JP2002173465A - Method for producing condensed dehydration product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing high-purity, light-colored condensed dehydration product(s). SOLUTION: This method for producing at least one condensed dehydration product selected from the group consisting of a (thio)ester, a (thio)acetal, a (thio)ketal, an amide, an aldimine and a ketimine comprises condensed dehydration between an organic carbonyl compound and a compound having 1-10 active hydrogen-containing one or more group(s) selected from the group consisting of an alcoholic hydroxy group, amino group and mercapto group in the presence of a titanium catalyst of the general formula 1; =Ti(OCOQCOOM)2 (M is an alkali metal; and Q is a direct bond or 1-10C alkylene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a dehydrated condensate obtained from an active hydrogen-containing compound and an organic carbonyl compound.

[0002]

2. Description of the Related Art Conventionally, a dehydration condensation reaction between an active hydrogen-containing compound and an organic carbonyl compound has been carried out by benzene, toluene,
It has been carried out in a solvent such as xylene or in the absence of a solvent using an acidic catalyst such as sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, phosphoric acid, boron trifluoride diethyl ether complex, aluminum chloride, and activated clay.

[0003]

However, the conventional dehydration / condensation method requires a large amount of an acid catalyst in order to carry out the reaction smoothly, and the resulting dehydration / condensation product has problems such as marked coloring. Was. Further, during the dehydration-condensation reaction, side reactions such as rearrangement of carbon-carbon unsaturated groups, isomerization, and cleavage of an ether bond occur, so that the purity of the product is reduced.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides a compound (A) having 1 to 10 one or more active hydrogen-containing groups selected from the group consisting of an alcoholic hydroxyl group, an amino group and a mercapto group,
Dehydration-condensation with the organic carbonyl compound (B) to give a (thio) ester [which represents an ester and / or a thioester; similar expressions will be used hereinafter], (thio) acetal, (thio) ketal, amide, aldimine and ketimine In the method for producing one or more dehydration condensates selected from the group consisting of the following, a titanium catalyst (C) represented by the following general formula (1) is used [however, where (A) is represented by the following general formula ( When esterifying with a carboxylic acid using only the polyoxyalkylene alcohol represented by 2), formic acid, oxycarboxylic acid, amino acid, alicyclic carboxylic acid and / or C21 or more are used as at least a part of the carboxylic acid. Using a carboxylic acid]; a dehydration condensate (D1) obtained by the production method. A compounding agent for producing a synthetic resin comprising the dehydration condensate (D1); and a resin composition containing the compounding agent and the synthetic resin; one or two selected from the group consisting of alcoholic hydroxyl groups, amino groups, and mercapto groups. A compound (A) having 1 to 10 or more kinds of active hydrogen-containing groups and an organic carbonyl compound (B) are dehydrated and condensed in the presence of a titanium catalyst (C) represented by the following general formula (1) ( An intermediate for producing a synthetic resin comprising one or more dehydration condensates (D2) selected from the group consisting of thio) esters, (thio) acetals, (thio) ketals, amides, aldimines and ketimines; An antistatic agent comprising a dehydration condensate (D2). O = Ti (OCOQCOOM) ₂ (1) [wherein, M represents an alkali metal, and Q represents a direct bond or an alkylene group having 1 to 10 carbon atoms. R- [O (AO) m-H] n (2) wherein R is an n-valent hydrocarbon group or hydrogen atom having 1 to 30 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, m Is 4 ~
An integer of 200 and n represents an integer of 1 to 10. ]

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), M includes lithium, sodium, potassium, rubidium and cesium. Preferred are lithium, and especially sodium and potassium. Q is a direct bond (single bond) or an alkylene group having 1 to 10 carbon atoms. Alkylene groups include straight-chain and branched alkylene groups, including methylene, ethylene, butylene, octylene and decylene groups. Preferred are an alkylene group having 1 to 4 (more preferably 1 to 2) carbon atoms, and particularly a direct bond. Specific examples of the catalyst (C) include alkylenedicarboxylic acids (C2 to C12, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid) titanium alkali (sodium, potassium, lithium, and the like). Preferred from the viewpoint of catalytic activity are titanium malonate alkali, and particularly titanium oxalate alkali.

The active hydrogen-containing compound (A) in the present invention
Is one or two selected from the group consisting of an alcoholic hydroxyl group, a mercapto group and a primary or secondary amino group
1 to 10 or more active hydrogen-containing groups, preferably 1 to
It is a compound having six. The compound (A) includes a compound (A1) having an alcoholic hydroxyl group, a compound (A2) having an amino group, and a compound (A3) having a mercapto group.
And combinations of two or more of these.

[0007] (A1) includes aliphatic, alicyclic and aromatic alcohols and (poly) oxyalkylene alcohols having 1 to 10 valences or more, and mixtures of two or more of these. These (polyoxyalkylene) alcohols include those represented by the following general formula (6) and modified products thereof. ^{R 0 - [(A 0 O} ) k-H] n (6) [ wherein, the remaining of A ⁰ is (substituted) alkylene group having 2 to 30 carbon atoms, R ⁰ is a compound having n active hydrogen atoms Group,
n is an integer of 1 to 10 or more, k is 0 or 1
It is an integer of 200 (however, when R ⁰ does not have an alcoholic hydroxyl group, at least one of the n k's is 1 or more). ]

The (substituted) alkylene group A ⁰ has 2 to 2 carbon atoms.
Includes 30 alkylene groups, phenyl substituted alkylene groups and halogen substituted alkylene groups. Oxyalkylene groups (A ⁰ O) (Where k is 1 or more) is formed by ring-opening polymerization (addition to an active hydrogen atom-containing compound) of an alkylene oxide (hereinafter abbreviated as AO). AO has C
2-30 (preferably 2-12, especially 2-4) AO, such as ethylene oxide (E
O), propylene oxide (PO), 1,2-, 2,
3-, 1,3- and 1,4-butylene oxide, C
5-30 α-olefin oxides; and substituted AO;
For example, styrene oxide and epihalohydrin (epichlorohydrin, epibromohydrin, etc.) are included.
AO may be used alone (eg, EO alone, PO alone, 1,4-butylene oxide (THF) alone) or in combination of two or more (eg, a combination of PO and EO, PO and / or E
O and THF). In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixture of both (chips after random addition) may be used. The preferred AO varies depending on the application of the dehydration condensate. For applications requiring hydrophilicity (for example, an antistatic agent or a precursor thereof), EO alone, or a combination of EO and other AO (PO and / or THF) (random) ,
Block and mixed system of both; EO content in AO is 1
0% or more, more preferably 50% or more, especially 60% or more); for other uses (where hydrophilicity is not required), PO alone, THF alone, a combination thereof, and EO and other AO containing less EO than the above. (PO and / or TH
Combination of F) (random, block and mixed system of both)
Is also preferred. Above and below,% represents% by weight. The addition of AO may be carried out in the presence of an alkali catalyst such as potassium hydroxide, sodium hydroxide or cesium hydroxide, or an acid catalyst such as boron trifluoride diethyl ether complex. Catalysts which give narrow molecular weight distribution AO adducts, such as perhalic acid (salt), sulfuric acid (salt), as described
The reaction may be performed in the presence of phosphoric acid (salt) or nitric acid (salt).

R ⁰ is a residue obtained by removing an active hydrogen atom from a compound having n active hydrogen atoms. The active hydrogen atom-containing compound constituting the residue R ⁰ includes compounds having one or two to ten or more active hydrogen atom-containing groups (hydroxyl group, amino group, mercapto group, etc.). Examples of the compound include an alcohol, a phenol, an amino group-containing compound, a mercapto group-containing compound, an active hydrogen compound having a (thio) ether bond, SO, SO ₂ , CO, a halogen atom, an ionic group or a salt-forming group, and Can be used. For example, an initiator constituting the residues R, R ¹ , R ² and R ³ of the (polyoxyalkylene) alcohol of the following general formulas (2) to (5) [general formula ^{R- (OH) n, R 1} -OH, R 2 - (OH) alcohols and phenols, monovalent and polyvalent represented by p + q (2-valent and 3 to 10-valent), and the general formula R ³ - ( H) Amino group-containing compounds, mercapto group-containing compounds and active hydrogen compounds represented by n].

As (A1), a polyoxyalkylene alcohol represented by the following general formula (2):
(Polyoxyalkylene) alcohols represented by formulas (1) to (5), modified (polyoxyalkylene) alcohols represented by formulas (2) to (5), and mixtures of two or more of these. ^{R 1 -O (AO) r-} H (3) [H- (OA) r-O] p-R 2 - [O (AO) m-H] q (4) R 3 - [(AO) k- H] n (5) [in the formula, a is an alkylene group having C2-4, 1 dihydric alcohol or phenol residue of R ¹ is H or C1-30, polyhydric alcohols R ² is 3-10 divalent, C5 and above 2
A residue of a polyhydric alcohol or a polyhydric phenol having 2 to 10 valences, r is an integer of 0 or 1 to 3 (provided that R ¹ is a residue of H or a monohydric phenol and R ² is a residue of a polyhydric phenol) Is an integer of 1 to 3), m is an integer of 4 to 200, p is an integer of 1 or more, q is 0 or an integer of 1 or more (provided that the sum of p and q is equal to the valence of R ² ) , R ³ has n active hydrogen atoms, a mercapto group-containing compound, an amino group-containing compound, or a (thio) ether bond, SO,
A residue of a compound having SO ₂ , CO, a halogen atom, an ionic group or a salt-forming group, n is an integer of 1 to 10, k
Is 0 or an integer of 1 to 200 (however, when R ³ is a compound having no alcoholic hydroxyl group, at least one of n k's is 1 or more). ]

In the general formula (2), as the n-valent hydrocarbon group R, a residue excluding a hydroxyl group among monovalent and polyvalent alcohols and phenols described below (the same applies hereinafter) is a hydrocarbon group. Alcohol and phenol residues are included. In the general formula (5), the residue R ³ is a compound having a mercapto group, a compound having an amino group, or an activity having a (thio) ether bond, SO, SO ₂ , CO, a halogen atom, an ionic group or a salt-forming group. It is a residue obtained by removing n active hydrogen atoms from a hydrogen compound. The active hydrogen compound constituting the residue R ³ includes mono- and polyhydric alcohols having a (thio) ether bond, SO, SO ₂ , CO, a halogen atom, an ionic group or a salt-forming group. Includes phenols, amino compounds and mercapto compounds.

In the general formulas (2) to (5), C2 of A
The alkylene groups of 1 to 4 include a 1,2-ethylene group,
-And 1,3-propylene groups, 1,2-, 2,3-,
Includes 1,3- and 1,4-butylene groups and isobutylene groups. m is preferably 4 to 100, especially 4 to 5
Integer of 0 and k are preferably integers of 1 to 100, especially 1 to 50, n m, p r and q m, n k
May be the same or different, and when two or more A are present, they may be the same or different. Among the (polyoxyalkylene) alcohols of the general formulas (2) to (5), a polyoxyalkylene alcohol [other than those having r of 0 in the general formula (3)] is used as an initiator [general formula R- (OH ) N, R ¹ -OH, R ^2- (OH) p + q, R ^3-
(H) n] and one or more C2-4 AOs. When two or more types are used in combination, A
As in the case of the general formula (6), the addition form of O may be random, block, or a mixture of both.

The monohydric alcohol constituting the residues R ⁰ , R ¹ and R ³ includes C1-30 (preferably 2-1)
8) the linear and / or branched, saturated and unsaturated, natural and synthetic, aliphatic alcohols [alkanols such as methanol, ethanol, n- and i-
Propanol, n-, i-, sec- and t-butanol, n-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, nonyl alcohol, lauryl alcohol, stearyl alcohol and synthetic alcohols (Tigler alcohol, oxo Alcohols, tridecyl alcohols, synthetic secondary alcohols, etc.); unsaturated alcohols such as (meth) allyl alcohol and oleyl alcohol]; C3-30
(Preferably 3 to 10) linear and / or branched saturated and unsaturated alicyclic alcohols (cycloalkanols, cycloalkenols and the like, for example, cyclopentanol, cyclohexanol, cyclododecanol and 2
-Cyclohexenol); 7 to 30 (preferably 7-1)
8) aromatic alcohols (eg, benzyl alcohol, phenethyl alcohol and 6-phenyl-1-hexanol); and heterocyclic alcohols (eg, tetrahydrofurfuryl alcohol).

The monohydric phenols constituting the residues R ⁰ and R ¹ include C6-30 mono- and polycyclic phenols, such as phenol, α- and β-naphthol, and 1-2 of these. C1-20 or more (cyclo) alkyl (methyl, ethyl, n- and i-
Substituents having propyl, nonyl, nonadecyl and tetracosyl, cyclohexyl, etc.), aryl (phenyl, etc.) and / or aralkyl (benzyl, styryl, etc.), for example o-, m- and p-cresol, 3,
5-xylenol, carvacrol, thymol, mono-
And di-nonylphenol, cyclohexylphenol, phenylphenol, cumylphenol, benzylphenol, styrene (1 to 3 mol) phenol, styrene (1 to 3 mol) benzylphenol, and the like.

The dihydric alcohols constituting the residues R ⁰ and R include C2-4 alkylene glycols (ethylene glycol, 1,2- and 1,3-propanediol, 1,2-, 2,3- , 1,3- and 1,4-butanediol). The C5 or more dihydric alcohols constituting the residue R ⁰ and R ^2, aliphatic C5-30, include cycloaliphatic and aromatic dihydric alcohol. Examples of the aliphatic dihydric alcohol include neopentyl glycol, 1,6-hexanediol, octanediol,
2,2,4-trimethyl-1,3-pentanediol,
1,12-dodecanediol and octadecanediol; alicyclic dihydric alcohols include 1,4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-cyclooctanediol, Cyclopentanediol, and 2,2-
Bis (4,4′-hydroxycyclohexyl) propane and the like; as the aromatic dihydric alcohol, xylylene diol, 1-phenyl-1,2-ethanediol, 1,4
-Bis (hydroxyethyl) benzene and the like. The dihydric alcohols that make up residues R ⁰ and R ³ include thiodiglycol.

³ constituting residues R ⁰ , R ¹ , R ² and R 3
As the alcohol having a valence of 10 or more, C3 to
30 or more alkane polyols having 3 to 10 valences or more, and intermolecular or intramolecular dehydrates thereof, saccharides and derivatives thereof (such as glycosides) are included. Specifically, triols (glycerin, trimethylolpropane, trimethylolethane, 1,2,3-heptanetriol, 1,2,6-hexanetriol and the like), tetravalent to octavalent or higher polyols [pentaerythritol , Diglycerin, sorbitol, xylitol, mannitol, sorbitan, dipentaerythritol, glucose, fructose, sucrose, α-methylglucoside, polyglycerin (tri-hexamer), polyvinyl alcohol and the like].

The polyhydric phenol constituting the residues R ⁰ , R ² and R ³ is a dihydric phenol, for example, C6-30
Monocyclic dihydric phenols (such as catechol, hydroquinone, pyrogallol, resorcinol and urushiol), fused ring dihydric phenols (such as dihydroxynaphthalene),
And a bisphenol compound [general formula: HO-Ar-Z
-Ar-OH (wherein, Ar is a phenylene or naphthylene group optionally substituted with halogen, Z is a covalent bond, a C1-6 alkylene group, an alkylidene group, a cycloalkylidene group, an arylalkylidene group, O, SO,
SO ₂ , CO, S, CF ₂ , C (CF ₃ ) ₂ or NH. ), For example, bisphenol A,
Bisphenol F, bisphenol S, bisphenol AD, bisphenol B, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, binaphthol, chlorinated bisphenol A, brominated bisphenol A, octachloro-4,4'-dihydroxybiphenyl 3) to 10-valent polyphenols, for example, monocyclic trihydric phenols (such as pyrogallol and phloroglucinol), polycyclic polyhydric phenols [1,1,1-tris (4-hydroxyphenyl) ethane and novolak] (Condensation degree 2 to 9), etc.].

The amino group-containing compounds constituting the residues R ⁰ and R ³ include ammonia; aliphatic, alicyclic, aromatic (fatty) and heterocyclic amines having a primary or secondary amino group; Other NH or NH ₂ group-containing compounds,
For example, amide compounds and (thio) urea compounds are included. Aliphatic amines include C1-40 (preferably 2-36) saturated and unsaturated aliphatic monoamines and polyamines. As the monoamine, C1 to
20 (preferably 1-4) alkyl or C3-2
Mono- and di-alkyl and / or alkenylamines having one or two zero alkenyl groups, such as primary amines (methylamine, ethylamine, n- and i-propylamine, n-, i-, sec- and t-
Butylamine, amylamine, isoamylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-
Dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, laurylamine, oleylamine, stearylamine, etc.) and secondary amines (dimethylamine, Diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, diamylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, etc.); C
Mono- and di-alkanolamines having 1 to 2 (preferably 1 to 4) hydroxyalkyl groups, such as monoethanolamine and diethanolamine, may be mentioned.

As the polyamine, a diamine such as C
2 to 12 alkylenediamines (ethylenediamine, propylenediamine, trimethylenediamine, 1,4-butanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc.), and their alkyl (C1-4) substitution (N-alkyl, N, N-dialkyl, N, N′-dialkyl-substituted); and polyfunctional (trifunctional or more; the same applies hereinafter) amines, for example, polyalkylene polyamines (C 2-6 of alkylene group, polymerization degree 2) ~ 5 or more: diethylenetriamine, 3,3'-imino-bispropylamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, etc., alkanetriamine (triaminomethylpropane, 1,6,11-undecanetriamine, 1,8- Amino-4-aminomethyl octane, 1,3,6-hexamethylene triamine), their alkyl (C1 -4) substituted products thereof.

Cycloaliphatic amines include C3-40 (preferably 3-36) cycloaliphatic monoamines and polyamines. Monoamines include primary amines such as cyclopropylamine, cyclopentylamine, cyclohexylamine, C1-20 linear or branched alkyl (such as methyl, n- and i-propyl, nonyl, lauryl and nonadecyl) groups 1-2. A mono- or dialkylcyclohexylamine having an alicyclic ring; a secondary amine such as dicycloalkylamine (such as dicyclohexylamine, dicyclopentylamine and dicyclopropylamine); and a C1-20 linear or branched bond to a nitrogen atom. N-alkyl-cyclohexylamine having an alkyl group of Polyamines include diamines such as 1,2-, 1,3- and 1,
4-cyclohexanediamine, diaminodicyclohexylmethane, isophoronediamine, N-aminoalkyl (C2-6) cyclohexylamine (eg, N-aminoethylcyclohexylamine, N-aminopropylcyclohexylamine) and dimer diamine [JP-B 39-39]
No. 17086, dimerized fatty acid (dimer acid)
Such as diamines obtained by nitrilation with ammonia and further hydrogenation]; and polyfunctional amines such as triamine (1,3,5-cyclohexanetriamine and bicycloheptanetriamine.

Aromatic (fatty) amines include C6-40.
(Preferably 6-36) mononuclear and polynuclear aromatic and araliphatic monoamines and polyamines. Monoamines include primary amines such as aniline, naphthylamine, C1-20 linear or branched alkyl (methyl, n- and i-propyl, nonyl,
Mono-) having one or two groups in the benzene nucleus
Or di-alkylaminobenzenes (toluidine, xylidine, cumidine and the like), araliphatic amines (benzylamine and the like); -Alkyl-phenylamine, diphenylamine and araliphatic amine (dibenzylamine). Polyamines include diamines such as phenylenediamine, diphenylmethanediamine, diphenyletherdiamine, naphthylenediamine, C1
Mono- or di-alkyl-substituted phenylenediamines having 1 to 2 linear or branched alkyl (such as methyl, n- and i-propyl, nonyl, lauryl and nonadecyl) groups and diphenylmethanediamine (tolylenediamine, Diethyltolylenediamine, dimethyldiphenylmethanediamine, etc.), araliphatic diamines (xylylenediamine, etc.); and polyfunctional amines such as triamines [triaminobenzene, Cl-
20 linear or branched alkyl (such as methyl, n- and i-propyl, nonyl and lauryl) groups
Mono- or di-alkyltriaminobenzene having two, triphenylmethanetriamine, polyphenylmethanepolyamine, etc.].

Heterocyclic amines include C2-40 (preferably 4-36) monoamines and polyamines. These include those described in U.S. Pat. No. 4,298,487; secondary amines such as 2
Having a primary amino group bonded to a hydrocarbon group [pyrrolidine,
Piperidine, pyrroline, pyrrole, (iso) indoline, (iso) indole, carbazole, etc.] in which a secondary amino group is bonded to an oxygen-containing hydrocarbon group [morpholine, xanthene, pyrrolidone, etc.] and a secondary amino group containing nitrogen Those bonded to a hydrocarbon group [imidazoline, imidazole, pyrazoline, purine, 1-H-indazole,
Piperazine, N-alkyl (C1-4) piperazine, imidazolidine, N-alkyl (C1-4) imidazolidine, etc.] and those in which a secondary amino group is bonded to a sulfur-containing hydrocarbon group [phenothiazine, etc.]; primary amines For example, N-aminoalkyl (C2-4) -substituted secondary amines (such as aminoethylpiperazine);
Heterocyclic polyamines described in JP 21044A are exemplified.

As the amide compound, US Pat.
No. 58,766, lactams [C4-13, preferably 6-12 (caprolactam, enantholactam, laurolactam, undecanolactam, etc.)] and polyamide oligomers [oligomers of the above lactams, ω of C3-12] A polycondensate of an aminocarboxylic acid, a polycondensate of a dicarboxylic acid and a diamine]; and the above-mentioned amine [primary monoamine or polyamine such as (polyalkylene) polyamine] and a carboxylic acid [(B1) described later)
For example, (poly) amides with dicarboxylic acids (such as adipic acid, dimer acid and the like) and / or monocarboxylic acids], for example, those described in US Pat. No. 3,992,312. Examples of the (thio) urea compound include (thio) urea, and a compound having a (thio) urea bond [for example, N- and N, N′-alkyl (C1-4) -substituted compounds, and the above amine and isocyanate compound (for example, Reaction product with)).

The mercapto group-containing compounds constituting the residues R ⁰ and R ³ include C1-24 (preferably 2-18) aliphatic thiols and C3-24 (preferably 3-10) alicyclic thiols. , C6-20 (preferably 6-18) araliphatic thiols and C6-20 (preferably 6-6)
10) The aromatic thiol and the like are included. These include those corresponding to hydroxyl group-containing compounds [(polyoxyalkylene) alcohols represented by the aforementioned general formulas (2) to (4), the above-mentioned phenols and the like] (hydroxyl groups are replaced with mercapto groups); glycidyl compounds (for example, See below)
And hydrogen sulfide (for example, hydrogen sulfide adduct of glycerin triglycidyl ether) and the like. Preferred are trithiols, and especially mono- and di-thiols.

Examples of the active hydrogen-containing compound having a (thio) ether bond constituting the residues R ⁰ and R ³ include the above-mentioned alcohols and phenols, as well as amino compounds such as thiodiethylamine and thioaniline.
The active hydrogen atom-containing compound having an ionic or salt-forming group constituting the residues R ⁰ and R ³ includes a compound having an ionic group (anionic group or cationic group) and a salt-forming compound which is a precursor thereof. Compounds having a sexual group are included. Specifically, dimethylolalkanoic acid (C4-2)
0, for example, dimethylolpropionic acid) and other compounds having a salt-type group or a salt-forming group described in JP-B-43-9076, JP-B-42-24192 and JP-B-42-19278. For example, an anionic group [a carboxylic acid (salt) group, a sulfonic acid (salt) group, a phosphorus-containing acid (phosphinic acid, phosphonic acid, phosphonous acid, phosphoric acid, phosphorous acid) (salt) group, etc.] or a cationic group Examples thereof include alcohols having [tertiary amino group, quaternary ammonium base, etc.], amino compounds and mercapto compounds.

Examples of the polyoxyalkylene alcohol represented by the general formula (2) include those obtained by adding AO to the above-mentioned alcohol or phenol in an amount of 4 × n mol or more, such as lauryl alcohol EO 10 mol adduct, dodecanediol EO 20 mol adduct and triol. Methylol propane P
O 30 mol adduct and the like. Examples of the alcohol represented by the general formula (3) include the above-mentioned monohydric or dihydric alcohol (for example, ethylene glycol or the like), and those obtained by adding 1 to 3 mol of AO to the above-mentioned monohydric alcohol or monohydric phenol (for example, lauryl alcohol EO2 mol) Adduct, cyclohexanol EO 3 mol adduct and phenol PO 2 mol adduct).

Examples of the alcohol represented by the general formula (4) include those obtained by adding [4 × (p + q) -1] mol or less of AO to the polyhydric alcohol or polyphenol (for example, 15 mol of pentaerythritol EO adduct) And the like. [3 × (p + q)] mol or less of PO and EO are added to the polyhydric alcohol or polyhydric phenol (for example, 20 mol of EO is added to 9 mol of pyrogallol PO adduct), hydroquinone, etc. EO
Examples include 2 mol / PO4 mol random adduct, 5 mol dodecanediol EO adduct, and 5 mol 1,4-cyclohexanediol PO adduct.

Examples of the alcohol represented by the general formula (5) include stearylamine EO 20 mol adduct, caprolactam EO 1-2 mol adduct, urea PO 2-4 mol adduct; dimercaptoethane PO 30 mol adduct; dimethylolpropionic acid (Salt) and its 1 to 2 mol adduct of EO, diethylethanolamine and its quaternary compound, and the like. Of these, preferred are 1 to 8 valent alcohols, more preferred are 1 to 6 valent alcohols, and particularly preferred are 1 to 3 valent alcohols.

Modified products of the (polyoxyalkylene) alcohols represented by the general formula (6) [such as the (polyoxyalkylene) alcohols represented by the general formulas (2) to (5)] include these (polyoxyalkylene) alcohols. ) 2 moles or more of an alcohol coupled with a polyhalide in the presence of an alkali (eg, caustic soda), linked via an ether linkage, coupled with a polyepoxide, and coupled with a polyisocyanate. Bonded via a urethane bond). Coupling agents used for denaturation (polyhalides,
The ratio of (polyepoxide, polyisocyanate) and (polyoxyalkylene) alcohol is such that 1 mole of (polyoxyalkylene) alcohol is equivalent to 1 mole of coupling agent (forming a modified product having one coupling agent residue in one molecule). Is preferred, but even if the mixture containing the unreacted (polyoxyalkylene) alcohol is formed using more than 1 mol of the latter, the latter is used in less than 1 mol within a range where the hydroxyl group becomes an excess equivalent, and the amount of the compound in one molecule is reduced. A modified product having two or three or more coupling agent residues may be formed.

Examples of the polyhalide include C1-10 polyhaloalkanes, for example, alkylene dihalides (such as methylene dichloride). Polyepoxides include aliphatic, alicyclic, heterocyclic and aromatic. Examples of aromatic compounds include diglycidyl ethers of dihydric phenols (for example, bisphenol A), polyglycidyl ethers of phenol or cresol novolak resin, glycidyl aromatic polyamines (eg, N, N-diglycidylaniline); As the cyclic system, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide,
Ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) Butylamine, a nuclear hydrogenated product of the aromatic diepoxide compound, and the like; and the aliphatic system includes polyhydric alcohols (such as those described above, for example, ethylene glycol, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether;
Examples thereof include polyglycidyl esters of polycarboxylic acids (described below, for example, adipic acid) and epoxidized oils (eg, epoxidized soybean oil).

As the organic polyisocyanate, C (N
6-20 aromatic polyisocyanates such as 1,3- and / or 1,
4-phenylenediisocyanate, 2,4- and / or 2,6-tolylenediisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) 4,4'-di Isocyanatobiphenyl, 3,3'-dimethyl-4,4 '
-Diisocyanatobiphenyl, 3,3'-dimethyl-
4,4'-diisocyanatodiphenylmethane, 1,5-
Diisocyanates such as naphthylene diisocyanate and polyphenylmethane polyisocyanate (crude MD
I) polyfunctional polyisocyanates such as triphenylmethane triisocyanate; C2-18 aliphatic polyisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate;
2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatoethyl caproate, bis (2-isocyanatoethyl)
Diisocyanates such as fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate; ), 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-
Polyfunctional polyisocyanate such as hexamethylene triisocyanate; C4-15 alicyclic polyisocyanate;
For example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5 Di- and / or diisocyanates such as 2,6-norbornane diisocyanate; and polyfunctional polyisocyanates such as bicycloheptane triisocyanate; C8-15 araliphatic polyisocyanates such as m- and / or p-xylylene diisocyanate, α, diisocyanates such as α, α ′, α′-tetramethylxylylene diisocyanate; modified products of these polyisocyanates, for example, urethane modified products [(h
Modified with the divalent or polyfunctional alcohol described in 1), Modified urea [Modified with the diamine or polyfunctional amine alcohol described in (h3)], Modified carbodiimide, Modified uretdione, and isocyanurate Modified products and the like; and mixtures of two or more thereof can be used.

The compound (A2) having an amino group includes the aliphatic, alicyclic, and aromatic compounds having a primary or secondary amino group described in the examples of the amino group-containing compound constituting the residues R ⁰ and R ^3. (Aliphatic) and heterocyclic amines; and those obtained by reducing the hydroxyl group of the (polyoxyalkylene) alcohol or the phenol of the above (A1) to an amino group (for example, a cyanoethylated compound obtained by reacting with acrylonitrile) Hydrogenated)
And so on. Compound having a mercapto group (A3)
Are the aliphatic, alicyclic, araliphatic and aromatic thiols mentioned in the examples of the mercapto group-containing compound constituting the residues R ⁰ and R ³ [the hydroxyl group of the (polyoxyalkylene) alcohol (A1)] Is replaced by a mercapto group (e.g., 1,4-butanedithiol)].
Preferred are trithiols, and especially monothiols, dithiols.

In the present invention, the organic carbonyl compound (B) includes a carboxyl group-containing compound (B1), an aldehyde (B2) and a ketone (B3). (B
1) includes aromatic (aliphatic), aliphatic and alicyclic mono- and poly- (di- to tetra- or higher)
Examples include carboxylic acids, heterocyclic-containing amino acids, carboxylic acids containing ionic or salt-forming groups, and oligomers containing carboxyl groups. Aromatic (fatty) carboxylic acids include C7-36 (preferably 7-18) mono- and poly-carboxylic acids, C7-36 (preferably 7-18).
Oxycarboxylic acid and C7-36 (preferably 7-36)
18) amino acids are included. Monocarboxylic acids include benzoic acid, naphthalene carboxylic acid and the like; polycarboxylic acids include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-
And 2,7- isomers), biphenyldicarboxylic acids (2,2'-, 3,3'-, 2,7- and 4,4'-
Diphenyldicarboxylic acid, etc.), diphenoxyethanedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,
4'-diphenylsulfonedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracenedicarboxylic acid (2,5- and / or 2,6
Polyfunctional (tri-, tetra- or higher) polycarboxylic acids such as trimellitic acid (1,
2,4-isomer), naphthalene tricarboxylic acid (1,
2,5- and 2,6,7- isomers), 3,3 ', 4-
Diphenyltricarboxylic acid, benzophenone-3,
3 ', 4-tricarboxylic acid, diphenylsulfone-3,
3 ′, 4-tricarboxylic acid, diphenyl ether-3,
3 ', 4-tricarboxylic acid, pyromellitic acid, diphenyl-2,2', 3,3'-tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2 ', 3,3'-tetracarboxylic acid, diphenylether-2,2', 3,3'-tetracarboxylic acid and the like; examples of oxycarboxylic acids include salicylic acid, 2-oxy-3- and 2-oxy-6-naphthoe Acids, gallic acid, mandelic acid, m- and p-hydroxybenzoic acid, tropic acid and the like; amino acids include phenylalanine, tyrosine, p-aminobenzoic acid, anthranilic acid and the like.

Aliphatic carboxylic acids include saturated and unsaturated, C1-50 (preferably 1-20) mono- and polycarboxylic acids, C1-50 (preferably 3-20).
Oxycarboxylic acid, and C1-50 (preferably 3
-20) amino acids. Monocarboxylic acids include formic acid; C2-20 monocarboxylic acids such as acetic acid;
Propionic acid, butyric acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, lauric acid, stearic acid, (meth)
Acrylic acid, oleic acid, sulfur-containing monocarboxylic acids (for example, thiofatty acids described in JP-B-59-47752), etc .; C21 or more monocarboxylic acids such as behenic acid; Acetylacetonic acid, acetoxystearic acid, pentachlorostearic acid and the like; polycarboxylic acids include dicarboxylic acids (oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid,
Dodecanedioic acid, maleic acid, fumaric acid, itaconic acid, etc. octenylsuccinate), sulfur-containing dicarboxylic acid [for example the general formula _{HOOC- (CH 2) p-S-} (CH 2) q-C
A dicarboxylic acid represented by OOH (where p is an integer of 1 to 8 and q is an integer of 1 to 6), etc., and a tricarboxylic acid (α, β, γ-
Oxycarboxylic acids having one carboxyl group (glycolic acid, lactic acid, β-hydroxypropionic acid, ω-oxycaproic acid, ω-oxyenanthic acid, ω-oxycaprylic acid, etc.); ω-oxyperargonic acid, ω-oxycapric acid, 11-oxyundecanoic acid, 12-oxidedecanoic acid, 12-hydroxystearic acid, malic acid, etc.),
Those having two carboxyl groups (such as tartronic acid, malic acid and tartaric acid) and 3 to 6 carboxyl groups
Or more (e.g., citric acid); amino acids include monoaminomonocarboxylic acids (glycine, alanine, valine, leucine, isoleucine, etc.), monoaminodicarboxylic acids (aspartic acid, glutamic acid, etc.) and oxyamino acids ( Serine and threonine).

Cycloaliphatic carboxylic acids include saturated or unsaturated, C4-50 (preferably 6-10) mono- and poly-carboxylic acids, oxycarboxylic acids and amino acids. Monocarboxylic acids include cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid (1,4-form) and the like; polycarboxylic acids include di- and tri- or higher polycarboxylic acids [1,3- Cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3-dicarboxymethylcyclohexane, isophoronedicarboxylic acid, dicyclohexyl-4,4′-dicarboxylic acid, camphor Acid, polymer fatty acid (C8-22, especially dimer acid, trimer acid and a mixture thereof obtained by polymerizing 12-18 fatty acids), etc.]; as the oxycarboxylic acid, 3-hydroxycyclopentanecarboxylic acid; 4-hydroxycyclohexanecarboxylic acid and the like; Examples of the amino acid include 3-aminocyclopentanecarboxylic acid and 4-aminocyclohexanecarboxylic acid. Heterocycle-containing amino acids include C5-50 (preferably 5-20) amino acids. For example, histidine, tryptophan, proline, oxyproline and the like can be mentioned. Among these, from the viewpoint of compatibility with the synthetic resin when used as a compounding agent for the production of a synthetic resin, preferred are saturated or unsaturated aliphatic and aromatic (fatty) oxycarboxylic acids, and especially saturated or unsaturated. And aliphatic (aliphatic) monocarboxylic acids and dicarboxylic acids. Examples of the carboxylic acid containing an ionic group or a salt-forming group include JP-B-43-197.
No. 9076, JP-B-42-24192 and JP-B-42-19278, carboxylic acids having an anionic group [sulfonic acid (salt) group or the like], for example, sulfoacetic acid, sulfobenzoic acid, sulfoisophthalate Acids.

The carboxyl group-containing oligomer has a number average molecular weight (hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC)) of 300-2.
000. Examples of the carboxyl group-containing oligomer include a polyamide oligomer having a carboxyl group at a terminal, a polyester oligomer, a polyether oligomer, and a polyolefin oligomer. Examples of the polyamide oligomer having a carboxyl group at a terminal include ring-opened polymers of lactams (C6-12, for example, caprolactam, enantholactam, etc.);
Polycondensates of aminocarboxylic acids (C2-12, such as ω-aminocaproic acid, ω-aminoenanthic acid and ω-aminocaprylic acid), dicarboxylic acids (C4-20,
For example, polycondensates of adipic acid, azelaic acid, isophthalic acid, etc.) and diamines (C4-20, for example, hexamethylene diamine, octamethylene diamine, etc.) can be mentioned.

Examples of the polyester oligomer having a carboxyl group at a terminal include a polycondensate of a polycarboxylic acid or an ester-forming derivative thereof and a polyol, and a reaction product of a polycarboxylic acid and a lactone. As the polycarboxylic acid, among the polycarboxylic acids, di-
And tri-carboxylic acids and mixtures of two or more thereof; ester-forming derivatives include these acid anhydrides, lower alkyl (C1-4) esters, and acid halides (such as chlorides). In the polycondensation reaction, the equivalent ratio of the carboxyl group to the hydroxyl group is usually 1.05
/ 1 to 1.3 / 1, preferably 1.07 / 1 to 1.2 /
It is one. Examples of the polyol include, among the (polyoxyalkylene) alcohols of the above (A1), di- and tri-ols and mixtures of two or more thereof. Examples of the lactone include those having C6 to 12, such as caprolactone and enantholactone. The polyester oligomer can be produced by a known polyester production method (dehydration esterification method, transesterification method, method of polycondensation after esterification, ring-opening polymerization method of lactone, etc.).

As the polyether oligomer having a carboxyl group at the terminal, divalent or trivalent Mn of 300 to 10,
Obtained by polycondensation of a polyether polyol with a polycarboxylic acid having a carboxylic acid content of 2 to 3 and a carboxylic acid having a carboxylic acid (C2 to C4) in the presence of an alkali (such as caustic soda). 8: monochloroacetic acid or the like). Examples of the polyether polyol include, among the polyoxyalkylene alcohols of the above (A1), di- and tri-ols and mixtures of two or more thereof. The above polycondensation can be carried out in the same manner as in the case of the polyester oligomer.

As the polyolefin oligomer having a terminal carboxyl group, the terminal of the polyolefin is α,
those modified with β-unsaturated carboxylic acids (anhydrides), those obtained by modifying polyolefins by oxidation with oxygen and / or ozone or hydroformylation by the oxo method, and those obtained by modifying these with lactams (C6-12, such as caprolactam, enantholactam, Laclolactam and undecalactam, etc.) or aminocarboxylic acids (C2-12, for example, glycine, alanine and leucine, etc.), and those modified secondarily. As the above-mentioned polyolefin, C2-30 (preferably C2
To 12), and a polyolefin obtained by polymerization of one or a mixture of two or more olefins, and a high molecular weight (Mn 20,000 to 1,000,000) polyolefin [C2 to 30 (preferably C2 to 12) olefin] Of polyolefins obtained by the polymerization of low molecular weight (Mn 800 to 20,000)
0) Polyolefin. α, β-unsaturated carboxylic acids (anhydrides) include C3-12 mono- and dicarboxylic acids (anhydrides) such as (meth) acrylic acid;
Mention may be made of (anhydride) maleic acid, fumaric acid and (anhydride) itaconic acid. α, β-unsaturated carboxylic acid (anhydride)
Is carried out by thermally adding (ene reaction) an α, β-unsaturated carboxylic acid (anhydride) to the terminal double bond of the polyolefin by either a solution method or a melting method. Can be. Introduction of a carboxyl group by oxidation can be carried out by the method described in US Pat. No. 3,692,877.

The aldehyde (B2) includes aromatic (fats)
Includes aliphatic, aliphatic and cycloaliphatic aldehydes. As the aromatic aldehyde, C7-18 (preferably 7-1)
0) mono- and poly-aldehydes. Monoaldehydes include benzaldehyde, naphthaldehyde, salicylaldehyde, anisaldehyde, vanillin and the like; polyaldehydes include dialdehydes such as 2,6-naphthdialdehyde, phthalaldehyde and isophthalaldehyde. As aliphatic aldehydes, saturated and unsaturated, C1-24
(Preferably 1-18) mono- and poly-aldehydes. Examples of the monoaldehyde include formaldehyde, acetaldehyde, n-, i- and sec-butyraldehyde, octylaldehyde, 2-ethylhexylaldehyde, octadecylaldehyde, (meth) acrolein, 2-hexene-1-al, geranial and the like; Examples thereof include dialdehyde (such as glyoxal and succindialdehyde) and trialdehyde (such as 1,2,4-butanetricarbaldehyde). As alicyclic aldehydes, saturated and unsaturated C4-20 (preferably 4-18) mono-
And poly-aldehydes. Examples of the monoaldehyde include cyclobutanecarbaldehyde, cyclopentanecarbaldehyde, cyclohexanecarbaldehyde, and the like;
Examples of the polyaldehyde include dialdehyde (such as 1,3-cyclohexanedialdehyde). Preferred among these are trialdehydes, and especially mono- and di-aldehydes.

The ketone (B3) includes aromatic (aliphatic), aliphatic and alicyclic ketones. Aromatic ketones include C8-24 (preferably 8-18) mono- and poly-ketones. Monoketones include acetophenone, propiophenone, benzophenone and the like; polyketones include diketones (such as o- and p-diacetylbenzene) and triketones (such as 1,3,5-triacetylbenzene). Aliphatic ketones include saturated and unsaturated, C3-24 (preferably 3-18) mono- and poly-ketones. Monoketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-octanone, di-n
-Octyl ketone, methyl vinyl ketone, etc .; Examples of polyketones include diketones (acetylacetone, 3,5-pentanedione, etc.). Alicyclic ketones include saturated and unsaturated, C4-20 (preferably 4-10) mono- and poly-ketones. Monoketones include cyclobutanone, cyclopentanone, cyclohexanone and the like; polyketones include diketones (such as 1,3-cyclopentanedione, 1,3- and 1,4-cyclohexanedione) and the like. Preferred among these are triketones, and especially monoketones and diketones. Among (B), from the viewpoint of usefulness as an intermediate for producing a synthetic resin and a compounding agent for a synthetic resin, (B2) and particularly (B2) are preferable.
1).

In the production method of the present invention, when (A) is esterified with (B1) using only the polyoxyalkylene alcohol represented by the general formula (2),
As at least a part of 1), a carboxylic acid other than C2-20 carboxylic acid [formic acid, oxycarboxylic acid, alicyclic carboxylic acid, amino acid and / or C21 or more carboxylic acid (C21 or more fatty acid such as behenic acid, carboxyl group) Oligomers) are used. If necessary, a C2-20 carboxylic acid may be used in combination with the above carboxylic acid. Further, (A) other than the polyoxyalkylene alcohol represented by the general formula (2) [(polyoxyalkylene) represented by the general formulas (3) to (5)]
Alcohols, modified (polyoxyalkylene) alcohols represented by the general formulas (2) to (5), (A1) and / or (A2)], and poly (alkylene) represented by the general formula (2) When an oxyalkylene alcohol is used in combination, (B) is not particularly limited, and when esterification is performed using (B1), both C2-20 carboxylic acids and other carboxylic acids are used. May be used in combination. When (B2) and / or (B3) are used as (B) in the production method of the present invention,
(A) is not particularly limited, and any of (polyoxyalkylene) alcohols represented by the general formulas (6), (2) to (5), and modified products thereof can be used. Or a combination of both. Dehydration condensate (D2) used as an intermediate for producing a synthetic resin and an antistatic agent of the present invention
When (A) is produced, (A) is not particularly limited, and even if only the polyoxyalkylene alcohol represented by the general formula (2) is esterified with a C2-20 carboxylic acid, Dehydration condensation may be carried out by using (A) and / or (B) other than and / or in place of or together with the C2-20 carboxylic acid.

Examples of the dehydration condensation reaction include (thio) esterification, amidation, (thio) acetalization, ketimine, and (thio) ketalization. The production method of the present invention can be applied to any of the reactions, but from the viewpoint of the reaction promoting effect, preferred are (thio) esterification, (thio) acetalization, and ketimine.

The amount of the catalyst (C) used is preferably from 10 ^{-8 to} 0.1 equivalent, more preferably from the carbonyl group of (B), from the viewpoint of reactivity and low coloration of the resulting dehydration condensate. Is 10 ^{-7 to} 0.05 equivalent, especially 10 ^{-6 to} 0.01
Is equivalent. In the present invention, the equivalent ratio [(A) / (B)] when reacting (A) and (B) is such that (A) is 1
When (B) is monovalent, usually 0.5 / 1 to 1 /
2, preferably 0.7 / 1 to 1 / 1.5, more preferably 0.8 / 1 to 1 / 1.2. (A) is 1
Value, when (B) is an x value, usually 0.5 / x to 1
/ 2x, preferably 0.7 / x to 1 / 1.5x, more preferably 0.8 / x to 1 / 1.2x. When (A) is x-valent and (B) is monovalent, usually 0.5x / 1
To x / 2, preferably 0.7x / 1 to x / 1.5, more preferably 0.8x / 1 to x / 1.2.

The reaction temperature of the dehydration condensation reaction in the present invention varies depending on the composition of the organic carbonyl compound and the active hydrogen-containing compound, and whether or not a solvent is used during the reaction.
To 230 ° C, preferably 80 to 200 ° C. The dehydration-condensation reaction in the present invention is usually carried out at normal pressure, and the reaction is carried out while removing generated condensed water to the outside of the system. Water can be azeotropically distilled off with the solvent. In order to promote the removal of condensed water out of the system, an inert gas such as nitrogen or argon is passed through the liquid (10 ^{−5 to 1} m ³ / min) or the gas phase (10 ^{−5 to 1} m ³ / min). Is also good. The amount used when using a solvent is
Usually 5 to 2 based on the total weight of the reaction system before adding the solvent.
00%, preferably 10 to 100%. In addition, pressurization (usually 0.02 to 0.5 MPa) or reduced pressure (usually -0.1 to
-0.01 MPa) A dehydration condensation reaction method can also be used.

In the dehydration condensation reaction of the present invention,
An antioxidant, a reducing agent, and the like can be added for the purpose of preventing coloring and thermal deterioration. As antioxidants,
Phenolic antioxidant [2,6-di-t-butyl-4
-Methylphenol, butylated hydroxyanisole,
2,2'-methylenebis (4-methyl-6-t-butylphenol) and 1,3,5-trimethyl-2,4
6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like]; sulfur-based antioxidants [dilauryl-3,3′-thiodipropionate and distearyl-3,3′-thio] Dipropionate, etc.]; phosphorus antioxidants [triphenyl phosphite, triisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite and 2,2-methylenebis (4,4
6-di-t-butylphenyl) octyl phosphite and the like; amine antioxidants [octylated diphenylamine, N, N-diisopropyl-p-phenylenediamine, N, N-bis (1-ethyl-3-methylpentyl) )
-P-phenylenediamine and phenothiazine, etc.]
And the like. Examples of the reducing agent include sodium hypophosphite, sodium borohydride and lithium aluminum hydride. The amount of the antioxidant and / or the reducing agent used is usually 1% or less, preferably 0.001% or less, based on the weight of the whole reaction system before adding them.
0.1%.

In the dehydration condensation reaction of the present invention, since the structure of the product differs depending on the type of the condensation reaction as described above,
The degree of progress of each condensation reaction can be confirmed by measuring the increase or decrease of the characteristic groups of the product and the starting material by nuclear magnetic resonance spectrum (NMR) or the like. The degree of condensation and the degree of increase in Mn of the product can be determined by GPC. The purity of the product can be determined by gas chromatography, high performance liquid chromatography, NMR, or the like.

In the dehydration condensation reaction of the present invention,
The organic carbonyl compound and the active hydrogen-containing compound can be subjected to a dehydration condensation reaction not only with a single compound but also with a mixture of two or more compounds at an arbitrary ratio. The end point of the dehydration-condensation reaction can be generally confirmed by measuring the amount of condensed water distilled, measuring the acid value of the reaction system, or quantifying the unreacted organic carbonyl compound by gas chromatography or high-performance liquid chromatography. Can be stopped at an arbitrary reaction rate by using a reaction terminator. Examples of the reaction terminator include sodium hydrogen carbonate and ammonium carbonate.

The dehydrated condensate obtained by the dehydration condensation reaction in the present invention can be used as it is according to the purpose. If necessary, distillation, filtration, water washing, alkali water washing, activated carbon and the like are used. Purification may be performed by decolorization treatment, chromatographic separation, adsorption treatment using a hydrotalcite-based treating agent, activated clay, or the like.

The dehydration condensate according to the present invention includes an ester formed by an esterification reaction between (A1) and (B1),
An acetal formed by an acetalization reaction between (A1) and (B2), a ketal formed by a ketalization reaction between (A1) and (B3), an amide formed by a reaction between (A2) and (B1), ( Adimine formed by the reaction between A2) and (B2), ketimine formed by the ketimination reaction between (A2) and (B3), and (A3) and (B
A thioester formed by a thioesterification reaction between (A3) and (B2), a thioacetal formed by a thioacetalization reaction between (A3) and (B3), and a thioketal formed by a thioketalization reaction between (A3) and (B3). Includes co-condensates, and mixtures of two or more thereof. The Mn of the dehydrated condensate in the present invention can have any value depending on the purpose, but preferably has a molecular weight of 59 or more and Mn of 500,000 or less. More preferably, Mn is 100 to 200,000,
Particularly, it is 200 to 100,000. Such dehydration condensates include, for example, synthetic resin production intermediates, synthetic resin compounding agents (eg, plasticizers and compatibilizers), antistatic agents, hot melt and pressure-sensitive adhesives, electrophotographic toner binders, It can be suitably used as a lubricant and a fiber treatment agent.

The synthetic resin to be mixed with the synthetic resin compounding agent comprising the dehydration condensate (D1) of the present invention includes a thermoplastic resin and a thermosetting resin. For example, polyester resin, polyamide resin, polyurethane resin, vinyl resin [polyolefin resin, styrene resin, acrylic resin, rubbery (co) polymer, etc.], polyacetal resin,
Acetal or ketal modified polyvinyl alcohol resin, polycarbonate resin, fluorine resin, silicone resin, polysulfide resin, polysulfone resin, and the like. As these resins, those conventionally known as molding resins and the like can be used. As a specific example,
Examples include polyester resin, polyamide resin, polyurethane resin, vinyl resin, polyacetal resin, and polycarbonate resin described in Japanese Patent Application No. 2001-2716. The melting peak temperature (melting point) of the thermoplastic resin by DSC (differential scanning calorimetry) is from 140 to 270 from the viewpoint of easy orientation of the modified polymer to the surface of the resin molded product and ease of kneading the resin. C. is preferable, more preferably 150 to 260C, and particularly preferably 160 to 240C. Intrinsic viscosity [η] of thermoplastic resin (for polyacetal resin, in a 0.5% parachlorophenol solution, 6
0 ° C., 25 ° C. in a 0.5% solution of orthochlorophenol for a polyester resin, and 25 ° C. for a polyamide resin in a 0.5% solution of orthochlorophenol. To 4 are preferable. Mn of the thermoplastic resin is preferably from 20,000 to 500,000.

The type and amount of the dehydration condensate (D1) used as the compounding agent for the synthetic resin are appropriately selected depending on the purpose of use and the type of the synthetic resin to be mixed.
As the plasticizer and compatibilizer, (polyether) polyester of (A1) and (B1), for example, polycarboxylic acid (anhydride) [adipic acid, sebacic acid, azelaic acid,
Citraconic acid, (maleic anhydride) maleic acid, fumaric acid, (phthalic anhydride), isophthalic acid, (trimellitic anhydride) trimellitic acid, etc.] and / or oxycarboxylic acids (glycolic acid, ricinoleic acid, ω-oxycaprylic acid, p- Oxybenzoic acid, etc.) and a (polyoxyalkylene) monool of the general formula (6), (3) or (5) (e.g.
Polyesters with 12 alkanols, cyclohexanol, tetrahydrofurfuryl alcohol, benzyl alcohol, their EO and / or PO adducts, and monocarboxylic acids (acetic acid, propionic acid, caprylic acid, 2-ethylhexanoic acid, lauric acid) , Myristic acid, stearic acid, oleic acid, benzoic acid, etc.) and / or oxycarboxylic acid (as described above) and general formula (6),
(2), (4) or (5) (polyoxyalkylene) polyols [eg (poly) ethylene glycol, (poly) propylene glycol, glycerin, sucrose, their EO and / or PO adducts and the like] and / or Or a (poly) ester with the above monol; (A
1) For example, (polyoxyalkylene) monool (as described above) of the general formula (6), (3) or (5) and (B)
2) Acetal with formaldehyde, for example (formal, for example dibutoxy-ethoxyethylformal)
Is mentioned. Specific examples thereof include those described as a solubilizing agent in US Pat. No. 3,489,723. When used as a plasticizer, the amount of (D1) varies depending on the application, but is generally 5 to 150%, preferably 5 to 100%, and more preferably 5 to 100% based on the resin.
~ 80%.

The intermediate for producing a synthetic resin comprising the dehydration condensate (D2) of the present invention includes an active hydrogen component for producing polyurethane and / or urea, an amine, carboxylic acid and / or alcohol component for producing polyamide or polyesteramide, Epoxy curing agents, bases for polymerization or monomer components may be mentioned.

The active hydrogen component for producing polyurethane and / or urea includes an active hydrogen atom-containing compound and its precursor (a compound that generates an active hydrogen atom-containing group by heating or moisture). As (D2) used as such an active hydrogen atom-containing compound, a (polyether) polyester of (A1) and (B1), for example, of the general formula (6), (2), (4) or (5) (Polyoxyalkylene) polyols, especially polyhydric alcohols [2
Polyhydric alcohols (eg, ethylene glycol, 1,4-
One or two of alkylene glycols such as butanediol and neopentyl glycol, and diethylene glycol;
Or more) or a trihydric or higher polyhydric alcohol (eg, glycerin, trimethylolpropane,
Pentaerythritol)] and / or polyoxyalkylene polyol [polyether diol (eg, polyethylene glycol, polypropylene glycol,
Polytetramethylene ether glycol, an EO and / or PO adduct of bisphenol A)] and a polycarboxylic acid (anhydride) [adipic acid, (phthalic anhydride),
(Anhydrous) maleic acid, (anhydride) itaconic acid, etc.] and / or oxycarboxylic acids (eg, ω-oxycaproic acid, ω-oxycaprylic acid, ω-oxycapric acid,
(Polyether) polyester polyol obtained by reacting (A1) and (A1)
2) a (polyether) polyamide polyester of (B1), such as a (polyoxyalkylene) polyol (the above-mentioned polyhydric alcohol and / or polyoxyalkylene polyol) and a polyamine (eg, ethylenediamine, hexamethylenediamine), and a carboxylic acid (Polyether and / or oxycarboxylic acid) and (polyether) polyamide polyester polyol. A polyol, an amine and / or a carboxylic acid having an ionic or salt-forming group in a part of the components (polyol, amine and / or carboxylic acid) used in the production thereof [ionic group or salt-forming group constituting R ^3] Compounds having an active hydrogen atom having a group (such as those described in JP-B-43-9076), for example, dimethylolpropionic acid (salt) and its 1 to 2 mol adduct of EO, diethylethanolamine and its quaternary compound, diamino (Polyether) (polyamide) polyester polyol having an ionic group or a salt-forming group using benzoic acid (salt), diaminobenzenesulfonic acid (salt), sulfoisophthalic acid (salt), or the like. Also, as another example,
(A1) (polyoxyalkylene) polyol and (B)
2) (polyether) polyacetals, such as formal of hexanediol and formaldehyde, 4,
Formal of 4'-dioxyethoxy-diphenyl-dimethyl-methane with formaldehyde.

(D2) used as a precursor of the compound containing an active hydrogen atom includes (A2) and (B2) and / or (B3) a (polyether) aldimine and / or (B3).
Or ketimines such as polyamines [diamines such as hexamethylenediamine, isophoronediamine, diphenylmethanediamine, tolylenediamine, diethyltolylenediamine, dimethyldiphenylmethanediamine,
Xylylenediamine, polyetherdiamine (polyoxyethylenediamine, polyoxypropylenediamine, etc.)] and an aldehyde (eg, formaldehyde, acetaldehyde) and / or a ketone (eg, acetone, methylethylketone, methylisobutylketone) and / or an aldimine and / or Or ketimine.

The polyol, aldimine and / or ketimine are used as at least a part of the active hydrogen component in producing a polyurethane and / or urea by reacting a polyisocyanate with an active hydrogen component. As the polyisocyanate used for producing polyurethane and / or urea, those described above can be used.
As the active hydrogen component, if necessary, another active hydrogen atom-containing compound [for example, the (polyoxyalkylene) polyol described in (A1) and / or the polyamine described in (A2)] can be used. The production of polyurethane and / or urea can be carried out by a usual method, such as a one-step method (one-shot method) or a multi-step method (prepolymer method).
May be. The aldimine and / or ketimine is
Usually, it is used in combination with an isocyanate-terminated prepolymer.

As the amine, carboxylic acid and / or alcohol component for producing polyamide or polyesteramide, polyamine (A2) [for example, alkylene diamine (ethylenediamine, hexamethylenediamine, octamethylenediamine, etc.) and / or polyalkylenepolyamine (diethylenetriamine) Such)]
And (B1) a polycarboxylic acid [for example, adipic acid, azelaic acid, isophthalic acid, dimer acid and / or a polyolefin oligomer having a carboxyl group at both terminals (polyethylene oligomer, polypropylene oligomer, etc.)] and / or an aminocarboxylic acid (ω -Aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, etc.) and a polyamide polyamine and a polyamide polycarboxylic acid; a polyamine (A2) (described above) and a monocarboxylic acid of (B1) [ For example, polyolefin oligomers having a carboxyl group at one end (polyethylene oligomers, polypropylene oligomers, etc.) with lauric acid, stearic acid, and, if necessary, polyolefins formed by reaction with aminocarboxylic acids (as described above) Bromide monocarboxylic acid; wherein the (polyether) polyester polyols of (polyurethane and / or urea listed manufacturing active hydrogen component) and (A1) and (B1) and the like. These may be used together or with other polyamide-forming components [polyamine (above), polycarboxylic acid (above), lactam (C6-1).
2, for example, caprolactam] to produce polyamide or polyester amide resin.

Examples of the epoxy curing agent include polyamines (A2) [for example, polyalkylene polyamines (eg, diethylenetriamine) and / or xylylenediamine and, if necessary, alkylene diamines (eg, ethylene diamine), dimer diamines, etc.] and (B1) Polycarboxylic acids [eg, polymeric fatty acids (dimer acids) and / or
Or aminocarboxylic acid (ω-aminocaproic acid, ω-
Polyamidepolyamines formed by reaction with aminoenanthic acid, ω-aminocaprylic acid) and optionally other dicarboxylic acids (adipic acid, alkenylsuccinic acid, etc.) and / or monocarboxylic acids (fatty acids such as acetic acid, lauric acid). No. These are reacted with the aforementioned polyepoxide and used for curing. Alternatively, an adduct may be formed by reacting with a small amount of polyepoxide in advance, and then cured by reacting with polyepoxide.

The base or monomer component for polymerization includes a base or monomer component for vinyl polymerization and a base for ring-opening polymerization. Used as a base for vinyl polymerization (D
Examples of 2) include the above-mentioned (polyether) polyester polyol, (polyether) polyamide polyester polyol, and polyacetal (listed as active hydrogen components for producing polyurethane and / or urea). These polyols are used for producing a so-called polymer polyol by polymerizing a vinyl monomer (acrylonitrile, styrene, etc.) therein, which is useful as an active hydrogen atom-containing component used for producing a polyurethane resin. is there.

Used as a base for vinyl polymerization (D2)
Other examples include the above-mentioned polyamide polyamines (listed for the production of polyamides or polyesteramides), polyamide polycarboxylic acids and polyamide monocarboxylic acids. (D2) used as a monomer component includes (B1) an unsaturated mono- or polycarboxylic acid (anhydride) [(meth) acrylic acid, (maleic anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid, (anhydride) ) Citraconic acid, etc.] and (polyoxyalkylene) monool of (A1) [C1-30 aliphatic alcohol and A
O adducts such as dodecyl alcohol, octadecyl alcohol, ethylene glycol, polyethylene glycol and the like; tertiary amino group-containing alcohols such as dialkyl (C1-4) alkanol (C2-4) amine (such as dimethylethanolamine), heterocyclic amine An AO adduct (such as N-hydroxyalkylmorpholine)] with an unsaturated polycarboxylic acid (anhydride) (above) of (B1) and a (polyoxyalkylene) polyol (poly) of (A1) E of alcohols such as ethylene glycol, 1,4-butanediol, diethylene glycol, glycerin, trimethylolpropane, and dihydric phenols (such as bisphenol A)
O and / or PO adducts); an unsaturated mono- or polycarboxylic acid (anhydride) of (B1) (described above) and a tertiary amino group-containing amine of [A2] [N, N -Dialkyl (C1-4) alkylene (C
2-12) unsaturated amides or imides with diamines (dimethylaminoethylamine, diethylaminoethylamine, dimethylaminopropylenepyramine, etc.), which may be (co) polymerized, if necessary, with other vinyl monomers to give vinyl Used for the production of system (co) polymers.

(D2) used as a base for ring-opening polymerization includes (polyether) polyester polyols (listed as active hydrogen components for producing polyurethane and / or urea), (polyether) polyamide polyester polyols and polyacetals; Polyamide polyamines (listed for the production of polyamide or polyester amide), polyamide polycarboxylic acids and polyamide monocarboxylic acids are mentioned. These are used as bases (initiators) for the ring-opening polymerization (addition) of AO (as described above, for example EO, PO) and / or polyepoxides (as described above, for example diglycidyl ether of bisphenol A). The addition of AO is carried out by the presence of an alkali catalyst (such as potassium hydroxide), an acid catalyst (such as boron trifluoride diethyl ether complex), or a catalyst (such as perhalic acid (salt)) that gives an AO adduct having a narrow molecular weight distribution. Can be done below.

The dehydration condensate (D2) used in the antistatic agent of the present invention includes a hydrophilic (polyoxyalkylene) polyol (A1), for example, a hydrophilic polyoxyalkylene polyol [initiator [general formula R- (OH) ) N, R ² −
(OH) p + q, R 3 - (H) compound represented by n (polyhydric alcohol such as ethylene glycol, glycerin; polyhydric phenols such as bisphenol A, hydroquinone; monoamines example butylamine, aniline) EO or EO and other (Polyethylene glycol, polyoxyethylene polyoxypropylene diol, bisphenol A polyoxy), to which a hydrophilic polyether polyol (polyethylene glycol, polyoxyethylene polyoxypropylene diol) obtained by adding AO (such as PO) (content in AO is 50% or more, preferably 60% or more, particularly 70% or more) is added. And / or (polyoxyalkylene) polyol having an ionic group [AO adduct of a polyol having an ionic group or a compound containing an active hydrogen atom having an ionic group, for example, dimethylolpropionic acid (salt)] And And its EO 1-2 mol adduct,
Diethylethanolamine and its quaternary products)],
(B1) polycarboxylic acid (anhydride) [adipic acid,
(Anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydride) itaconic acid, etc.] and / or oxycarboxylic acids (eg, ω-oxycaproic acid, ω-oxycaprylic acid, ω-
(Polyether) polyester obtained by reacting oxycapric acid, 12-oxidedecanoic acid) with the above-mentioned hydrophilic (polyoxyalkylene) polyol (A1) and polyamine (eg, ethylenediamine, hexamethylenediamine) with (A2). (Polyether) polyamide polyesters obtained by reacting the carboxylic acid of (B1) (the above-mentioned polycarboxylic acids and / or oxycarboxylic acids); these (polyether) (polyamide) polyesters and the carboxyl group-containing (B1) Esterified product with an oligomer [for example, a carboxyl group-containing polyolefin (such as polypropylene) and a carboxyl group-containing polyamide]; By reacting a mine [a polyamine obtained by cyanoethylating and hydrogenating the above hydrophilic polyoxyalkylene polyol (eg, polyethylene glycol)] and, if necessary, a (polyoxyalkylene) polyol [such as the above hydrophilic (polyoxyalkylene) polyol] (Polyether (polyester) polyamide). Examples of these are WO 00/4
No. 7652, Japanese Patent Application No. 2001-2716, a block polymer having a hydrophilic polymer block having a polyolefin block;
No. 67, JP-A-63-313342, and polyether polyester polyamide and polyether polyamide described in JP-B-7-116290; and JP-B-38-11298 and JP-B-7-33484. Dehydrated condensate [produced using the titanium catalyst (C) in the present invention] corresponding to the polyether polyester of the present invention.

The antistatic agent comprising the dehydrated condensate (D2) of the present invention may be incorporated into a synthetic resin (for example, the one described above) as an internal antistatic agent. It may be used for the surface treatment of a molded product (a molded product, a film, a sheet, a fiber, a fiber product (a knitted fabric, a nonwoven fabric, or the like)) of a synthetic resin (for example, the one described above). When used in combination, the amount of (D2) can be variously changed according to the required performance, but from the viewpoint of imparting sufficient antistatic properties and mechanical strength, (D2) and the synthetic resin Based on the total weight, 0.5-40%, especially 1-3
0% is preferred. At the time of compounding, a resin composition (master batch) containing (D2) in a high concentration (for example, 10 to 80%) may be formed in advance.

The (D2) used in the hot melt and pressure-sensitive adhesive includes (B1) polycarboxylic acid (anhydride) [adipic acid, (anhydride) phthalic acid, isophthalic acid,
Terephthalic acid, olefin oligomers having carboxyl groups at both terminals] and / or oxycarboxylic acids (ω-oxycaprylic acid, p-oxybenzoic acid, etc.) and, if necessary, monocarboxylic acids (fatty acids, olefin oligomers having one terminal carboxyl group) And a polyamine (such as ethylenediamine) of (A2) and a (polyoxyalkylene) polyol of (A1) [eg, ethylene glycol, (poly) propylene glycol, polytetramethylene ether glycol, bisphenol A EO and / or PO adduct, etc. And (polyoxyalkylene) monools (eg C2-12 alkanol, cyclohexanol, tetrahydrofurfuryl alcohol, benzyl alcohol, their EO and / or PO Obtained by reacting an object, etc.) and, polyether polyester polyamides can be used. For example, those described in Japanese Patent Application No. 2001-48674 can be mentioned.

Used as a binder for electrophotographic toner (D
2) As the polycarboxylic acid (anhydride) of (B1)
[Adipic acid, alkenyl succinic acid, fumaric acid, (anhydride) phthalic acid, isophthalic acid, terephthalic acid, (anhydride)
And (A1) a (polyoxyalkylene) polyol [(polyoxyalkylene) diol such as ethylene glycol, neopentyl glycol, EO and / or PO adduct of bisphenol A, EO of novolak type phenol resin and And / or PO adducts] can be used. For example, JP-A-5-27478
And JP-A-61-105563.

(D2) used for lubricant and fiber treatment agent
As the polycarboxylic acid (anhydride) of (B1) [adipic acid, fumaric acid, (phthalic anhydride), isophthalic acid, (trimeric anhydride), trimellitic acid, sulfur-containing dicarboxylic acid, etc.] and the long chain of (A1) Polyesters with alcohols (C8-18 aliphatic monools, for example stearyl alcohol), (B1) long chain monocarboxylic acids (C8-18)
Fatty acids such as stearic acid and thio fatty acids) and (polyoxyalkylene) polyols of (A1) [for example, (poly) ethylene glycol, (poly) propylene glycol, glycerin, sucrose, thiodiglycol,
With the above polycarboxylic acids (anhydrides) of (B1) and long-chain monoamines (C8-18 fatty acids such as laurylamine, stearylamine); And a polyamide of the above (B1) long-chain monocarboxylic acid and a polyamine of (A2) (such as ethylenediamine, hexamethylenediamine); and a long-chain of the above-mentioned polycarboxylic acid (anhydride) of (B1) and (A3) Mercaptan (C8-1
8, polythioesters with alkyl mercaptans, such as dodecyl mercaptan), (B1) long-chain monocarboxylic acids (C8-18 fatty acids, such as stearic acid)
And the polythiol of (A3) (e.g., 1,4-butanedithiol). Specific examples of the sulfur-containing polyester are described in JP-A-52-10358.
No. 9, JP-A-54-27088, JP-A-54-27088
-27089 and JP-B-59-47552.

[0067]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Parts in the text indicate parts by weight.

Example 1 In a 1-L glass reaction vessel equipped with a Dean-Stark apparatus and a nitrogen inlet tube, 424 parts of oleic acid (1.
5 equivalents), 402 parts (1.5 equivalents) of oleyl alcohol, 0.31 part (0.000 parts) of potassium potassium oxalate
9 eq.), And the temperature was raised to 140 ° C. while bubbling the liquid at a flow rate of 2 × 10 ⁻⁵ m ³ / min. After reaching 140 ° C., a dehydration condensation (esterification) reaction was performed at that temperature, and the condensed water generated during the reaction was removed to the outside of the reaction system. The reaction was completed in 3 hours. The obtained esterified product was 798 parts. The purity of the dehydrated condensate (oleyl oleate, molecular weight = 534) (by high performance liquid chromatography analysis; the same applies hereinafter) was 99.5%, and the hue (Hazen unit color number; the same applies hereinafter) was 80.
(In the above and below, purity is by high performance liquid chromatography unless otherwise specified.)

Comparative Example 1 A dehydration-condensation (esterification) reaction and a post-treatment were performed in the same manner as in Example 1 except that 3 parts (0.017 equivalent) of p-toluenesulfonic acid was used instead of potassium titanium oxalate of Example 1. Was done. The reaction was performed for 6 hours. The obtained esterified product was 797 parts. The purity of the dehydrated condensate (oleyl oleate) was 92.1%, and the hue was 500.

Example 2 In a 1-L glass reaction vessel equipped with a Dean-Stark apparatus, 304 parts (2 equivalents) of geranial, 1,3-
152 parts (2 equivalents) of propanediol, 0.51 part (0.0014 equivalents) of potassium potassium oxalate, 1 part of benzene
Then, dehydration condensation (acetalization) reaction was carried out at 80 ° C. under reflux of benzene. The reaction was completed in 3 hours. After the reaction, benzene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained acetalized compound was 418 parts. The purity of the dehydrated condensate (acetalized product of geranial, molecular weight = 210) was 99.2%, and the hue was 70.

Comparative Example 2 A dehydration-condensation (acetalization) reaction was carried out in the same manner as in Example 2 except that 4.1 parts (0.024 equivalent) of paratoluenesulfonic acid was used instead of potassium titanium oxalate of Example 2. Post-processing was performed. The reaction was performed for 13 hours. The obtained acetalized compound was 417 parts. The purity of the dehydrated condensate (acetalized product of geranial) was 68.3%, and the hue was 250.

Example 3 Using the same reaction vessel as in Example 1, 288 parts (4 equivalents) of methyl ethyl ketone, 340 parts (2 equivalents) of isophoronediamine, and 0.51 part of potassium potassium oxalate (0.1 equivalent) were used.
0014 equiv.) And 80 parts of n-hexane, and the temperature was raised to 85 ° C. while bubbling nitrogen in the liquid at a flow rate of 2 × 10 ⁻⁵ m ³ / min. ) The reaction was performed. The reaction was completed in 5 hours. After the reaction, n-hexane was heated to 110 ° C and -0.09MP
A was distilled off under reduced pressure. A dehydrated condensate (a ketimine compound of isophoronediamine and methyl ethyl ketone) was obtained. The obtained ketimine compound was 554 parts. The purity (by gas chromatography) of the dehydrated condensate (ketimine compound, molecular weight = 278) was 95.3%, and the hue was 50%.
Met.

Comparative Example 3 Dehydration condensation (ketimine The reaction and post-treatment were carried out. The reaction was performed for 8 hours. The obtained ketimine compound was 553 parts. The purity (by gas chromatography) of the dehydrated condensate (ketimine compound) was 80.6%, and the hue was 450.

Example 4 Using the same reaction vessel as in Example 1, acrylic acid 43
2 parts (6 equivalents), 254 parts of dipentaerythritol (1
Equivalent), potassium titanium oxalate 0.51 part (0.00
14 equivalents), 200 parts of toluene and 2 × 10 ⁻⁵ using a mixed gas of nitrogen / dry air = 1/1 (v / v).
12 while performing bubbling in the liquid at a flow rate of m ³ / min.
The temperature was raised to 0 ° C., and a dehydration condensation (esterification) reaction was performed at 120 ° C. under reflux of toluene. The reaction was completed in 5 hours. After the reaction, toluene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained esterified product was 575 parts. The purity of the dehydrated condensate (hexaacrylate of dipentaerythritol, molecular weight = 578) was 98.4%, and the hue was 50.

Comparative Example 4 A dehydration-condensation (esterification) reaction was carried out in the same manner as in Example 4 except that 5.0 parts (0.03 equivalent) of paratoluenesulfonic acid was used instead of potassium titanium oxalate of Example 4. Post-processing was performed. The reaction was performed for 10 hours. The obtained esterification product was 576 parts. The purity of the dehydrated condensate (hexaacrylate of dipentaerythritol) was 88.6%, and the hue was 500 or more.

Example 5 Using the same reaction vessel as in Example 2, 196 parts (2 equivalents) of 1,3-cyclopentanedione, 304 parts (4 equivalents) of 1,3-propanediol and potassium titanium oxalate were used. 0.26 parts (0.0008 equivalent) and 150 parts of toluene were charged, and a dehydration condensation (ketalization) reaction was performed at 120 ° C. under reflux of toluene. The reaction was completed in 6 hours. After the reaction, toluene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained ketalized compound was 426 parts.
The purity of the dehydrated condensate (diketal of 1,3-cyclopentanedione, molecular weight = 214) was 99.3%, and the hue was 60.

Comparative Example 5 A dehydration-condensation (ketalization) reaction was carried out in the same manner as in Example 5 except that 2 parts (0.02 equivalent) of sulfuric acid (concentration: 98%) was used instead of potassium titanium oxalate of Example 5. Post-processing was performed. The reaction was performed for 12 hours. The obtained ketalized compound is 4
25 parts. The purity of the dehydrated condensate (diketal of 1,3-cyclopentanedione) was 91.5%, and the hue was 450.

Example 6 Using the same reaction vessel as in Example 1, a polyethylene oligomer having carboxyl groups at both ends (Mn = 110)
0) in 550 parts (0.5 equivalent), stearylamine 26
9 parts (1 equivalent) and 0.51 part (0.0015 equivalent) of potassium titanium oxalate were charged, and nitrogen was added to 1 × 10 ⁻⁵ m ^3.
180 ° C while bubbling in liquid at a flow rate of / min
To perform a dehydration condensation (amidation) reaction. The reaction was completed in 5 hours. The obtained dehydrated condensate (amidized polyethylene oligomer having carboxyl groups at both terminals, Mn =
1600) was 798 parts. As a result of measuring the acid value,
98.7% of the terminal carboxyl groups were amidated.

Comparative Example 6 A dehydration-condensation (amidation) reaction was carried out in the same manner as in Example 6 except that 1 part (0.01 equivalent) of phosphoric acid (concentration: 90%) was used instead of potassium titanium oxalate of Example 6. Was done. The reaction was performed for 15 hours. The obtained amidated compound was 797 parts. As a result of measuring the acid value, 8
0.1% was amidated.

Example 7 Using the same reaction vessel as in Example 2, 224 parts (2 equivalents) of 1,4-cyclohexanedione, 432 parts (4 equivalents) of 1,3-propanedithiol, and potassium titanium oxalate 0 parts Then, 0.4 parts (0.0011 equivalents) and 200 parts of toluene were charged, and a dehydration condensation (thioketalization) reaction was performed at 130 ° C. under reflux of toluene. The reaction was completed in 5 hours. After the reaction, toluene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained thioketal compound was 582 parts. The purity of the dehydrated condensate (dithioketalized product of 1,4-cyclohexanedione, molecular weight = 292) is 99.5.
% And the hue was 50.

Comparative Example 7 A dehydration-condensation (thioketalization) reaction was carried out in the same manner as in Example 6 except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used instead of potassium titanium oxalate of Example 7. Post-processing was performed. The reaction was performed for 12 hours. The obtained thioketalization reaction product was 581 parts. The purity of the dehydrated condensate (dithioketalized product of 1,4-cyclohexanedione) is 8
0.2% and a hue of 400.

Example 8 Using the same reaction vessel as in Example 2, 228 parts (1 equivalent) of octenyl succinic acid and dodecyl mercaptan 202 were used.
Parts (1 equivalent), 0.26 parts (0.0007 equivalents) of potassium titanium oxalate and 100 parts of toluene were charged, and a dehydration condensation (thioesterification) reaction was carried out at 130 ° C. under reflux of toluene. The reaction was completed in 4.5 hours. After the reaction, toluene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained thioester was 410 parts. Dehydration condensate (thiododecyl octenyl succinate,
(Molecular weight = 412) has a purity of 98.0% and a hue of 2
It was 50.

Comparative Example 8 A dehydration-condensation (thioesterification) reaction was carried out in the same manner as in Example 6, except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used instead of potassium titanium oxalate of Example 8. Post-processing was performed. The reaction was performed for 10 hours. The obtained thioester was 409. The purity of the dehydrated condensate (thiododecyl octenyl succinate) is 79.0%, and the hue is 5%.
00.

Example 9 Using the same reaction vessel as in Example 2, 536 parts (2 equivalents) of octadecylaldehyde and dimercaptoethane 18
8 parts (2 equivalents), 0.26 parts (0.0007 equivalents) of potassium titanium oxalate and 100 parts of toluene were charged, and a dehydration condensation (thioacetalization) reaction was carried out at 130 ° C. under reflux of toluene. The reaction was completed in 5 hours. After the reaction, toluene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained thioacetal compound was 686 parts. The purity of the dehydrated condensate (thioacetalized product of octadecylaldehyde, molecular weight = 344) was 99.0%, and the hue was 100.

Comparative Example 9 A dehydration condensation (thioesterification) reaction was carried out in the same manner as in Example 9 except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used in place of potassium titanium oxalate of Example 9. Post-processing was performed. The reaction was performed for 10 hours. The obtained thioacetal compound was 685 parts. The purity of the dehydrated condensate (thioacetalized octadecanal) was 76.0%, and the hue was 500.

Example 10 Using the same reaction vessel as in Example 2, 536 parts (2 equivalents) of octadecylaldehyde and cyclohexylamine 1
98 parts (2 equivalents), 0.26 part (0.0007 equivalents) of potassium titanium oxalate and 100 parts of toluene were charged, and a dehydration condensation (aldimination) reaction was carried out at 130 ° C. under reflux of toluene. The reaction was completed in 4 hours. After the reaction,
Toluene was distilled off at 120 ° C. under a reduced pressure of −0.09 MPa. The obtained aldiminate was 696 parts. The purity of the dehydrated condensate (aldimine of octadecylaldehyde, molecular weight = 349) is 99.0%, and the hue is 100%.
Met.

Comparative Example 10 The same procedure as in Example 10 was repeated except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used instead of the potassium titanium oxalate of Example 10, and the dehydration condensation (aldimination) reaction was carried out. Post-processing was performed. The reaction was performed for 9 hours. The obtained aldiminate was 695 parts. The purity of the dehydrated condensate (octadecyl aldehyde aldiminate) was 76.0%, and the hue was 500.

Example 11 Using the same reaction vessel as in Example 1, 500 parts of polytetramethylene ether glycol (Mn = 500) (1
Equivalent), 69 parts (0.5 equivalent) of p-hydroxybenzoic acid, 0.26 part (0.000 parts) of potassium titanium oxalate.
7 equivalents) and 100 parts of xylene, and a dehydration condensation (esterification) reaction was performed at 190 ° C. under xylene reflux. The reaction was completed in 5 hours. After the reaction, 120 ° C, -0.09
Xylene was distilled off under reduced pressure of MPa. The obtained dehydrated condensate (esterified product of polytetramethylene ether glycol, Mn = 740) was 738 parts. When the hydroxyl value and the saponification value were measured, 99.0% of the hydroxyl groups were esterified and the hue was 150.

Comparative Example 11 A dehydration-condensation (esterification) reaction was carried out in the same manner as in Example 11 except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used instead of potassium titanium oxalate of Example 11. Post-processing was performed. The reaction was performed for 9 hours. The obtained esterification product was 738 parts. When the hydroxyl value and the saponification value were measured, 75.8% of the hydroxyl groups were esterified and the hue was 450.

Example 12 Using the same reaction vessel as in Example 1, 500 parts (0.25 equivalent) of polytetramethylene ether glycol (Mn = 2000) and 64 parts (0.5 part) of p-aminobenzoic acid were used.
Equivalent), 0.26 parts (0.00) of potassium titanium oxalate
07 parts) and 100 parts of xylene, and a dehydration condensation (esterification) reaction was performed at 190 ° C. under xylene reflux. The reaction was completed in 5 hours. After the reaction, 120 ° C,-
Xylene was distilled off under reduced pressure of 0.09 MPa. The obtained dehydrated condensate (esterified product of polytetramethylene ether glycol, Mn = 2240) was 558 parts. When the hydroxyl value and saponification value were measured, 9
8.5% was esterified and the hue was 140.

Comparative Example 12 A dehydration-condensation (esterification) reaction was carried out in the same manner as in Example 12, except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used instead of potassium titanium oxalate of Example 12. Post-processing was performed. The reaction was performed for 11 hours. The obtained esterification product was 557 parts. When the hydroxyl value and the saponification value were measured, 75.8% of the hydroxyl groups were esterified,
The hue was 450.

Example 13 Using the same reaction vessel as in Example 2, 272 parts (2 equivalents) of pentaerythritol and 512 parts of octylaldehyde were used.
Parts (4 equivalents), 0.3 parts of potassium titanium oxalate (0.
0008 equivalents), and a dehydration condensation (acetalization) reaction was performed at 100 ° C. The reaction was completed in 4 hours. The obtained acetalized compound was 710 parts. The purity of the dehydrated condensate (acetalized formic acid, molecular weight = 356) is 9
8.0% and a hue of 100.

Comparative Example 13 A dehydration-condensation (acetalization) reaction was carried out in the same manner as in Example 13 except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used in place of potassium potassium oxalate of Example 13. went. The reaction was performed for 13 hours. The obtained acetalized compound was 708 parts. The purity of the dehydrated condensate (acetalized formic acid) was 72.3%, and the hue was 300.

Example 14 Using the same reaction vessel as in Example 2, 184 parts (4 equivalents) of formic acid, 388 parts (2 equivalents) of tetraethylene glycol, 0.3 part of potassium potassium oxalate (0.0008)
Equivalent) and a dehydration condensation (esterification) reaction was performed at 100 ° C. The reaction was completed in 4 hours. The obtained esterification product was 497 parts. The purity of the dehydrated condensate (esterified product of formic acid, molecular weight = 250) is 98.4%,
The hue was 80.

Comparative Example 14 A dehydration-condensation (esterification) reaction was carried out in the same manner as in Example 14 except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used instead of potassium titanium oxalate of Example 13. went. The reaction was performed for 8 hours. The obtained esterified product is 49
7 parts. The purity of the dehydrated condensate (esterified product of formic acid) was 89.6%, and the hue was 400.

Test Example 1 95 parts of dipentaerythritol hexaacrylate obtained in Example 4 Irgacure 184 [photopolymerization initiator manufactured by Ciba Geigy] 4 parts Aerosil 200 [manufactured by Nippon Aerosil Co., Ltd., thixotropic agent] 1 part Was uniformly mixed with a planetary mixer, coated on a PVC sheet so as to have a thickness of 25 μm, and irradiated with ultraviolet rays (UV) at 500 mJ / cm ² . JIS K-
When a wear resistance test was performed in accordance with 6902.9 (1998), the amount of wear was 30 mg.

Comparative Test Example 1 The same procedure as in Test Example 1 was repeated, except that the dipentaerythritol hexaacrylate obtained in Example 4 was replaced with the dipentaerythritol hexaacrylate obtained in Example 4 to coat a vinyl chloride sheet. UV irradiation was performed similarly. When the abrasion resistance test was performed, the substrate was scraped off.

Test Example 2 A mixture of 10 parts of the esterified product of polytetramethylene ether glycol obtained in Example 11 and 90 parts of polyethylene terephthalate (Mn = 30000) was mixed.
The resulting mixture was melted and kneaded at a temperature of 0 ° C. to form a film having a thickness of 0.5 mm. Then, the appearance after standing at 100 ° C. for 24 hours was observed. No change was observed in the appearance of the film as compared to immediately after the preparation.

Comparative Test Example 2 Comparative Example 1 was repeated, except that the esterified product of polytetramethylene ether glycol obtained in Example 11 in Test Example 2 was used.
A film was similarly prepared using the esterified product of polytetramethylene ether glycol obtained in 1 and
The appearance after standing at 0 ° C. for 24 hours was observed. The film had numerous cracks.

[0100]

According to the method for producing a dehydrated condensate of the present invention, the amount of a catalyst is extremely small, and the obtained dehydrated condensate is light-colored and of high purity. Therefore, the production method of the present invention is extremely useful.

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[Procedure amendment]

[Submission date] April 5, 2001 (2001.4.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction contents]

The dehydration condensate (D2) used in the antistatic agent of the present invention includes a hydrophilic (polyoxyalkylene) polyol (A1), for example, a hydrophilic polyoxyalkylene polyol [initiator [ general formula R- (OH) ) N, R ² −
(OH) p + q, R 3 - (H) compound represented by n (polyhydric alcohol such as ethylene glycol, glycerin; polyhydric phenols such as bisphenol A, hydroquinone; monoamines example butylamine, aniline)]
To which EO or EO and other AO (such as PO) (content in AO is 50% or more, preferably 60% or more, especially 70% or more) are added. (Polyethylene glycol, polyoxyethylene polyoxypropylene) Diol, bisphenol A polyoxyethylene ether, etc.) and / or (polyoxyalkylene) polyol having an ionic group [polyol having an ionic group or an AO adduct of an active hydrogen atom-containing compound having an ionic group, Methylolpropionic acid (salt) and its EO 1-2 mol adduct,
Diethylethanolamine and its quaternary compound ]When,
(B1) polycarboxylic acid (anhydride) [adipic acid,
(Anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydride) itaconic acid, etc.] and / or oxycarboxylic acids (eg, ω-oxycaproic acid, ω-oxycaprylic acid, ω-
(Polyether) polyester obtained by reacting oxycapric acid, 12-oxidedecanoic acid) with the above-mentioned hydrophilic (polyoxyalkylene) polyol (A1) and polyamine (eg, ethylenediamine, hexamethylenediamine) with (A2). (Polyether) polyamide polyesters obtained by reacting the carboxylic acid of (B1) (the above-mentioned polycarboxylic acids and / or oxycarboxylic acids); these (polyether) (polyamide) polyesters and the carboxyl group-containing (B1) Esterified product with an oligomer [for example, a carboxyl group-containing polyolefin (such as polypropylene) and a carboxyl group-containing polyamide]; By reacting a mine [a polyamine obtained by cyanoethylating and hydrogenating the above hydrophilic polyoxyalkylene polyol (eg, polyethylene glycol)] and, if necessary, a (polyoxyalkylene) polyol [such as the above hydrophilic (polyoxyalkylene) polyol] (Polyether (polyester) polyamide). Examples of these are WO 00/4
No. 7652, Japanese Patent Application No. 2001-2716, a block polymer having a hydrophilic polymer block having a polyolefin block;
No. 67, JP-A-63-313342, and polyether polyester polyamide and polyether polyamide described in JP-B-7-116290; and JP-B-38-11298 and JP-B-7-33484. Dehydrated condensate [produced using the titanium catalyst (C) in the present invention] corresponding to the polyether polyester of the present invention.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction contents]

Example 13 Using the same reaction vessel as in Example 2, 272 parts (2 equivalents) of pentaerythritol and 512 parts of octylaldehyde were used.
Parts (4 equivalents), 0.3 parts of potassium titanium oxalate (0.
0008 equivalents), and a dehydration condensation (acetalization) reaction was performed at 100 ° C. The reaction was completed in 4 hours. The obtained acetalized compound was 710 parts. Dehydration condensate (acetalized pentaerythritol , molecular weight = 3
The purity of 56) was 98.0%, and the hue was 100.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction contents]

Comparative Example 13 A dehydration-condensation (acetalization) reaction was carried out in the same manner as in Example 13 except that 1 part (0.01 equivalent) of sulfuric acid (concentration: 98%) was used in place of potassium potassium oxalate of Example 13. went. The reaction was performed for 13 hours. The obtained acetalized compound was 708 parts. The purity of the dehydrated condensate (acetalized product of pentaerythritol ) was 72.3%, and the hue was 300.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction contents]

[0095] Instead of the potassium titanium oxalate in Comparative Example 14 Example 14, a similarly dehydration condensation to Example 14 (esterification) reaction except using sulfuric acid (98% concentration), 1 part (0.01 equiv) went. The reaction was performed for 8 hours. The obtained esterified product is 49
7 parts. The purity of the dehydrated condensate (esterified product of formic acid) was 89.6%, and the hue was 400.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 69/08 C07C 69/08 69/54 69/54 69/58 69/58 69/84 69/84 249 / 02 249/02 251/08 251/08 321/14 321/14 321/16 321/16 327/22 327/22 C08K 5/00 C08K 5/00 C08L 101/00 C08L 101/00 // C07B 61 / 00 300 C07B 61/00 300 F-term (reference) 4G069 AA06 BA21A BA21B BC01A BC02A BC03A BC03B BC04A BC05A BC06A BC50A BC50B BE08A BE08B CB25 CB61 CB71 CB75 CB77 4H006 AA02 AC43 AC48 GP52 CB63 BB01BA10 BA50 TC09 4H039 CA61 CA66 CA71 CL25 4J002 BD121 BE061 CB001 CF001 CG001 CK021 CL001 CN011 CN031 CP031 EP016 EP026 ER006 EV096 EV306 FD106

Claims (12)

[Claims] 1. A compound (A) having 1 to 10 one or more active hydrogen-containing groups selected from the group consisting of alcoholic hydroxyl groups, amino groups and mercapto groups;
The organic carbonyl compound (B) is dehydrated and condensed to form one or more dehydration condensates selected from the group consisting of (thio) ester, (thio) acetal, (thio) ketal, amide, aldimine and ketimine. In the production method, a titanium catalyst (C) represented by the following general formula (1) is used [However, a carboxylic acid and an ester are used by using only a polyoxyalkylene alcohol represented by the following general formula (2) as (A)] In the case where the carboxylic acid is used, formic acid, oxycarboxylic acid, amino acid, alicyclic carboxylic acid and / or carboxylic acid having 21 or more carbon atoms are used as at least a part of the carboxylic acid]. O = Ti (OCOQCOOM) ₂ (1) [wherein, M represents an alkali metal, Q represents a direct bond or an alkylene group having 1 to 10 carbon atoms. R- [O (AO) m-H] n (2) wherein R is an n-valent hydrocarbon group or hydrogen atom having 1 to 30 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, m Is 4 ~
An integer of 200 and n represents an integer of 1 to 10. ] 2. The method according to claim 1, wherein (B) is one or more selected from the group consisting of formic acid, oxycarboxylic acid, amino acid, alicyclic carboxylic acid and carboxylic acid having 21 or more carbon atoms. . 3. The method according to claim 1, wherein (B) is an aldehyde and / or ketone. 4. At least a part of (A) is an amine, a thiol, a polyoxyalkylene alcohol represented by the general formula (2), or a polyoxyalkylene alcohol represented by the following general formula (3), (4) or (5). Claims: One or more selected from the group consisting of modified products of (oxyalkylene) alcohol and (polyoxyalkylene) alcohol represented by formula (2), (3), (4) or (5). 4. The method according to 1, 2, or 3. ^{R 1 -O (AO) r-} H (3) [H- (OA) r-O] p-R 2 - [O (AO) m-H] q (4) R 3 - [(AO) k- H] n (5) wherein A is an alkylene group having 2 to 4 carbon atoms, R ¹ is H or a residue of a monohydric alcohol or phenol having 1 to 30 carbon atoms, and R ² is A polyhydric alcohol, a dihydric alcohol having 5 or more carbon atoms or a residue of a polyhydric phenol having 2 to 10 valences, r is an integer of 0 or 1 to 3 (provided that R
^{When 1} is a residue of H or a monohydric phenol and R ² is a residue of a polyhydric phenol, an integer of 1 to 3), and m is 4
An integer of ~ 200, p is an integer of 1 or more, q is an integer of 0 or 1 or more (provided that the sum of p and q is equal to the valence of R ² ), and R ³ has n active hydrogen atoms. A residue of an active hydrogen compound having a mercapto group-containing compound, an amino group-containing compound, or a (thio) ether bond, SO, SO ₂ , CO, a halogen atom, an ionic group or a salt-forming group; Integer, k is 0 or an integer of 1 to 200 (however, when R ³ is a compound having no alcoholic hydroxyl group, at least one of n k's is 1 or more). ] 5. An amine, a thiol, a (polyoxyalkylene) alcohol represented by formula (3), (4) or (5) and a compound represented by formula (3) or (4) as at least a part of (A). 5. The method according to claim 4, wherein one or two or more selected from the group consisting of modified (polyoxyalkylene) alcohols represented by (5) are used. 6. The method according to claim 1, wherein (C) is used in an amount of 10 ^{-8 to} 0.1 equivalent based on the carbonyl group of (B). 7. (Thio) ester, (thio) acetal, (thio) ketal obtained by the method according to claim 1 and having a molecular weight of 59 or more and a number average molecular weight of 500,000 or less. One or more dehydration condensates selected from the group consisting of amides, amides, aldimine and ketimines. 8. A compounding agent for a synthetic resin, comprising the dehydration condensate according to claim 7. 9. A polyester resin, a polyamide resin, a polyurethane resin, a vinyl resin, a polyacetal resin,
A resin composition comprising a synthetic resin selected from the group consisting of an acetal or ketal modified polyvinyl alcohol resin, a polycarbonate resin, a fluorine resin, a silicone resin, a polysulfide resin and a polysulfone resin, and the compounding agent according to claim 8. 10. A compound (A) having 1 to 10 or more active hydrogen-containing groups selected from the group consisting of an alcoholic hydroxyl group, an amino group and a mercapto group, and an organic carbonyl compound (B). 1 selected from the group consisting of (thio) esters, (thio) acetals, (thio) ketals, amides, aldimines and ketimines obtained by dehydration condensation in the presence of a titanium catalyst (C) represented by the following general formula (1): An intermediate for producing a synthetic resin comprising one or more dehydration condensates. O = Ti (OCOQCOOM) ₂ (1) [wherein, M represents an alkali metal, Q represents a direct bond or an alkylene group having 1 to 10 carbon atoms. ] 11. An active hydrogen component for producing polyurethane and / or urea, an amine, carboxylic acid and / or alcohol component for producing polyamide or polyesteramide, an epoxy curing agent, or a base or monomer component for polymerization. The intermediate for producing a synthetic resin according to the above. 12. A compound (A) having one to ten or more active hydrogen-containing groups selected from the group consisting of an alcoholic hydroxyl group, an amino group and a mercapto group, and an organic carbonyl compound (B). 1 selected from the group consisting of (thio) esters, (thio) acetals, (thio) ketals, amides, aldimines and ketimines obtained by dehydration condensation in the presence of a titanium catalyst (C) represented by the following general formula (1): An antistatic agent comprising one or more dehydration condensates. O = Ti (OCOQCOOM) ₂ (1) [wherein, M represents an alkali metal, and Q represents a direct bond or an alkylene group having 1 to 10 carbon atoms. ]