parts by weight of L-lactide (optical purity 100%, manufactured by Wucang wild chemical research, Ltd.), the reaction was carried out at 180 ℃ for 2 hours in a nitrogen atmosphere using a reactor equipped with a stirring paddle, 1.2 times equivalent of phosphoric acid was added to tin octylate as a catalyst deactivator, and then the remaining lactide was removed at 13.3Pa to prepare a poly-L-lactic acid which was flaked (チツプ). The carboxyl group concentration of the obtained poly L-lactic acid was 14 equivalents/ton.

Each 100 parts by weight of the obtained poly L-lactic acid was melt kneaded with 0.5 parts by weight of CC1 using a 2-shaft extruder (cylinder temperature 260 ℃ C.) for a residence time of 3 minutes. The carboxyl group concentration is reduced to 0.4 equivalent/ton or less. In addition, the extruder outlet after kneading was free from isocyanate odor.

Reference example 3 end-capping of polylactic acid by CC2

In reference example 2, a cyclic carbodiimide: CC1 was replaced with a cyclic carbodiimide: CC2 was reacted under the same conditions as above, and the carboxyl group concentration was reduced to 0.3 eq/ton or less. In addition, the extruder outlet after kneading was free from isocyanate odor.

Reference example 4 capping of polylactic acid by straight-chain carbodiimide Compound

In reference example 2, a cyclic carbodiimide compound: CC1 was replaced with linear carbodiimide "Stabaxol (スタバクゾ - ル)" I manufactured by RheinChemie Japan (ラインケミ - ジヤパン) (strain) under the same conditions, and the reaction was carried out under a carboxyl group concentration of 0.4 equivalents/ton, but a strong isocyanate-malodor was generated at the extruder outlet.

Reference example 5 end-capping of Polyamide by CC2

Poly (m-xylylene adipamide) (MX ナイロン S6001, manufactured by Mitsubishi Gas Chemical Company, Inc. (Mitsubishi ガス Chemical Co., Ltd)) is a polyamide containing m-xylylenediamine and adipic acid, and the carboxyl group concentration is 70 equivalents/ton. Each 100 parts by weight of the above-mentioned polymetaxylxylylene adipamide was melt kneaded together with 2.0 parts by weight of CC2 using a 2-shaft extruder (cylinder temperature 260 ℃ C.) for a residence time of 3 minutes. The carboxyl group concentration is reduced to 1.2 equivalents/ton or less. In addition, the extruder outlet after kneading was free from isocyanate odor.

Reference example 6 blocking of Polyamide by a Linear carbodiimide Compound

In reference example 2, a cyclic carbodiimide compound: CC2 was replaced with linear carbodiimide "Stabaxol" I manufactured by RheinChemie Japan, and the reaction was carried out under the same conditions, wherein the carboxyl group concentration was 2.2 equivalents/ton, but a strong isocyanate-malodor was generated at the extruder outlet.

ADVANTAGEOUS EFFECTS OF INVENTION

The cyclic carbodiimide compound obtained from the intermediate of the present invention is effective for stabilizing the hydrolyzable component of the polymer compound. In addition, the secondary generation of free isocyanate compounds can be suppressed at this time. The cyclic carbodiimide compound obtained from the intermediate of the present invention can block the terminal of the polymer compound, suppress the generation of an offensive odor caused by the isocyanate compound, and prevent the deterioration of the working environment. When the terminal of the polymer compound is blocked with the cyclic carbodiimide compound, an isocyanate group is formed at the terminal of the polymer compound, and the polymer compound can be increased in molecular weight by the reaction of the isocyanate group.

The cyclic carbodiimide compound of the present invention also has an effect of trapping a free monomer or a compound having another acidic group in a polymer compound.

In addition, the cyclic carbodiimide compound obtained from the intermediate of the present invention has a cyclic structure, and therefore has an advantage that the end-capping can be performed under milder conditions than the linear carbodiimide compound.

According to the production method of the present invention, a cyclic carbodiimide can be easily produced. The cyclic carbodiimide compound obtained from the intermediate of the present invention is useful as a blocking agent for a polymer compound. The cyclic carbodiimide compound obtained from the intermediate of the present invention is useful as a scavenger of an acidic group, particularly a scavenger of a free compound in a polymer compound.

The difference between the linear carbodiimide compound and the cyclic carbodiimide compound in the reaction mechanism of the end-capping is as follows.

If the linear carbodiimide compound (R) is used₁-N＝C＝N-R₂) When used as an end-capping agent for a polymer compound having a carboxyl terminal, a reaction represented by the following formula occurs. Wherein W is the main chain of the polymer compound. The linear carbodiimide compound reacts with a carboxyl group to form an amide group at the terminal of the polymer compound, thereby forming an isocyanate compound (R)₁NCO) is free.

On the other hand, when a cyclic carbodiimide compound is used as a blocking agent for a polymer compound having a carboxyl terminal, a reaction represented by the following formula occurs. It is known that the cyclic carbodiimide compound does not release an isocyanate compound by reacting with a carboxyl group to form an isocyanate group (-NCO) at the terminal of the polymer compound via an amide group.

(wherein Q represents an aliphatic group, an alicyclic group, an aromatic group or a 2-to 4-valent bonding group which is a combination of these groups, and may contain a hetero atom or a substituent.)

Further, if 1 ring has 2 or more carbodiimides, there is a disadvantage that an isocyanate compound is liberated due to the reaction of the carbodiimides.

Industrial applicability

The cyclic carbodiimide compound obtained from the intermediate of the present invention is preferably suitable for stabilizing an organic polymer compound containing a hydrolyzable functional group as a constituent.

Claims

1. A compound represented by the following formula (S),

wherein X is a 4-valent group represented by the following formula (i-4),

wherein Z is an oxygen atom or a sulfur atom.

2. The compound of claim 1, wherein Ar¹～Ar⁴Each independently an o-phenylene group or a 1, 2-naphthalenediyl group which may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

3. The compound of claim 1 represented by the following formula (C),

in the formula, X, Ar¹～Ar⁴The same as the above formula (S).

4. The compound of claim 1 represented by the following formula (D),

in the formula, X, Ar¹～Ar⁴The same as the above formula (S).

5. The compound of claim 1 represented by the following formula (E-1),

in the formula, X, Ar¹～Ar⁴、Ar^aThe same as the above formula (S).

6. The compound of claim 1 represented by the following formula (E-2),

in the formula, X, Ar¹～Ar⁴And Z is the same as the above formula (S).

7. The compound of claim 1 represented by the following formula (G),

in the formula, X, Ar¹～Ar⁴The same as the above formula (S).