JPS5874714A - Production of polyepoxide/aliphatic alcohol adduct - Google Patents

Abstract

PURPOSE:To obtain smoothly a variety of the titled adducts without encountering catalyst deactivation by water or the like, by reacting a polyepoxide with an aliphatic alcohol in the presence of a heteropoly acid actalyst. CONSTITUTION:A polyepoxide/aliphatic alcohol adduct is obtained by reacting a polyepoxide (e.g., epichlorohydrin oligomer, epoxide obtained by oxidation of dicyclopentadiene) with a monohydric or polyhydric aliphatic alcohol (e.g., methanol, ethylene glycol) in the presence of a heteropoly acid (e.g., 12-tungustophosphric acid, 9-molybudo-3-vanadophosphoric acid). The heteropoly acid can be obtained by condensing an oxyacid or its salt which is a starting material in an aqueous solution to form a corresponding heteropoly acid or its salt and, in case of the salt, recovering the free acid by, for example, solvent extraction from an acidic aqueous solution thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an alcohol adduct of the Cyto/111+ItFj group in polyepoxy resin, and more specifically, the present invention relates to a method for producing an adduct of an alcohol in the polyepoxy group, and more specifically, as a catalyst, hete vsdl! The chemical compound is reacted with an aliphatic alcohol using @, and polyepoxide 7kEH is produced.
11 relates to a method for producing an alcohol adduct t-.

Polyepoxide and monohydric or polyhydric aliphatic alcohol undergo an addition reaction as shown by the following reaction formula and/or to produce polyepoxide/aliphatic alcohol or monoadduct.

This addition reaction is generally slow, and in order to accelerate this reaction, the # reaction is conventionally carried out in the presence of a catalyst. Traditionally, boron trifluoride (B^
) and amines, alcohols, phenols, ethers, etc. (for example, see Japanese Patent Publication No. 1851-88160). Now, dissociation 7. Because it releases trifluoride gas, it is difficult to use reaction K which requires high temperature69, and disadvantages include easy deactivation due to moisture K and troublesome handling. There is.

It is also known to use citric acid, quaternary anneptaecum salts, and alkali metal salts or alkaline earth metal salts of fatty acids as other catalysts, but these catalysts lack activity and cause scissor reactions. 1#-υ, related Fi4
There are drawbacks such as making Rie 4 Kikudo into a kin.

Therefore, the present inventors have conducted various studies on catalysts that do not have such drawbacks and can smoothly promote the addition reaction between 4-Lipo-Cyto and monohydric or polyhydric aliphatic alcohol.
They discovered that hetyl phosphoric acid is extremely suitable and completed the present invention.

Therefore, according to the present invention, a heteropolyacid can be used as a catalyst in a method for producing a polyepoxide/aliphatic alcohol adduct by reacting a polyamide acid with a monohydric or polyhydric aliphatic alcohol. A method is provided which is characterized in that:

The "heteropolyacids" used as catalysts in carrying out the method of the present invention are various inorganic oxyacids produced by condensation between two or more types of inorganic oxyacids, and their central heteroatom is 11. s, p1A#, Zs, Co
, Cm, G-, etc., can be a wide range of elements from Groups 1 to 1 of the periodic table. On the other hand, as the polyatom to be coordinately condensed to the hetero atom, atoms of Group 1 or Group V of the periodic table are usually separated, and W and No%V are particularly common. These heteropoly I! l! is synthesized by condensation of starting oxyacids or oxyacids in aqueous solution to obtain the corresponding heteropolyacids or hetero-I phosphates, respectively. method) as the free acid. For a more detailed description of such hetaI24 phosphoric acid and its synthesis method K1m, please refer to the literature mentioned below = (1) G, A,
Taiydimoa, I'd, Esg, Chaq
Prod.

Ram Develop 3 @ 111th block (I11
Ma4) 12) Iserg, Sys, a 1 #
1111MmGr*w-H4ll (18B9) 43) G, A, Taiydimoa, C, J, E
aLlads.

Isarg, Chaqma, 4st (leas) (4Q
P,, S collection, M, T, Pops, I attack O det,
Cλ-1.

1! , 331 (1913).
It is difficult to give an example of F1. :l - Tandust phosphoric acid, l! - Molybdophosphoric acid, 18-tangest silica 1% 1! -4 Ribdosilicic acid, -Molybdo-6-tungsilinic acid, l.-Molybdo-2-vanadophosphoric acid, 11-4 Ribdo-1-vanadori 7g, 9-
Molybdo-3-vanadophosphate, 11-tungst-2-
vanadric acid etc.

These heteropolyacids can be used individually or in combination of two or more. The amount of heteropolyacid to be used is not strictly limited and can vary widely depending on the species of epoxy compound and/or aliphatic alcohol used, reaction conditions, etc., but it is generally based on the weight of the epoxy compound. e-user terms
ov'pm to i=6'X, preferably 20(
lvk to goo.

νpwh (It is advantageous to use it within the Q range. In addition, in this reaction, the combined use of groton # such as para-toluene sulfone # will further accelerate this reaction, shorten the reaction time, and reduce the concentration of the reaction vessel. The temperature can be lowered by 6.

It is a low-molecular weight or high-molecular compound having an average of more than 1@, preferably more than Fig groups, in one molecule of the polyepoxide that can be reacted in the presence of the above-mentioned heteropolymer. The 4-epoxide used in addition reactions with aliphatic alcohols will eventually be produced in one bottle f! It can be used in A. Such polyepoxides can generally have number average molecular weights ranging from about .0 to about 7000, and also generally from .0 to 4600. It is advantageous to have an epoxy content preferably within the range of Fi 150 to 5ooo. Further, it is preferable that the polyeixide melts into the alcohol used in this reaction at room temperature or under heating conditions, or forms an emulsion when mixed with the alcohol.

Specific examples of polyethylene oxide that can be used in the present invention 1jQ are as follows, but these are merely examples, and the epoxy compounds that can be used in the method of the present invention are as follows. It should be understood that the examples are not limited to those shown.

(→ Epoxide obtained by oxidation of dienes such as dicyclopentadiene, 7-chlorohexadiene, cyclododecadie/, cyclododecatriene, isoprene, l,5-hexadiene, butadiene, 4y-butadiene, divinylbenzene; (&) of epihalohydrin Oligomers of epihalohydrin such as; (C) polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, polyglycol, thiodiglycol, glycerin', pentaerythritol, nrubit, polyvinyl alcohol, -realyl alcohol and epihalohydrin/and and reaction products of glycidyl ether and ethylene oxide and/or pyrene oxide; (b) resorcinol, hydroquinone, g, g'-
18,4- and/or i4.4'-dihydroxydiphenylmethane, bis-(4-hydroxy-3-methylphenyl)-methane, bis-(4-hydroxy-3,S-dimethylphenyl)-methane , bis-(4-hydroxyl-3,5-dibromphenyl)-methane, bis-(4-
Hydroxyphenyl)-ethane,! , 2-bisou (4
-hydroxyphenyl)-propane, jl, 2-bis-
(4-Hydroxy-3-methylphenyl)-bootdan,! , 1-bis(4-hydroxy-3-chlorophenyl)-propane, 2,2-bis-(4-hydroxy-8
,5-dichlorophenyl)-glu/example/,his-(4-
Hydroxyphenyl) -phenylmethane.

Bis-(4-hydroxyphenyl)-diphenylmethane, bis-(4-hydroxyphenyl)-a#-methylphenylmethane, 1,1-bis-(4-human-xyphenyl)-gag-)9 chloroethane, bis-( 4-hydroxyphenyl) -4-purphenylmethane, 1.
1-(4-diphenyl) -cyclohexane, 'bis(4-hydroxyphenyl)cyclohexylmethane, 4,4'-dihydroxydiphenyl,!
,! Glycidyl ethers derived from the reaction of epiverhydrin with polyhydric phenols or phenol-formaldehyde synthesis products such as hydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone, and the hydroxyethyl ethers of these. Joy (-) S
- and N-containing epoxides, such as 911 N,N-di/I
J cidylaniline, N,Nl-dimethyldiglycidyl-
4,4-Cyanodifermethane, etc. (a) Adipic acid, pimeline #t% sebacic acid, sperinic acid, azetuic acid, phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, hexahytophthalic acid, etc. di-, tri-, or detraglycidyl esters of (I/) and other p-oxybenzoic acid glycidyl ester ethers.

On the other hand, the monohydric or polyhydric aliphatic alcohols reacted with the polyepoxide include almost all saturated and unsaturated alcohols, including KiE monobranched, monobranched, etc. Its use is not limited by its structure, aromatic product, presence or absence of halogen atoms, etc.

][Although there are differences in reactivity, any of the 81st class, 1st fi, and 111th class types can be conveniently used as alcoholic soap-based soaps.

A specific example of such alcohol is 54D described below.
Although the aliphatic alcohols that can be used in the method of the present invention are not limited to these examples, it is understood that other aliphatic alcohols can be used. Should.

(--th aliphatic alcohol: methanol, ethanol, noropanol, isobutanol, butanol, isobutanol, a-butanol, t
-butanol, pentanol, 4-methylbutanol,
2-pentanol, 2-methyl-2-butanol, 3-
Methyl-2-butanol, hexanol, cyclohexylmethanol, cyclohexyl alcohol, 4-methyl-2-
Pentanol, hexanol, 2-hexanol, octatool, 2-octatool, 2-ethylhequinanol, nonanol, mixture of isomers of nonanol, tecanol, allyl alcohol, l-butene-reef-ol, l
-Buten-3-ol, 3-hexen-1-ol, methyl cellosolve, methyl cellosolve, bunal cellosolve, diethylene glycol 7-methyl ether, diethylene glycol%/! ? ether, diethylene glycol methyl ether, benzyl alcohol, (4-methenodiphenyl)methanol, 1-phenyl-1-buten-3-ol,! - Cool ethanol.

1.3-dichloro-2-bupanol, 3-dichlorobupanol, 3-chloropro/#nol, 1-cool-tomi-pro/#nol, etc.

(1) Polyvalent l1lD group alcohols: ethylene glycol, neopentyl/9:2-At, propylene glycol, butylene glycol, hequinanediol, for example, higher glycols found in K when dical & 3/II tube hydrogenation, Xylylene glycol, hequinahydride, 1,4-cytane diol, glycerin.

Diglycerin, triglycerin and higher polyglycerols, methylglycerin, trimethylethane, trimethylol depan, pentaerythritol, pennut, hexite and hexa-, di- and polysaccharides (optionally partially etherified or esterified) Polyglycols, polyvinyl alcohols, polyvinyl alcohols, etc., which may be produced by polymerization or copolymerization of olefin oxides) and which include low-molecular products such as diethylene glycol, triethylene glycol, etc., as well as high-molecular weight products. acylated 4-rivinyl alcohol, polyallylic alcohol, copolymers of alllylic alcohol and other unsaturated compounds, or completely or partially hydrolyzed 109-denecarbonate compounds, etc. .

The reaction between a nixyl compound and a monohydric or polyhydric aliphatic alcohol is usually carried out in the absence of a bath medium or in an aggressive inert bath medium, such as dioxane, tetrahydrofuran, benzene, toluene, xylene, etc. In general, temperatures between #1 room temperature and 2sOCfk+ are preferred! IO ~ approx. 1
It can be carried out at a temperature of 60C.

According to the method of the present invention described above, a wide range of I11! Epoxy compounds/aliphatic alcohol adducts with moderate physical properties are obtained, and these adducts are used in a variety of ways depending on their physical properties. For example, by using a large amount of alcohol component to open the epoxy group When ringed, it can be used as an 49-ol component in polyester, polyurethane, alkyd resin, etc., and when a small amount of the alcohol component is used to leave an epoxy group, 9 and ti can be used as epoxy resins with increased molecular weight. It will be done.

Next, the present invention will be explained in detail with reference to examples.

Implementation 1i111 Stirrer, warm needle and lllllll flow cooling pipe equipment *11d-4
A 4-liter amount of bisphenol A epoxy (if 150 f (α78 g equivalent) and monoethylene glycol!!io? (371 mol) was added to a 7-liter tube, and the mixture was heated in an oil bath at 6 csoC under an atmosphere of 11. When the contents of the flask become a white emulsion, add 100q of phosphotungstic acid (P, 0124WO, Hatsuru O trial grade) to 100q of monoethylene glycol. Add the solution.The reaction solution becomes carcinogenic, and when the temperature inside the flask reaches about 12 (IK), the reaction solution becomes transparent and homogeneous.
Then, the temperature of the oil bath was increased to tBfil 14oC, and the reaction was continued for an additional 8 hours.

After completion of the reaction, unreacted monoethylene glycol is distilled off under reduced pressure on an oil bath of the reaction mixture t-1103:. Recovery amount of monoethylene glycol SlI&
5F (71 L ethylene glycol 1 for 1 epoxy group)
Synthesis theory of infusion assuming that the molecules have reacted: 196.
Of).

The product thus obtained is a highly viscous liquid that is colorless and transparent at room temperature, has a hydroxyl value of Fi4'l01111KOH/f (one molecule of ethylene glycol per 111 epoxy groups Assuming that there is a reaction, the theoretical hydroxyl value in the case of light -4@"l"fKOH/l
)Met.

Example 2 In the same apparatus as in Example 1, an appropriate amount of epoxy (f/m
e, )'s Bi x Fu x ) - Lu A li x Poki VII
10Of ((16 equivalents of Li)) and 8.@f (!4!! moles) of diethylene glycol are prepared and heated and stirred on a 1..C oil bath in a phonetic atmosphere.The contents of the 7 rasus are uniformly transparent. If you get to 1, 1 phosphorus tungstic acid 6 tons of diethylene glycol l if in ****
Add. Although the reaction solution generates heat, unreacted ethylene glycol is distilled off under reduced pressure on an 18 Org oil path after the reaction is completed for 0 hours. Recovery of diethylene glycol @t21. zt (theoretical recovery assuming that one molecule of sitaethylene glycol reacts with one epoxy group) 12! &4 f). The product thus obtained is a highly viscous liquid that is colorless and transparent at room temperature, has an epoxy weight of 100,000 f/aq or more, and a hydroxyl value of 404 MIKOH/l (diethylene glycol 1 for 1 epoxy group). Theoretical hydroxyl value lx a s 2 wgKOH/f)' assuming that the molecules have reacted
Terrorism nine.

Example 3 ＼＼ Same as Example 1, epoxy 1i190<f/a
q) bisphenol Alt epoxy resin spirit 0(1(t
Os per k) and methanol 15Of (Table 68 mol) were charged, and the mixture was heated and stirred on a fourth lupus at 80C under an ia atmosphere. When the contents of the flask become uniformly transparent, add phosphotungsten @ 130'lf of methanol 18.
Add VR solution in 6 f. Under reflux of methanol, 6
Allow time to react.

After the reaction is completed, unreacted methanol is distilled off under reduced pressure on a 120C oil path. Recovery amount of methanol 18
41F (Theoretical recovery amount 13411F assuming that 1 molecule of methanol reacts with 9 epoxy groups) 1
．． The product thus obtained is a pale yellow and transparent high viscosity liquid at room temperature, with an epoxy unit of 160,000 r/sq or more and a hydroxyl value of m6GwvKOH/f (one molecule of methanol per one hydroxyl group). The theoretical hydroxyl value was 0 vqKOH/l) assuming that the product reacted and was eaten.

Example 4 The same 6!11 as in Example 1 was added with an epoxy commercial amount of 190 (t/
ag) bisphenol Afjl epoxy resin 120?
(0682 equivalents) and Zorobire/Glywol 2tO
t (18,114 l) and heated under nitrogen atmosphere.
Heat and stir on an oil bath. When the flask becomes a white emulsion, a solution of 90 ml of phosphotungstic acid in 2α3f of propylene glycol is added. The reaction solution generates heat and becomes uniformly transparent after ft.
The temperature of the oil bath was raised to 140°C and the reaction was carried out for 1Q hours.After the reaction was completed, unreacted propylene glycol was distilled off under reduced pressure on a 110t:' oil path. Yield of 1gl of propylene glycol 1i1915f (Assuming that one molecule of propylene glycol reacts with one epoxy group, Haniwa recovery 1i1913F in case of 7) This lid is over 100,000 (f/#f) and has a hydroxyl value of 44.
0yqKOH/f (epoxy) fat for 1
Assuming that one molecule of lengelicol has reacted, the theoretical hydroxyl value of 436 WKOH/f).

Example S Example 1 and lWiw's installation @ K x I! Ki V equivalent 1
116 (f/me) bisphenol A type engineering Iki v11
Fat II! Of (17811 weights) and xp/-Jl
Charge y11@f (7.1@mol), heat and stir on a C oil path in a nitrogen atmosphere. The contents of Mukuro 7 TSU; were in the form of a white emulsion @flcfk':)*, and 110 tsp of phosphotungstic acid was dissolved in ethanol $40F. Ethanol will reflux. Let the reaction continue for 14 hours. After the reaction is complete, unreacted ethanol tIl is discharged under reduced pressure on the oil path of C. Recovery amount of ethanol s * v, o
r (theoretical recovery amount smy, st assuming that 1 molecule of ethanol reacts with 4 key groups 1@), the product thus obtained is 11IIi and pale yellow 6% 11B (D high volume 1 liquid) The epoxy tI is 100,000 (f/ge) at 1%, and the water base value is 249 WIIKOE/l. l).

Example 6 Similar to Example 1 #C to which epoxy 1i1110 (t
t/aq) bisphenol A removed epoxy m8 effect 1 oa
r (asgsam) and methyl cellosolve 3 fields 0f
(499 mol) was charged and heated and stirred on a 90C oil path under an i1 element atmosphere. When the contents of the flask become uniform and transparent, phosphotungsten @ 80 ml of methyl cellosolve! Add solution in air. The reaction solution generates heat, but then the oil bath a! Raise the temperature to 1tttgoc and allow to react for 3 hours. After the reaction is completed, unreacted methyl cellosolve is distilled off under reduced pressure on an oil path at 1401:'. Recovery amount of methyl cellosolve 351L3F (theoretical recovery amount msa assuming that one molecule of methyl cellosolve reacts with one epoxy group by burning).

f) The product thus obtained is a high viscosity liquid that is yellow and transparent at room temperature, has an epoxy equivalent of 100,000 <t/aq> or more, and a hydroxyl value of galqA□#/r (1 epoxy group to 1 methyl cellosolve). The theoretical hydroxyl value **@IIKOH/l) assuming that the molecules have reacted.

Example 7 An amount of epoxy 110 (
r/sa)'s bisphenol Am 4Ki machine fat@Of
(a411fi amount) and inoyl alcohol s 5
Of (1974) was prepared and heated under nitrogen atmosphere for 90 minutes.
Heat and stir on an oil bath of C.・The contents of the 7 rasu become a white emulsion. x s oq of isoar alcohol '1LOt
0 reaction 9F1 in which the solution solution is added generates heat, but after that the temperature of the oil path is raised to xROc and the reaction is continued for 5 hours.

Reaction range f: 16 ml of isoamyl alcohol is distilled off under reduced pressure on a 14 oc oil bath. Recovery amount of inoyl alcohol: 5 shots (theoretical recovery i33&9F assuming that one molecule of isoamyl alcohol reacts with one epoxy group). The product obtained by peeling Fi is a pale yellow transparent liquid at this temperature, the epoxy equivalent is 1.10,000 (f/aQ) or more, and the hydroxide value is 210 Cape KOH.
/f (1 isoamyl alcohol to 41 epoxy
Yangse's theoretical hydroxyl value assuming that the molecules have reacted! 1
6IlvA(/#/f) Terror &.

Example 8 Epoxy equivalent weight 190 (r
/gq) of bisphenol A-filled epoxy side fat tgor
(αsag to jk) Jf and isopropano-885
0t (N 82 mol) and Ks under ia elementary atmosphere.
Heating on an oil bath at oC, 1. kj, stir. When the contents of the flask become a white emulsion, a solution of 300q of phosphotungstic acid in 30f of isozolopanol is added. The reaction is continued for 10 hours under refluxing isopropanol. After the completion of the reaction, unreacted iodineol is distilled off under reduced pressure on a 116c oil bath. Amount of isopropanol recovered: 842. (Yield of 34 LOf when it is assumed that one molecule of isopropanol reacts with one unit of 4x) The product obtained in this way is a pale yellow transparent high viscosity liquid at room temperature. Keishi Todoroki has a water e1M value of 100,000 (f/sq) or more.
t weAOH/f (theoretical hydroxyl group @2a6wpKOH/l assuming that one molecule of isopur/monol reacts with epoxy group 111).

Example-Example 111 and fjjl&notillKz/*shit t t
60 tons (0,316 parts i) of bisphenol A type Nyxy resin of 90 (f/a e) and 2909 [90 moles] of cyclohexanol were charged, and heated and stirred on an oil bath at 90C in a concave atmosphere. . When the contents of the flask become a white emulsion, a solution of 150q of phosphotungstic acid in 2a3f of cyclohexanol is added. After the reaction solution generates heat and becomes uniformly transparent,
The temperature of the oil bath was raised to 140C and the reaction was carried out for 8 hours. After the reaction is completed, unreacted cyclohexanol is removed under pressure on an oil bath at 140C. Recovery amount of cyclohexanol: 284.1-9<Assuming that one molecule of cyclohexanol reacts with one epoxy base, the theoretical recovery in the following case: 1128, 4.7F). The product thus obtained is a pale yellow, transparent, highly viscous liquid at temperature. The xy equivalent is 100,000<t/aq) or more and the hydroxyl value is 200qKO
II/f (theoretical hydroxyl value of the combination tO1qlKOE/l assuming that one molecule of cyclohexanol is anti-Lf; L for each Eikile group).

Example 1G Epoxy commercial amount 1116 (?/$
4F) bisphenol A type epoxy resin set (α
4! 1 lid) and 5 sets of S-butanediol
(lsg mol) and heated and stirred on an -oC oil path under a nitrogen atmosphere.

If the domestic product in the carpet flask becomes a white emulsion &':), is it phosphotungstic acid? 1,3-butanediol L of OI9
Add solution in IQ, By. The reaction solution generates heat and becomes uniform.
After the arms become transparent, the temperature of the oil bath is set to 14 (IK) and the reaction is carried out for 12 hours. .1. Recovery amount of 3-butanediol 34a8F
(Assuming that 1 molecule of 1,3-butanediol reacts with 11 epoxies, the theoretical recovery amount is $41.1!)
f).

The raw tc thus obtained, 'Fk1, has a high viscosity for colorless filtration at a temperature of 1 [+ liquid and epoxy M is 100,000 (t/aq)]
Above, the hydroxyl group S is 420 to 011/f (epoxy 11
Assuming that 1 molecule of 1.3-butafdimer reacted with each 1.3-butafdimer, the fermented water base value of ft.

Example 11 1I! Epoxy Tohan 190 (F
/sa) bisphenol A type epoxy street fat 1201
(2 moles of CL6B) and 5 sets of Tei-Proper Tools
(582 mol) and 900 mol in 1Ill system atmosphere.
Heat and stir on an oil bath. When the contents of the flask become a white emulsion, phosphotungstic acid 151
Add 1j of n-propatool 30 to the bath solution. In this state, the reaction is continued for 12 hours under reflux of S-P-A-Nol. After the completion of the reaction, unreacted S-P-A-Nol is distilled off under pressure on a TGOC oil bath. Recovery amount of pseudo-PlIj danol s4x, tr (Theoretical recovery amount when assuming that 1 molecule of pseudo-PlIj panol reacts with 1 sK of epoxy group s a to F) @The product thus obtained is pale yellow at room temperature. Since it is transparent, the viscosity of the liquid is 4 and the amount is 1.
Hydroxyl value F at 00,000 (r/go) or more! ! $8wgKOE
/l (Theoretical hydroxyl value assuming that 1 molecule of 1-bootnol reacts with 11 epoxies! 40 Cape K
OH/f) I got it.

Souse IPII! The same device # as in Example 1 was used with 1 dF seam amount l$・(#/
me) Bispheno-#A1M Nyxy Resin Mallo t(a
s @ 8 volumes) and benzyl alu-s, 5 top (
&414#), heat and stir on the oil path of (C) under mIAws air.* Make sure the contents of the flask are even
Transparent 11 &) Also, V tungsten 11!1@・
Add the solution in Allure 11LJf to the cape vent. The reaction t & generates heat, but then the temperature of the oil path is reduced to 1
The temperature was raised to 20c and the reaction was carried out for 10 hours. 160c after completion of reaction
Unreacted benzyl alcohol is distilled off under reduced pressure on an oil path. Benzyl alcohol recovery lid 357
, (Theoretical recovery amount 35 kg 6 tons assuming that 1 molecule of benzyl alcohol reacts with 1 (4 groups))
The product thus obtained is a highly viscous liquid that is yellow and transparent at room temperature, and has an epoxy reaction temperature of 100,000 (f7gQ) or more.
Assuming that one molecule of be/zyl alcohol reacts with IK, the theoretical hydroxyl value of 7t [combination M 111 "IF KOH
/l) Terrorism Example 13 The same equipment as in Example 1 was used with a
f) bisphenol A type epoxy resin 1 or (o,
sts common) and allylfurcor 1lof (41
Heat and stir on an oil bath at 100C under nitrogen SS atmosphere and stir until the contents of the flask become uniformly transparent.
Add the solution in allyl alcohol 0. The reaction solution generates heat, but 11 hours. Perform the flowing reaction of allyl alcohol. 0. Reaction completed @ 1 0970 Oi, II//
(Unreacted allyl alcohol is distilled off under reduced pressure on the top. Allyl alcohol recovery Sagiyuki 1 Kamema f (Assuming that 1 molecule of allyl alcohol reacts with 1 xyl group) 0 * mm Yield: 1 [1°] The product thus obtained is colorless and transparent at room temperature, with a high sugar content, and the amount of epoxy is 1
・Over 10,000 (f/11), hydroxyl group i1 hits 3・Misaki KOH
/l (Assuming that 1 molecule of allyl alcohol reacts with 1 acetic V group, if π, e1m theory water moiety value feces 4 * q
KOH/f).

Example 14 Epoxy resin @410 (f/mq) was applied to the same device as in Example 1.
) of Bisphenol A9-4Ki cloth resin 11SOf (1
31g) and diethylene glycol 250? (2
, 36 mol), heated on an @OC oil bath under an i1 element atmosphere, and pressed horizontally.

7. When the contents of the rasu become white emulsion, diethylene glycol g of phosphotungstic acid 1001119
Add as to the bath solution in t-. The reaction * generates heat and becomes uniformly transparent, but after that the temperature of the oil bath [t14 (
After 5 hours of reaction on the IK top, distill off unreacted diethylene glycol under reduced pressure using the oil path on the tsoc.
13&7F (Theoretical recovery amount 1!8 assuming that one molecule of diethylene glycol reacts with one 4-oxy group)
7. Of), the product obtained in this way is a colorless solid at room temperature, has a hydroxyl value of 100,000 (f/*v) or more, and a hydroxyl value of KOIi/? (Assuming that one molecule of diethylene glycol reacted with one epoxy group, the chemical strength value was 1 m 9 tjW9KOE/f).

Example tS II! In the apparatus of Example Coloring 1, a chemical equivalent of 4 mmO (f/
go > bisphenol A11i engineering 4 xy resin goat
(α426 normal) and ethanol 1? Of (
! L69 model #) prepared -), nitrogen ays lower LC90C
Heat and stir on an oil bath. When the contents of the armpit 7 lasco become white emulsion, use phosphotungsten@Hiroshi00
11110 solution in ethanol is added. The reaction solution generates heat and becomes uniformly transparent, but the reaction is completed for 20 hours under 31 t IL of cott ethanol.
・Unreacted ethanol t*m under reduced pressure on the oil path of C
The theoretical recovery amount is 17a4F). The product 1Ithll obtained in this way is a colorless solid at room temperature and has an engineering equivalent of 1
00,000 (f/mq) or more, the hydroxyl value is 220M9KOH/
l (theoretical hydroxyl value 2111111KOH assuming that one molecule of ethanol reacts with one epoxy group and dew)
/f).

Example 16 In the same apparatus as in Example 1, 1i47G<t/I of epoxy
Bisphenol A type epoxy fat gsot (α
631! Equivalent amount) and methanol l5Of (4118 mol) were charged, and heated and stirred on an oil bath at 80C in an atmosphere of m atoms. When the contents of the 7th layer become a white emulsion, add 150 μm of phosphotungstic acid to 2 μm of methanol.
The reaction solution to which the f14 solution in 14f is added generates heat and becomes uniform.
Once the mixture becomes transparent, the reaction is continued for 9 hours under refluxing methanol. After the reaction is completed, unreacted methanol is distilled off under reduced pressure on a 120C oil path.

Methanol recovery i11! $2.8F (Theoretical recovery amount based on the assumption that one molecule of methanol reacts with one epoxy group is 15 & 4F). The product thus obtained is a pale yellow solid at room temperature, has an epoxy ratio of 100,000 m (f/go) or more, a hydroxyl value of 2 t, and a hydroxyl value of 'rqKOH/1 (one molecule of methanol reacts with one epoxy group). Assuming that, the hydroxyl value is 230~KOH/l).

Example 1 The same equipment as in Example 1 was used to produce 470 (f/me)
) bisphenol A epoxy resin goor (a<
gs 1t) and isoproper tool 2801 (18
8 mol) and heated and stirred on a 90t:' oil path under a nitrogen atmosphere. When the contents of the scissors 7 are in the state of white pore oil, add the solution in 'ff to the isopropanol of phosphotungsten@@0OIIF. '* Under reflux of isopropanol! Time to perform the reaction 0 After the reaction is completed 110
Unreacted isopropanol is distilled off under reduced pressure on oil path C. Amount of isopropanol recovered! 3 turtles 41
(Theoretical recovery amount 1141F assuming that 1 molecule of isopro/4-nol reacts with 1 4-oxy group (11)).

The product obtained in this way is a pale yellow solid at room temperature, with a molecular weight of 10,000 or more and a hydroxyl value of 218W.
eKOIi/l (iso! fight against one epoxy group)
Theoretical hydroxyl value assuming that one molecule of f-nol reacts! ! 11qAO#/F) and large.

Implementation f11 Epoxy equivalent 4'1<f/ to ktlt similar to Hatake implementation pH
Bisphenol A type epoxy resin from aq>! 5ep(a
sss amount) and ethylene glycol 14 m?
Charge (11,144 liters) and heat and grind on the oil path of KIOC under nitrogen atmosphere. When the contents of the flask become a white emulsion, add 180 q of phosphotungstic acid in Ethylene Dalitu #jlalF. 0 reaction 11 adding a solution of! After the mixture generates heat and becomes uniformly transparent, the temperature of the oil path is raised to 14@C and the reaction is carried out for 16 hours.After the reaction is completed, unreacted ethylene glycol is distilled off under reduced pressure on the 110r oil path. Amount of recovered ethylene/so-called 11L4F (assuming that one molecule of ethylene glycol reacts with one epoxy group, the theoretical recovery amount of 18
11t), thus the 116h product is a colorless O solid at room temperature, has a lifespan of 1,000 t/gal, and has a hydroxyl value of allllffOff/1 (19M- The theoretical hydroxyl group of pigeonhole was 1i812111KOH/l), assuming that one molecule of the molecule reacted.

Example! - an epoxy equivalent of 47 (1 (f/m
e) Bisphenol A-type epoxy resin 0f (a4
28 equivalents) and allylalbo,-ru2!・t(179
mol) and heated and stirred on a 1...C oil path under a nitrogen atmosphere.

When the contents of the axillary bath become white and milky, remove phosphotungsten [allyl alcohol of 25011f? ,
Add 1 f solution. The reaction solution generates heat, and under reflux of allyl alcohol l! Perform a time reaction.

After the reaction is complete!・Unreacted allyl alcohol is distilled off under reduced pressure on the oil path of C. Recovery amount of allyl alcohol 22α-t (theoretical yield wrinkle 2 assuming that one molecule of allyl alcohol reacts with epoxy group l-
g2.4F). The product thus obtained is a colorless solid at room temperature, has an epoxy equivalent of more than 10,000 (t/se), and a hydroxyl value of 10,000 KOH/v (one molecule of allyl alcohol reacts with one V group in Step 4). If we assume that
■Lonsui Mongki 1@IHsyf□ff/f).

Example 3 Epoxy equivalent of 4 m<f/- in the same equipment as in Example 111
(a8)
111) and methyl 4-solp S snow or (ts・
mol), heated and stirred on a Co oil pump under nitrogen SS atmosphere. # When the contents of the flask become homogeneous and transparent, add phosphotungsten@11 and ** in 111f of methyl cellosolve.The reaction solution generates heat. - Raise the CK and conduct the reaction for 4 hours. Reaction completion @14 Unreacted methyl cellosolp was distilled off under reduced pressure on a CO oil path. Methyl cellosolve's llI station amount 11 turtles of (technical 4 xy groups 11!
Assuming that 71 molecules of methylcelonol reacted with 1, the theoretical recovery amount in the following case is 1&@f). The product thus obtained is a colorless solid at room temperature, and 1 ton of epoxy is 10,000 (r/
sq) or more, the hydroxyl value is 216W9KO1i/l (
Situation theory assuming that one molecule of methyl cellosolve reacts with one epoxy group - Hydroxyl value 211 Misaki Koji/
f).

Example 81 Epoxy equivalent of 197G (F/
go) bisphenol A type engineered d-oxy resin 150F (
α11? equivalent) and methyl cellosolve 170F (
! ! 8Mo#)-i preparation, KI under nitrogen atmosphere! Heat and stir on an oil bath at loC.

When the contents of the flask become uniformly transparent, flIi[t-0 in methyl cellosolve 1111f of phosphotungsten@200q is added.Although the reaction solution generates heat, the reaction is continued for 116 hours.

After the reaction is completed, unreacted methyl cellosolve is distilled off under reduced pressure on a 1@OC oil bath. Recovery amount of methyl cellosolve 1 @ 142 (Theoretical recovery amount 1 assuming that 1 molecule of methyl cellosolve reacts with 1 Ake V group and 9)
814t), the product thus obtained is pale yellow at room temperature.
For 81 bodies, the E/*V quotient is over 100,000 (f/, #f) and the hydroxyl value is 11 wg @Fuji・*we KOH/t).

Example 1m The same apparatus 1 as in Example 1 was equipped with a knee xy equivalent of 111 ff·(
t, /B) bisphenol Afli engineering Iki V11 fat snow l・f (at snow i insect amount) and ethyf Lee ■
]t (!11 peak le) prepared, Nitakatai-kiki ■・C
t) Heat and stir on an oil bath. When the contents of the flask become a white emulsion, add phosphotungsten AK3.
Add a solution of 50 wII of ethylene glycol in 17.5 f. When the reaction solution heats up and becomes uniformly transparent,
The temperature of the oil bath was raised to 140C4C and reacted for 15 hours.

After the reaction is completed, one molecule of unreacted ethylene glycol is released under reduced pressure τ on a 160C oil bath.

Recovery of ethylene glycol k18111 (dioxy group 1
Theoretical recovery lid (lss, sr) assuming that one molecule of ethylene glycol reacts with 11.

The product thus obtained is a colorless solid at room temperature, has a nixie equivalent of 100,000 (f/*g) or more, and a hydroxyl value of M3BI.
IKOH/f (Assuming that one molecule of ethylene glycol reacts with x4dtV group l-011I theory hydroxyl value it m OQKOIi/t) Te4':
)7t@夷jlliF[113 In the same apparatus as in Example 1, an equal amount of epoxy saO (t/aQ
>(D Hydrogenated Phenol A [l Engineering 4*V@.

@zoot (0,8Woat)>XtD-fvyf9
2501 (403 mol) was added, heated and stirred on a 90C oil path in a phonetic atmosphere.

When the contents of the flask become a white emulsion, add 1 kettle of ethylene glycol of 10011 phosphotungstic acid and 9 f.
After the reaction solution generates heat, raise the temperature of the oil path by 140GK and let it react for 3 hours.After the reaction is complete,
1@(Unreacted ethylene glycol is distilled off under reduced pressure on the oil path of IC'. Recovery amount of ethylene glycol is 1147f (ethylene glycol per one V group in knee;
-Theoretical recovery amount 5 tons assuming that 1 molecule of the compound reacts
The product obtained in this way is a colorless and transparent high-volume liquid at room temperature, has an air volume of more than 1.10,000 (f/If), and has a hydroxyl value of 414 KOH/f (one life group). On the other hand, assuming that one molecule of ethylene glycol reacted, the acid group value of one N acid group was 419 KOB/f).

Implementation iPg124 Epoxy Yuki 1?0<f/aq on the same mounting W as in Example 1
> bisphenol F type epoxy Isl resin 1eaf (
118 mol) and methanol lmaot<hs*mol)
The mixture was heated and stirred on an oil path of KIOt:' under an electric atmosphere. When the contents of the flask are homogeneous and clear, add 130 wg of phosphotungstic acid in methanol IJLgf. Under reflux of methanol 6
Perform a time reaction.

After the reaction is completed, unreacted methanol is distilled off under reduced pressure on a 12 oc oil path. Methanol yield 111
50. or (theory assuming that one molecule of methanol reacts with the epoxy group 14-) @@7 t a a
s#) , -i-<si"C get real generation-?'1
It is a highly viscous liquid that is yellow and transparent at room temperature and has a lifespan of 100,000 yen (
t/aQ> or more -f: Hydroxyl value FX*I@qKOH/f
) (:g, assuming that 1 molecule of methanol reacts with ! groups in Il and 9) O1l theory hydroxyl group ! 3q J
KOH/t).

Example si The same equipment as in Example S
) Bisphenol F Knee Medium v @ Fat 111# (LS
I! Inspection) Oyobi Zf%/7g W: I-ru aSof (
4.S.) and stirred on a -.C oil path under a nitrogen atmosphere.

Wrinkle Futus: The spring material in the IO becomes a white emulsion state, and the reaction solution heats up and becomes a uniform state Kt'
:) Raise the temperature of the oil path by 14 eCK and allow the reaction to take place for S hours. After the reaction is complete, unreacted ethylene glycol is distilled off under reduced pressure on a 1...C'0 oil bath. Yield of ethylene glycol! If (theoretical recovery amount 211 Ljlf assuming that one molecule of ethylene glycol reacts with one 4-oxy group). The product thus obtained is a pale yellow, highly viscous liquid at room temperature and has an epoxy capacity of 1.
10,000<t/mQ) or more, hydroxyl value B50BaiKOH/l
(!1+?/Ml (1 for ethylene glycol for IK)
Assuming that the molecules react, the theoretical hydroxyl value of the combination is 4.1
qKOH/l).

Example s6 Same as Example 1 & Epoxy on crucian carp! 1i190 (f/m
e) Bisphenol A! J epoxy resin 1807 (
α78g equivalent weight) and ethylene glycol i! 80t (
171 mol) and heated and stirred on a 90C oil path under a nitrogen atmosphere.

When the contents of the 75F Sue become a white emulsion, add phosphotungsten filo019 and p-toluene xh*
y acid (CH5C6H4So, H-H,0)SOqO:L
When the reaction solution to which the solution in the green grill is added generates heat and becomes uniformly transparent, the temperature of the oil bath is raised by 140 cK and the reaction is further carried out for an extended period of time.

After the reaction is completed, unreacted ethylene glycol is distilled off under reduced pressure on a 1@OC oil path.

Amount of ethylene glycol recovered: 19! LIF (the yield of 1@tOf when it is assumed that one molecule of ethylene glycol reacts with 4xyl groups).

The product thus obtained is a colorless and transparent highly viscous liquid at room temperature, has a functional equivalent of 1.1 million (f/ur) or more, and a hydroxyl value of F.
i4 T *qKOH/l (Assuming that 1 molecule of ethylene glycol reacts with 1 nitrogen group, if large, 0
The hydroxyl value is 4@1TIIILOH/l)*.

Claims (1)

[Claims] 1. A method for producing a polyepoxide/aliphatic alcohol adduct by reacting a polyepoxide with one or more aliphatic alcohols, characterized in that a Hela 0-9 acid is used as a catalyst.