JP2001329043A - Glycidyl ester compositions and methods for producing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glycidyl ester composition having high epoxy group contents and low hydrolyzable chlorine contents. SOLUTION: The glycidyl ester composition and its production method comprise reacting a diacid anhydride, a monoglycidyl ester, according to demand a carboxyl functional polyester resin which is obtained by reacting a dicarboxylic acid with a monoepoxide, and an epihalohydrin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to glycidyl ester compositions, their preparation, coating compositions, other curable compositions containing glycidyl ester compositions, and the use of such curable compositions. It relates to the resulting cured product.

[0002]

BACKGROUND OF THE INVENTION Coating compositions based on the reaction product of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are known. Cured products made on the basis of these compositions are resistant to hydrolysis, but have low UV resistance, which requires a high degree of outdoor durability, such as building components or automotive topcoats. Not suitable for use.

[0003] Triglycidyl esters which can be used in outdoor durable paints and molding compositions are disclosed in European Patent Application No. 447360A (EP-A-447,360). This application discloses a product having a high level of hydrolysable chlorine content. EP-A-44 for a 2: 1 adduct of hexahydrophthalic anhydride and dimethylolpropionic acid
In Example 2, 7,360, the product obtained was 1.0% (10,0
(00 mg / kg). Such high levels of residual chlorine are generally undesirable in coating compositions.

[0004] European Patent Application No. 0518408A2,
(i) (a) Diglycidyl ester of α, α′-dibranched dicarboxylic acid of the following general formula (I):

[0005]

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And (b) α, α'-dibranched dicarboxylic acid of the following general formula (II):

[0007]

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Wherein n is 0 or 1, R is independently selected from the group consisting of linear and branched alkyl, cycloalkyl, arylalkyl, and aryl, and two Rs are 5, 6 and 8 may form part of an alicyclic ring system, substituted or unsubstituted carbon atoms, when n should is 0, R ₁ is hydrogen atom or a methyl group independently, R ₂ Is a single bond substituted or unsubstituted alkylene or arylene, or a radical of the following formula (III):-(R ₃ ) m ₁ -X- (R ₃ ) m _2- (III), wherein m ₁ and m ₂ is independently 0 or 1, R ₃ is independently selected from the group consisting of substituted or unsubstituted alkylene, X is a single bond or one of the following bridging groups (I) to (V) Is:

[0009]

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[0010] In the formula, R ₄ is when X is bridging group (V) is m ₁ is 0 and when X is bridging group (VI) is m ₂
Is independently selected from the group consisting of C ₁ -C ₄ alkyl, provided that R ₂ is a single bond when n is 0, to form a precursor resin obtained by reaction with Material: and (ii) amino resin block or unblocked
(Alicyclic) aliphatic isocyanate, α, α′-dibranched cyclic anhydride, α, α′-dibranched acid and acid-functional polyester containing only ester group, (alicyclic) aliphatic amine, (alicyclic) A) a thermosetting resin comprising: a curable compound selected from the group consisting of aliphatic polyaminoamides, blocked or unblocked Lewis acids, and tertiary amines.

The molar ratio between the compounds (a) and (b) was preferably in the range from 0.5 to 2.0. Preferred reactant (a)
Is selected from diethylmalonic acid, 2,2,5,5-tetramethyladipate, diglycidyl ester of sulfodipivalic acid and tetrapropyladipate, and a preferred reactant
(b) is selected from dimethylmalonic acid, 2,2,5,5-tetramethyladipic acid, sulfodipivalic acid and tetrapropyladipic acid.

[0012] Only diglycidyl esters of α, α'-dibranched dicarboxylic acids of very specific structure exhibit coating compositions which exhibit an acceptable combination of hydrolysis stability, transesterification resistance and acceptable weatherability. It will be recognized from the cited European patent applications and other publications that they can be used as reactants.

[0013] International application WO 96/11238 shows that epoxy resins having alicyclic nuclei have the disadvantage of giving only brittle coatings when cured. This brittleness often leads to poor adhesion and is not suitable for coating applications.

European Patent Application No. 0634434 A2
(A) at least one compound A 'having a monofunctional primary or secondary hydroxyl group and / or at least one compound A "having a primary or secondary hydroxyl group and a tertiary aliphatic carboxyl group; (B) at least one aromatic or alicyclic dicarboxylic acid compound B having two aromatic or secondary aliphatic carboxyl groups, or anhydrides thereof; (c) independently a primary or secondary hydroxyl group At least one diol compound C having two aliphatic hydroxyl groups, which can be: and (d) one tertiary aliphatic carboxyl group, and each independently a primary or secondary hydroxyl group. Can do 2
At least one dihydroxymonocarboxylic acid compound D having two aliphatic hydroxyl groups;
A ": B: C: D molar ratio is M: N: X + Y + 1: X:
In Y, (where M + N is 2, X is in the range of 2 to 8,
Y ranges from 2-N to 8) by reacting at a temperature of from 100 to 240 ° C. until essentially all of the non-tertiary carboxyl groups initially present in the reaction mixture have reacted. Discloses a method for producing a linear tertiary aliphatic carboxyl functional polyester resin. Linear tertiary aliphatic carboxyl-functional polyester resins have been reacted with an excess of epihalohydrin in the presence of a suitable base and optionally a catalyst to produce polyglycidyl ester resins.

European Patent Application No. 0720997A2 discloses certain linear tertiary carboxyl-functional polyester resins and epoxy-functional polyester resins. These polyester resins include: (a) at least one aromatic or alicyclic carboxylic acid compound A having two aromatic and / or secondary aliphatic carboxyl groups, or an anhydride thereof; At least one hydroxyl compound B having two aliphatic hydroxyl groups which can be primary or secondary hydroxyl groups; and (c) at least one tertiary aliphatic carboxyl group, and each independently primary Or at least one hydroxyl-substituted carboxylic acid compound C having two aliphatic hydroxyl groups which can be a secondary hydroxyl group; and (d) optionally one aliphatic carboxylic acid compound having one carboxyl group D; with compound A: B: C:
The molar ratio of D is (X + Y-1): X: Y: Z (where X is in the range of 2-8, Y is in the range of 2-8, and Z is in the range of 0-2); It is obtained by reacting.

The international application WO 98/23661 is a) (i) Synthesis of the formula: (R ₁ ) (R ₂ ) (R ₃ ) -C-COOH with glycidyl esters of a mixture of isomers of highly branched saturated monocarboxylic acids. Wherein R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 15 carbon atoms, at least one of which is methyl, and each acid has 5 to 19, preferably 5 to
At least one compound A1 containing the reaction product of (ii) a mixture of the synthetic hyperbranched saturated monocarboxylic acids in a molar ratio of 1: ₁ ; ₁ is optionally mixed with hydroxypivalic acid (A ₂ ) and / or hydrogenated diphenylolpropane (A ₃ ); b) at least one fragrance having two aromatic or secondary aliphatic carboxyl groups C) one tertiary aliphatic carboxyl group and two aliphatic groups, each of which can be independently a primary or secondary hydroxyl group. At least one dihydroxymoncarboxylic acid compound C having a hydroxyl group; and optionally d) two aliphatic hydroxyls, each of which can be independently a primary or secondary hydroxyl group. One diol compound D having Le group; _{a, A 1: A 2 + A} 3: B: C: molar ratio of D compounds _{A 1: (2-A 1} ): X + Y + 1: X: with Y
Wherein A ₁ is in the range of 0.1 to 2, Y is in the range of 0 to 6, and X is in the range of 2 to 8, and essentially all that is initially present in the reaction mixture A linear tertiary carboxyl-functional polyester resin obtained by reacting at a temperature of 100 to 225 ° C. until the non-tertiary carboxyl group has reacted, and a polyglycidyl ester derived from the polyester resin, and a polyester resin. And / or a coating composition containing a polyglycidyl ester resin.

International application WO 98/24828 discloses that (a) at least one 1,4-mixed with a small amount of an alkanedicarboxylic acid (A ') optionally having from 8 to 16 carbon atoms.
(B) at least one hydroxyl monocarboxylic acid compound having one tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups (B); optionally, (c) each independently One diol compound (C) having two aliphatic hydroxyl groups which can be primary or secondary hydroxyl groups; and, optionally, (d) containing one monofunctional primary or secondary hydroxyl group (D ′), and / or a compound (D ″) having one primary or secondary hydroxyl group and one tertiary aliphatic carboxyl group; a compound (A + A ′): B: C:
When the molar ratio of D ′: D ″ is (X + Y + 1): Y: X: M: N (where M + N is in the range of 0 to 2, X is in the range of 2 to 8, and Y is
Ranges from [2- (M + N)] to 8), and is reacted at a temperature of 100 to 225 ° C. until essentially all of the non-tertiary carboxyl groups initially present in the reaction mixture have reacted. A tertiary carboxylic functional polyester resin obtained by the above method, a polyglycidyl ester derived from the polyester resin, and a coating composition containing a polyester resin and / or a polyglycidyl ester resin are disclosed.

International application WO 98/42768 describes carboxyl-functional polyester resins, epoxy-functional polyester resins derived therefrom, and coating compositions containing these polyester compounds. The carboxyl-functional polyester resin comprises: a) optionally at least one of the following formulas, mixed with a small amount of the corresponding compound (A2) wherein x is 0 in formula I:
Kinds of compounds (A1) or their anhydrides:

[0019]

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(Wherein R ₁ and R ₂ each independently represent 1 to 4
Or an alkyl group having the carbon atoms of
H- (CH ₂₎ x-CH- group, can form a cycloalkyl group), preferably is a 1,4-cyclohexanedicarboxylic acid; is b) each independently primary or secondary hydroxyl groups At least one diol compound B having two aliphatic hydroxyl groups which can be optionally c) one tertiary aliphatic carboxyl group and two independently each being a primary or secondary hydroxyl group A dihydroxymonocarboxylic acid compound (C) having an aliphatic hydroxyl group; and, optionally, d) a trihydroxyalkane (D1) or a tetrahydroxyalkane (D2): (A1 + A2): B: C: D1:
When the molar ratio of the D2 compound is X + Y + 2Z + 3Q + P: X:
Y: Z: Q (where X is in the range of 1 to 8 and Y is 0
-8, Z is in the range of 0-4, and Q is in the range of 0-
3 and P is in the range of 1 to 5, preferably 1 to 3, most preferably 1), and when compound C is present, essentially all of the hydroxyls initially present in the reaction mixture 100-240 until the group has reacted
C., preferably at a temperature of 180 to 210.degree.

The linear tertiary fatty acid carboxyl-functional polyester resins and polyglycidyl esters provided in certain processes provide, for modern economically applied coatings, outdoor durability (UV stability) and curing in the cured state. Although directed to the requirement of hydrolysis resistance, there is still a need to further improve properties and / or reduce manufacturing costs.

The above-mentioned EP 0634434A2, EP 720997A2, WO 9
8/23661, WO 98/24828, WO 98/42768, i.e.
(I) To obtain improved cured coating properties derived from carboxyl-functional and epoxy-functional polyester resins, it is necessary to incorporate terminal tertiary carboxyl groups made from dicarboxylic reactants in the polyester core block. By introduction (where the carboxyl groups are removed from each at least three methylene carbon atoms) or the original terminal carboxyl groups in the initially formed carboxyl-functional polyester resin react with the hydroxy-branched alkanecarboxylic acid And (ii) the starting carboxy-functional polyester resin made from dicarboxylic acid or anhydride reactants, wherein the carboxylic group is phthalic acid or anhydride. Or 1,
Only two methylene carbon atoms are removed, such as 2-cyclohexanedicarboxylic acid or its anhydride)
It can be appreciated that the corresponding polyglycidyl polyester is not efficiently glycidylated and must be avoided.

[0023]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a glycidyl ester composition having a high epoxy group content and a low hydrolyzable chlorine content, and a process for producing the same.

[0024]

SUMMARY OF THE INVENTION Accordingly, the present invention provides 280 mg KOH / g in the presence of a suitable base and optionally a catalyst.
A glycidyl ester composition prepared by reacting a carboxy-functional polyester compound having an acid number of less than with an excess of epihalohydrin, wherein the carboxy-functional polyester resin comprises: (a) at least one compound A; Compound A has the following formula (I)
Is an anhydride of:

[0025]

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Wherein R and R ′ are each independently hydrogen,
Or an alkyl group having 1 to 4 carbon atoms bonded to the cyclohexane ring, or can form a cyclohexane ring together, or one secondary acid group and one tertiary acid group (B) at least one compound B; compound B has an oxygen content of at most 35% and contains two aliphatic or cycloaliphatic hydroxyl groups, and β- If the compound is a di- or di-hydroxyl compound containing no hydrogen atom and having at least 3 carbon atoms between the two hydroxyl groups, or if compound C is present, the monoepoxide D The monoepoxide D is a monoglycidyl ester of an α-α-branched carboxylic acid having 5 to 19 carbon atoms; and, optionally, (c) at least one compound C; Compound C is di -2
A carboxylic acid or an anhydride; in a molar ratio of compound A: B: C of 2: X: Y, where Y is in the range of 0-3 and X is Y + 1, Wherein the carboxy-functional polyester compound is prepared by reacting at a temperature effective to react essentially all of the hydroxyl groups initially present and formed therein. It is intended to provide a glycidyl ester composition substantially free of.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of intensive studies and experiments,
The glycidyl ester compositions of the present invention containing certain terminal carboxyl groups made from dicarboxylic acid or anhydride reactants have a high epoxy group content (ie, close to theoretical value) and a low hydrolyzable halogen content, especially It has been found that with a combination of chlorine contents, it can be effectively glycidylated to glycidyl esters, and more particularly has no negative effect on resins, paint formulations, and cured coating properties.

Several aspects of the invention are described herein. Any of the requirements of the invention may include any one or combination of the features described herein.

As mentioned above, the present invention relates to glycidyl ester compositions and their curable compositions. The glycidyl ester composition is produced by glycidylation of the carboxyl-functional polyester compound produced by the reaction of compounds A and B, and optionally compound C, specified above.

Compound A can be an anhydride having the formula (I):

[0031]

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Wherein R and R ′ are each independently hydrogen,
Or an alkyl group having 1 to 4 carbon atoms bonded to the cyclohexane ring, or can form a cyclohexane ring together, or one secondary acid group and one tertiary acid group Represents a diacid having 200 to 2000
It has an acid number of mgKOH / g, preferably 400-1500 mgKOH / g, most preferably 500-1000 mgKOH / g.

Compound A is, for example, 1,2-cyclohexanedicarboxylic acid (hexahydrophthalic acid), 5-methyl-1,2-cyclohexanedicarboxylic acid, 2,3-dimethyl-5-isobutyl-1,2-cyclohexanedicarboxylic acid Acid, anhydrides of acids such as endomethylenetetrahydrophthalic acid and 5-methylendomethylenetetrahydrophthalic acid, or 1-alkyl-1,4-cyclohexanedicarboxylic acid, wherein the alkyl group has 1 to 4 carbon atoms A), more preferably 1-methyl-1,4-cyclohexanedicarboxylic acid. As the preferred compound A, an anhydride in which R and R ′ are each independently hydrogen or a methyl group is used. The most preferred compound A is hexahydrophthalic anhydride.

Component (b) has an oxygen content of at most 35%, preferably at most 30%, more preferably at most 20% and has two trialiphatic or cycloaliphatic hydroxyl groups, And a di- or di-primary hydroxyl compound containing no β hydrogen atom and having at least three carbon atoms between the two hydroxyl groups, or a monoepoxide D when C is present. Compound B can be: Monoepoxide D is a monoglycidyl ester of an α-α-branched carboxylic acid having 5 to 19, preferably 9 to 19, carbon atoms.

Suitable examples of compounds B and D include neopentyl glycol, diphenylolpropane hydride (H
DPP) CARDURA E10 monomer (α with 10 carbon atoms
-α-branched carboxylic acid; (CARDURA is a trademark), hydrogenated
There are 4,4'-dihydroxydiphenyl, 1,4-dihydroxycyclohexane, neopentyl glycol hydroxypivalate, and 2-butyl-2-ethyl-1,3-propanediol, or a mixture thereof. preferable. More preferred compounds used as compound B are found to have an oxygen content of 30-5%.
Preferably, compound B is a di-secondary hydroxyl compound.

Compound C can be a di-secondary carboxylic acid or anhydride. Compound C can be any di-secondary carboxylic acid or anhydride not used as component (a). Typical examples of compound C include 1,4-cyclohexanedicarboxylic acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2,3-dimethyl-1,4-cyclohexanedicarboxylic acid, and 2,5-dimethyl-1, 4-cyclohexanedicarboxylic acid, with 1,4-cyclohexanedicarboxylic acid being most preferred.

Glycidyl ester compositions wherein Y has a value of 0 to 2, more preferably 0 or 1, and most preferably 0 are more preferred.

The glycidyl ester composition of the present invention has been found to exhibit attractive properties, such as outdoor durability or dispersibility of the product.

In order to obtain good properties in products derived from the glycidyl ester composition according to the invention, the glycidyl ester composition preferably has a hydrolyzable halogen content of at most 6000 mg / kg.

The glycidyl ester composition can be used with co-reactants or co-reactants or hardeners to provide a curable composition. Thus, the curable or co-reactable compositions are useful as outdoor durable paints, especially for metal substrates, used outdoors, for example in windmills, automobiles, aircraft, and for resin-impregnated webs, such as woven or nonwoven. Glass, aramid or carbon fiber webs or fabrics can be used as a curable system for the production of technical buildings. The curable coating composition can be applied in the form of a powder coating or a liquid coating based on the type and amount of each component forming the backbone of the polyester resin.

Another aspect of the present invention is a glycidyl ester that is substantially free of by-products, especially those that degrade the final properties of the curable composition applied to a metal substrate, such as an outdoor application. In the composition. The curable coating composition can be applied in the form of a powder coating or a liquid coating based on the type and amount of the reactive component forming the skeleton of the polyester resin.

Accordingly, the present invention provides (a) (i) at least one
Species of compound A; compound A is an anhydride of formula (I):

[0043]

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Wherein R and R ′ are each independently hydrogen,
Or an alkyl group having 1-4 carbon atoms attached to the cyclohexane ring, or can form a cyclohexane ring together, or has one secondary and one tertiary acid group (Ii) at least one compound B; compound B has an oxygen content of at most 35% and contains two aliphatic or cycloaliphatic hydroxyl groups and a β-hydrogen atom Is a di- or di-hydroxyl compound having at least 3 carbon atoms between the two hydroxyl groups, or if compound C is present, the above monoepoxide D And optionally (iii) at least one compound C; wherein compound C is di-2
A carboxylic acid or an anhydride; in a molar ratio of compound A: B: C of 2: X: Y, where Y is in the range of 0-3 and X is Y + 1, By reacting at a temperature effective to react essentially all the hydroxyl groups initially present and formed therein, 280 mg
Producing a carboxy-functional polyester compound having an acid number of less than KOH / g, preferably in the range of 150-280 mg KOH / g and substantially free of diacids having an acid number of more than 280 mg KOH / g; (b) A) reacting said carboxy-functional polyester compound from step (a) with essentially all carboxyl groups initially present and formed in the reaction mixture in the presence of a suitable base and optionally a catalyst; At a temperature effective for
Producing a glycidyl ester composition by reacting excess epihalohydrin; a glycidyl ester composition having a hydrolyzable chlorine content of at most 6000 mg / kg and an epoxy group content of 90% or more of the theoretical value. The present invention relates to a method for manufacturing a product.

The reaction of step (a) is preferably carried out at 100 to 2
The reaction is carried out at a temperature in the range of 00 ° C, more preferably in the range of 120 to 175 ° C, for a time effective to react essentially all the hydroxyl groups initially present in the reaction mixture. The remaining hydroxyl groups are preferably less than 5%, more preferably less than 2% of the amount of initially present hydroxyl groups, most preferably all of the first present hydroxyl groups have been reacted.

The reaction of step (b) is preferably carried out at 20 to 12
At a temperature of 5 ° C, more preferably in the range of 40-100 ° C,
The reaction is carried out for a time effective to react essentially all the carboxylic acid groups initially present in the reaction mixture. The remaining carboxylic acid groups are preferably less than 5%, more preferably less than 2% of the amount of initially present hydroxyl groups, most preferably all of the first present carboxylic acid groups have been reacted. . Hydroxyl and carboxylic acid groups can be monitored by conventional methods, including infrared spectroscopy, NMR spectroscopy or titration.

The polyester product prepared in step (a) is substantially free of diacid monomers having an acid number greater than 280 mg KOH / g. The diacid monomers include the starting diacid components A and / or C and the starting anhydride components A and / or
Or a diacid derived from C. The carboxyl-functional polyester product of step (a) is preferably less than 5%,
More preferably it contains less than 2%, most preferably no detectable amount of diacid. These low molecular weight diacid components are undesirable in the final product.

The curable or co-reactable coating composition of the present invention can be prepared by adding a curing agent (crosslinkable resin) or a co-reactant to the glycidyl ester composition specified above. The amount of curing agent or co-reactant used in the coating composition of the present invention is usually such as to provide an amount approximately equal to the reactive groups of the curing agent or co-reactant and the epoxy groups present in the glycidyl ester composition. Will be quantity.

The coating composition can be applied by impregnation, spraying, brushing, roll coating, or other suitable technique. Curing agents suitable for use in combination with the polyglycidyl ester resin of the present invention include:
For example, the (corresponding) acid-functional polyester compositions of the present invention; solid polyacids, such as sebacic acid, 1,12-dodecandionic acid; anhydrides such as polyazeleic polyanhydrides;
Acid-functional polyesters, for example the reaction product of 1 mol of trimethylolpropane with 3 mol of hexahydrophthalic acid, the reaction product of 1,6-hexanediol with an excess of 1,12-dodecandioic acid, 4 mol Of 1,10-decanedicarboxylic acid, 1.49 mol of hexanediol, 0.47 mol of 1,1,1-tris- (hydroxymethyl) -propane and 0.27 mol of pentaerythritol,
Moles of 1,10-decanedicarboxylic acid, 1.2 moles of hexanediol, 0.45 moles of trimethylolpropane,
A reaction product of 0.29 mol of pentaerythritol and 0.21 mol of dimethylolpropionic acid, and a reaction product of 1 mol of hexamethoxymethylene melamine and 3 mol of hydroxypivalic acid; and an amine-type curing agent .

The combination of the glycidyl ester composition and the polyester compound from which the glycidyl ester is derived is most preferred.

The coating composition of the present invention may further contain catalysts known in the art suitable for use in the coating composition and optionally other additives. Suitable catalysts are, for example, quaternary ammonium and phosphonium salts; metal salts / compounds, such as stannic (II) octoate; basic compounds, such as imidazole; and tertiary amines, such as diazabicyclo / undecene. The amount of catalyst used will usually range from 0.1 to 2% by weight of the total coating composition.

Suitable curing or reaction times for reacting the epoxy groups, and the reactive groups of the curing agent or co-reactant, and the temperature of the coating compositions of the present invention are those conventional for coating systems. .

[0053]

The following examples illustrate the invention but do not limit the scope of the invention to these particular embodiments. Example 1 Preparation of linear aliphatic carboxyl-functional polyesters 1 to 6 according to the invention and comparative linear aliphatic carboxyl-functional polyesters a, b, c, d and e: Table 1 shows the respective components of each polyester resin. At the indicated molar amount, and supplied to a round bottom glass reactor equipped with a reflux condenser, a temperature controller, a nitrogen inlet and a stirrer. The mixture was then heated to 150 ° C. for 30 minutes. The temperature of the reaction mixture is raised to 170 ° C. in 30 minutes and the
Maintained at 0 ° C. The acid-functional polyester thus formed was removed and cooled to room temperature.

[0054]

[Table 1]

HHPA: hexahydrophthalic anhydride mHHPA: 5-methyl-1,2-cyclohexanedicarboxylic anhydride HDPP: hydrogenated diphenylolpropane BEPD: 2,2-butyl-ethyl-1,3-propanediol NPG: Neopentyl glycol HPA: hydroxypivalic acid HD: 1,6-hexanediol 1,4: 1,4-cyclohexanedicarboxylic acid CE-10: CARDURA E10 glycidyl ester EG: ethylene glycol DMPA: dimethylolpropionic acid

[0056]Example 2  Polyglycidyl ester resins I-VI of the present invention and ratio
Polyglycidyl ester resin (formed only from HHPA)
Production: functional polyester resins 1 to 6 produced in Example 1,
And one carboxyl group of the comparative polyester resins a to e
Amount equal to the amount, and only HHPA to epichlorohydrin (EC
H) 8 mol, isopropyl alcohol (IPA) 7.68 mol
And 7.68 mol of water. Solution to a temperature controller,
3 liter glass reactor with stirrer and reflux condenser
Supplied. Then the temperature was raised to 75-85 ° C and
Over time, add successively the first 0.17 molar aqueous solution of NaOH.
Done. After 50 minutes of additional reaction, the reactor contents are
Cool to 55 ° C. in 30 minutes, then NaOH over 60 minutes
A second sequential addition of a 0.94 mole aqueous solution was made. 5
After an additional minute of reaction, the reactor contents are allowed to settle and the aqueous phase
Was separated from the organic phase. The organic phase is vacuum flashed
Water, IPA and ECH were removed. The resulting product is
Dissolve in sodium butyl ketone and wash the organic layer four times with water.
After that, the organic phase is vacuum flushed to give methyl isobutyl keto
Was removed. Polyglycidyl obtained in this way
The ester was removed and cooled. Polyglycidyl esthetic
The properties of the resin are shown in Table 2.

Hydrolyzable chlorine (without correction for possible organic chlorine) was determined by the following method. A weighed amount of the test sample was added to 15 mL of toluene and 50 mL.
It was dissolved in mL of ethyl ketone, and when the sample was a solid resin, dissolved in 50 mL of tetrahydrofuran (THF). Then, 50 mL of methanol solution of KOH (0.1 mol / L)
Was added and the mixture was refluxed for 30 minutes. After adding 1 mL of acetic acid, the chlorine content in the sample was determined by potentiometric titration with standard silver nitrate, and the hydrolyzable chlorine content was calculated from the data obtained.

[0058]Example 3  Polyglycidyl ester resin VII of the present invention, and comparative
Production of polyglycidyl ester resin: 2 types of linear tertiary fat
Aliphatic carboxyl functional polyester resins 1 and 3-5
A 0:50 equivalent blend is treated with epichlorohydrin (ECH).
3.4 moles in isopropyl alcohol (IPA) and water
Dissolve in the ratio of 60:30:10 ECH, IPA and water
Was. Dissolve the solution in a 1 liter gas
Feed to the lath pressure reactor. Adjust temperature to 78-83 ° C
And the first 0.09 mole of NaOH in 20% by weight aqueous solution
The addition was made to the reactor under pressure over 12 minutes and additional
The reaction was performed for 8 minutes. While adjusting the temperature to 83-88 ° C
Et al., Sequential addition of a 0.27 mol 20% by weight aqueous solution of a second NaOH.
The addition was made to the reactor under pressure over 15 minutes and additional
The reaction was performed for 4 minutes. React reactor contents to 52 ° C in 10 minutes
Cool and add a third addition of a 0.07 molar aqueous solution of NaOH
Place the reactor under pressure for 1 minute, then add additional reaction
For 4 minutes. Finally, the final NaOH 0.023 mol
The sequential addition of the aqueous solution is carried out by pressing the reactor over 1 minute.
An additional reaction was then performed for 4 minutes. Reactor contents
Settled and the aqueous layer was separated from the organic layer. Organic layer is 3 with water
And then the organic phase is vacuum flashed and
Rohydrin and other volatile components were removed. like this
Take out the polyglycidyl ester obtained in
Rejected. Table 2 shows the properties of the polyglycidyl ester resin.
did. Hydrolysable chlorine (organic that may be present
Was determined in the same manner as in Example 2.

[0059]

[Table 2]

[0060]

[Table 3]

[0061]Example 4  Polyester 1 or 2 was converted to epichlorohydrin (ECH) 8
7.68 mol of isopropyl alcohol (IPA) and water
Dissolved in 7.68 moles. Solution with temperature controller, stirrer
And supply to 3 liter glass reactor with reflux condenser
did. Then the temperature was raised to 75-85 ° C and the initial NaOH
Sequential addition of 0.195 molar aqueous solution over 20 minutes
Was. After an additional reaction of 50 minutes, the reaction contents are
And cooled to 55 ° C., followed by the addition of 1.105 mol of a second NaOH.
The sequential addition of the aqueous solution was performed over 60 minutes. Additional reactions
After 5 minutes, the contents of the reactor are allowed to settle, and
Separated from the formation. The organic phase is vacuum flushed with water, IP
A and EPH were removed. The resulting product is
Dissolved in water and the organic layer was washed four times with water.
Empty flush to remove methyl isobutyl ketone.
The polyglycidyl ester thus obtained is removed.
Dispensed and cooled. The epoxy group content of the obtained resin is
They were 2908 and 2834 mmol / kg, respectively. Hydrolysis
Possible chlorine contents are 0.13% and 0.14% respectively
there were.

Continued on the front page (72) Inventor Edward John Marks Oakcroft Drive, Houston, Texas, USA 11902 (72) Inventor Josef Jacobs Titus Sumits 1031 Seem Amsteldam, Badfischwech 3 Netherlands F term (reference) 4J029 AA03 AB02 AC01 AC02 AD02 AE17 BA02 BA07 BA10 CD03 KH01 4J036 AG03 AK19 DB15 DB18 DC02 DC46 GA02 GA04 GA11 JA01 4J038 DB091 KA03 KA04 LA02 NA03 NA05 NA27 PB07

Claims (30)

[Claims] 1. A glycidyl ester composition prepared by reacting a carboxy-functional polyester compound having an acid number of less than 280 mg KOH / g with an excess of epihalohydrin in the presence of a suitable base and optionally a catalyst,
The carboxy-functional polyester resin then comprises: (a) at least one compound A;
Is an anhydride of: Wherein R and R ′ are each independently hydrogen or an alkyl group having 1-4 carbon atoms attached to the cyclohexane ring, or can form a cyclohexane ring together. Or one secondary acid group and one 3
(B) at least one compound B; compound B has an oxygen content of at most 35% and contains two aliphatic or cycloaliphatic hydroxyl groups, and If it is a di- or di-primary hydroxyl compound containing no β-hydrogen atom and having at least three carbon atoms between the two hydroxyl groups or if compound C is present, Epoxide D; this monoepoxide D
Is a monoglycidyl ester of an α-α-branched carboxylic acid having 5 to 19 carbon atoms; and, optionally, (c) at least one compound C;
A carboxylic acid or an anhydride; in a molar ratio of compound A: B: C of 2: X: Y, where Y is in the range of 0-3 and X is Y + 1, Wherein the carboxy-functional polyester compound is prepared by reacting at a temperature effective to react essentially all of the hydroxyl groups initially present and formed therein. A glycidyl ester composition substantially free of. 2. The glycidyl ester composition according to claim 1, wherein the compound A is an anhydride in which R and R ′ each independently represent hydrogen or a methyl group, or a mixture thereof. 3. The method according to claim 1, wherein the compound A is 1,2-cyclohexanedicarboxylic acid or hexahydrophthalic acid, 5-methyl-1,2-
An anhydride of an acid selected from the group consisting of cyclohexanedicarboxylic acid, 2,3-dimethyl-5-isobutyl-1,2-cyclohexanedicarboxylic acid, endomethylenetetrahydrophthalic acid, and 5-methylendomethylenetetrahydrophthalic acid, or 1 The glycidyl ester composition according to claim 1, which is a diacid selected from the group consisting of -alkyl-1,4-cyclohexanedicarboxylic acid, wherein the alkyl group has 1 to 4 carbon atoms. 4. The glycidyl ester composition according to claim 1, wherein said compound B is a diol having an oxygen content of at most 30% by weight. 5. The glycidyl ester composition according to claim 1, wherein said compound B is a di-secondary hydroxyl compound. 6. The compound B is neopentyl glycol, hydrogenated diphenylolpropane (HDPP), hydrogenated 4,4 ′
2. The composition of claim 1, wherein the composition is selected from the group consisting of -dihydroxydiphenyl, 1,4-dihydroxycyclohexane, neopentyl glycol hydroxypivalate, and 2-butyl-2-ethyl-1,3-propanediol, and mixtures thereof. Glycidyl ester composition. 7. The glycidyl ester composition according to claim 1, wherein said compound B has an oxygen content of 30 to 5% by weight. 8. The glycidyl ester composition according to claim 6, wherein the compound B is hydrogenated diphenylolpropane. 9. The glycidyl ester composition according to claim 1, having a hydrolyzable chlorine content of at most 6000 mg / kg and an epoxy group content of at least 90% of theory. 10. The glycidyl ester composition according to claim 9, wherein Y is in the range of 0 to 1. 11. The glycidyl ester composition according to claim 9, wherein Y is 1. 12. The glycidyl ester composition according to claim 11, wherein said component (b) is a mixture of compounds B and D. 13. The compound C according to claim 1, wherein the compound C is 1,4-cyclohexanedicarboxylic acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2,3-dimethyl-1,4-cyclohexanedicarboxylic acid, and 1,4-dicarboxylic acid. The glycidyl ester composition according to claim 11, which is selected from the group consisting of 2,5-dimethylcyclohexane. 14. The glycidyl ester composition according to claim 13, wherein compound C is 1,4-cyclohexanedicarboxylic acid. 15. The glycidyl ester composition according to claim 9, wherein Y is 0. 16. The glycidyl ester composition according to claim 1, wherein Y is 0. 17. A composition comprising the glycidyl ester composition of claim 1 and a curing agent or co-reactant. 18. The composition according to claim 17, which has been cured or reacted. 19. A braid comprising the glycidyl ester composition of claim 9 and a curing agent or co-reactant. 20. The composition according to claim 19, which has been cured or reacted. 21. A composition comprising the glycidyl ester composition of claim 16 and a curing agent or co-reactant. 22. The composition according to claim 21, which has been cured or reacted. 23. A glycidyl ester composition prepared by reacting a carboxy-functional polyester compound having an acid value of less than 280 mg KOH / g with an excess of epihalohydrin in the presence of a suitable base and optionally a catalyst,
The carboxy-functional polyester resin is then (a) at least one compound A; compound A is an anhydride of the following formula (I): Wherein R and R ′ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms attached to the cyclohexane ring; and (b) at least one compound B;
Compound B is hydrogenated diphenylolpropane;
Prepared by reacting at a temperature effective to cause essentially all of the hydroxyl groups initially present and formed in the reaction mixture to react in a molar ratio of compound A: B of about 2: 1. A glycidyl ester composition wherein the carboxy-functional polyester compound is substantially free of unreacted diacid monomer. 24. (a) (i) at least one compound A;
Compound A is an anhydride of formula (I): Wherein R and R ′ are each independently hydrogen or an alkyl group having 1-4 carbon atoms attached to the cyclohexane ring, or can form a cyclohexane ring together. Or diacids having one secondary and one tertiary acid group; (ii) at least one compound B; compound B has an oxygen content of at most 35% and two aliphatic Or a di- or di-hydroxyl compound containing an alicyclic hydroxyl group and containing no β-hydrogen atom and having at least 3 carbon atoms between the two hydroxyl groups. Or, if compound C is present, a monoepoxide D; this monoepoxide D is a monoglycidyl ester of an α-α-branched carboxylic acid having 5 to 19 carbon atoms; iii) at least one compound C; this compound C is di-2
A carboxylic acid or an anhydride; with a molar ratio of compound A: B: C of 2: X: Y, where Y is in the range of 0 to 3 and X is Y + 1, By reacting at a temperature effective to react essentially all the hydroxyl groups present and formed in the reacted reaction mixture, it has an acid number of less than 280 mg KOH / g and 280 mg KOH / g
Producing a carboxy-functional polyester compound substantially free of diacids having a higher acid number; (b)
The carboxy-functional polyester compound from step (a) is reacted in the presence of a suitable base and optionally a catalyst such that essentially all of the carboxyl groups initially present and formed in the reaction mixture are reacted. Producing a glycidyl ester composition by reacting with an excess of epihalohydrin at an effective temperature;
A process for producing a glycidyl ester composition having a hydrolyzable chlorine content of mg / kg and an epoxy group content of at least 90% of theory. 25. The method of claim 24, wherein said carboxy-functional polyester compound has an acid number ranging from 150 mg KOH / g to 280 mg KOH / g. 26. The method according to claim 24, wherein compound B is hydrogenated diphenol propane. 27. The method according to claim 24, wherein Y is zero. 28. The method according to claim 27, wherein the reaction of step (a) is performed at a temperature in the range of 100 to 200 ° C. 29. The method according to claim 27, wherein the reaction of step (b) is performed at a temperature in the range of 20 to 125 ° C. 30. (a) (i) at least one compound A;
Compound A is an anhydride of the following formula (I): Wherein R and R ′ are each independently hydrogen or an alkyl group having 1-4 carbon atoms attached to the cyclohexane ring, or can form a cyclohexane ring together. Or diacids having one secondary and one tertiary acid group; and (ii) at least one compound B; the compound B has an oxygen content of at most 35% and Di-2 containing aromatic or cycloaliphatic hydroxyl groups and containing no β-hydrogen atom and having at least 3 carbon atoms between the two hydroxyl groups
A primary hydroxyl compound or a di-primary hydroxyl compound, or a mixture thereof; in a molar ratio of compound A: B of about 2: 1, the essence formed in the initially present and reacted reaction mixture. By reacting at a temperature effective for all of the hydroxyl groups to react, 280
producing a carboxy-functional polyester compound having an acid number less than mg KOH / g and having substantially no diacid having an acid number greater than 280 mg KOH / g; (b) said carboxy function from step (a); By reacting the reactive polyester compound with an excess of epihalohydrin at a temperature effective to react essentially all the carboxyl groups initially present in the reaction mixture in the presence of a suitable base and optionally a catalyst. Producing a glycidyl ester composition, at most 6000 mg /
A process for producing a glycidyl ester composition having a hydrolyzable chlorine content of kg and an epoxy group content of at least 90% of the theoretical amount.