JPH0414698B2 - - Google Patents

Description

[Detailed description of the invention]

SUMMARY OF THE INVENTION TECHNICAL FIELD This invention generally relates to a method for making low viscosity adducts of polycaprolactone polyols and epoxides, which adducts are useful in the formulation of high solids coatings, polyurethane elastomers, inks, sealants, adhesives, and the like. . BACKGROUND OF THE INVENTION Products made from the reaction of polycaprolactone polyols with epoxides are known in the art. See, eg, US Pat. No. 3,896,303 to Gerkin and Comstock. One of the drawbacks of many products produced in the prior art is their relatively high viscosity, which poses problems in their production and use. The use of these highly viscous products in the manufacture of curable high solids coatings often requires the addition of solvents and produces curable coating compositions that are not necessarily curable high solids coating compositions.
The amount of organic solvent present in a curable high solids coating composition should be the minimum amount that produces little or no environmental pollution during the curing operation of the coating composition. Due to their high viscosity, many of these curable coating compositions produced in the prior art cannot be easily coated by roll coating, spraying and other application methods in the absence of viscosity-reducing solvents as described above. These compositions cannot be applied to suitable substrates by conventional techniques. Moreover, the solvent must be volatilized at some point during the curing operation; such volatilization consumes additional energy, wastes raw materials, and negates the benefits of high solids coatings against environmental pollution. This is important in light of public regulations that have ever-increasing limits on the amount and type of organic volatiles that can escape from coating compositions into the atmosphere. U.S. Pat. No. 3,896,303 to Gherkin and Comstock discloses (1) a caprolactone polyol having an average of at least three hydroxyl groups per molecule; (2) a polyepoxide having at least two adjacent epoxy groups per molecule; discloses a highly viscous polyol composition prepared by the reaction of Comparative Example A of the specification and US Pat. No. 4,045,474
Reference should also be made to Comparative Example 5 in the specification. These high viscosity polyol compositions can be reacted with aliphatic polyisocyanates to produce polyurethane coatings useful in high performance coatings. Such coatings exhibit the properties of high hardness, good impact resistance, low temperature flexibility and chemical resistance. No. 4,045,474 to Taller and Erder, the temperature is 54.5°C.
Highly functional polyol compositions having a viscosity of less than 5000 centistokes and an equivalent weight of at least 150 centistokes are described. Reference should be made to Comparative Examples B to E in the specification. These highly functional polyol compositions have (1) an average hydroxyl value of
(2) a cycloaliphatic diepoxide; and (2) a cycloaliphatic diepoxide. Such polyol compositions can be used with particular advantage in forming light-stable polyurethane coatings having a good balance of hardness, flexibility and abrasion resistance as well as weatherability and chemical resistance. DISCLOSURE OF THE INVENTION It has been found that the present invention can produce adducts of polycaprolactone polyols and polyepoxides having both an oxirane content of less than about 0.10% and a viscosity of less than about 3700 centistokes at 54.5°C. These low viscosity adducts contain at least 1
a polycaprolactone polyol and a polyepoxide having two or more epoxy groups per molecule in a polycaprolactone polyol to polyepoxide molar ratio of about 2:1 to about 3:1.
is the reaction product in. The low viscosity adducts of the present invention include polyepoxides, polyisocyanates, melamine formaldehyde, urea formaldehyde,
Little or no organic solvent is required to improve flowability during application to a suitable surface or substrate by conventional methods when mixed with a suitable cross-linking agent such as benzoguanamine formaldehyde and the like. It can be made into a curable high solids coating composition that does not contain any solids. Containing a low viscosity adduct of polycaprolactone polyol and polyepoxide,
Cured coatings prepared from these curable high solids coating compositions exhibit highly desirable coating properties. In one embodiment, the present invention provides at least one polycaprolactone polyol and a polyepoxide having two or more epoxy groups per molecule in a polycaprolactone polyol to polyepoxide molar ratio of about 2:1 to about 3. :
1, having an oxirane content of less than about 0.10% and a viscosity of less than about 3700 centistokes at 54.5°C. In another embodiment, the invention comprises a reaction product of at least one polycaprolactone polyol and a polyglycidyl epoxide having two or more epoxy groups per molecule,
The polycaprolactone polyol herein refers to an adduct of polycaprolactone polyol and polyepoxide used in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the polyglydyle epoxide. In yet another embodiment, the present invention provides one polycaprolactone polyol and 2 polycaprolactone polyols per molecule.
The reaction product comprises a polycaprolactone polyol to polyepoxide molar ratio of about 2:1 to about 3:1 with a polyepoxide having one or more epoxy groups, with an oxirane content of about 0.50% and at 54.5°C. Adduct of polycaprolactone polyol and polyepoxide having a viscosity of 20,000 centistokes. In yet another embodiment, the present invention relates to a method for preparing a low viscosity adduct of a polycaprolactone polyol and a polyepoxide, the method comprising at least one polycaprolactone polyol and two or more epoxy groups per molecule. at a temperature of about 80°C to about 225°C in the presence of a sulfonic acid catalyst or a derivative thereof,
using the polycaprolactone polyol, polyepoxide and sulfonic acid catalyst or derivative thereof in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the epoxide to provide an oxirane content of about 0.10% or less; It also includes reacting for a time period of 6 hours or less, which is short enough to minimize the formation of highly viscous products. In yet another embodiment, the present invention relates to a method for producing a low viscosity adduct of a polycaprolactone polyol and a polyepoxide, the method comprising at least one polycaprolactone polyol and two or more epoxides per molecule. The polycaprolactone polyol, the polyglycidyl epoxide, and the sulfonic acid catalyst or derivative thereof are combined in the presence of a sulfonic acid catalyst or a derivative thereof at a temperature of about 80°C to about 225°C. This includes using an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the syl epoxide, yet reacting for a time sufficiently short to minimize the formation of highly viscous products. In yet another embodiment, the present invention relates to a process for producing a low viscosity adduct of a polycaprolactone polyol and a polyepoxide, the process comprising a polycaprolactone polyol and two or more epoxy groups per molecule. The polycaprolactone polyol, polyepoxide and sulfonic acid catalyst or derivative thereof are added to the polyepoxide in the presence of a sulfonic acid catalyst or a derivative thereof at a temperature of about 80°C to about 225°C until substantially all of the epoxy groups of the polyepoxide are completely removed. This includes using in an amount at least sufficient to carry out the reaction and reacting within a sufficiently short time to minimize the formation of highly viscous products. The low viscosity adducts of this invention can be mixed with polyepoxides, polyisocyanates, melamine formaldehyde, urea formaldehyde, benzoguanamine formaldehyde, etc. to produce low viscosity curable high solids coating compositions which, after curing, , provides a high performance paint with improved properties such as improved flexibility and paint toughness. In addition to its usefulness as a high solids coating composition, the polycaprolactone polyol and epoxide adduct of the present invention is useful as a polyurethane elastomer, ink, sealant, etc.
It is also useful in the formulation of adhesives and the like. JP-A-60-120717 discloses a reaction product of a poly(active hydrogen) organic compound and a polyepoxide having two or more epoxy groups per molecule, wherein the poly(active hydrogen) organic compound is describes adducts of poly(active hydrogen) organic compounds and polyepoxides used in amounts at least sufficient to effect substantially complete reaction of the epoxy groups of the polyepoxides. The adducts are useful in the formulation of high solids coating compositions, polyurethane elastomers, inks, sealants, adhesives, and the like. JP-A-60-120718 discloses a reaction product consisting of at least two types of poly(active hydrogen) organic compounds that differ in classification and a polyepoxide having two or more epoxy groups per molecule; at least two poly(active hydrogen) organic compounds and a polyepoxide, wherein said poly(active hydrogen) organic compound is used in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of said polyepoxide. Regarding the appendages. The adduct is a high solids coating composition, a polyurethane elastomer,
Useful in formulating inks, sealants, adhesives, etc. DETAILED DESCRIPTION The polycaprolactone polyols, alone or in mixtures, which can be used to prepare the adduct compositions of the process of the invention are commercially available and those described in detail in, for example, U.S. Pat. No. 3,169,945. and any of the well-known polycaprolactone polyols such as polycaprolactone polyols. As described in the above patent specification, the polycaprolatone polyol is prepared by catalytic polymerization of an excess of lactone with an organic polyfunctional polymerization initiator having at least two reactive hydrogen atoms. . The organic polyfunctional polymerization initiator can be any polyhydroxyl compound as shown in the aforementioned US Pat. No. 3,169,945. Examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, Poly(oxyethylene-oxypropylene) glycols and the like, whether blocked, capped, or heterogeneous, containing up to about 40 or more alkyleneoxy units in the molecule Polyalkylene glycol, 3-methyl-1-5-pentanediol, cyclohexanediol, 4,
4'-methylene-bis-cyclohexanol, 4,
Diols such as 4'-isopropylidene-bis-cyclohexanol, xylediol, 2-(4-hydroxymethylphenyl)ethanol, 1,6-hexanediol, etc.; glycerin, trimethylolpropane, 1,2,6- Triols such as hexanetriol, triethanolamine, triisopropanolamine, etc.; erythritol, pentaerythritol, dipentaerythritol, sorbitol, N,N,N',N'-
Includes tetraols such as tetrakis(2-hydroxyethyl)ethylenediamine and the like. When the organic functional polymerization initiator and caprolactone are reacted, the following equation is expressed in the simplest form: A reaction occurs which can be expressed as: In this equation, the organofunctional polymerization initiator is R″(OH) _x
and the caprolactone has the formula: , which is ε-caprolactone itself, or an alkyl, alkoxy, aryl, cycloalkyl, alkaryl or aralkyl compound in which R' has up to 12 carbon atoms as shown in the aforementioned U.S. Pat. No. 3,169,945. is the basis,
Moreover, it can be a substituted caprolactone in which at least 6 R' groups are hydrogen atoms. The polycaprolactone polyols used are shown by the formula on the right side of the above equation, and they have an average molecular weight of
200 to about 6000. Preferred polycaprolactone polyol compounds are those having an average molecular weight of about 290 to about 6,000, most preferably about 290 to 3,000. Most preferred is an average molecular weight of about 290 to about 1500.
polycaprolactone diol compounds having an average molecular weight of about 290 to about 3000; and polyprolactone tetraol compounds. This is most preferred because of its low viscosity. In the above formula, m is an integer representing the average number of repeating units necessary to produce a compound having the above molecular weight. In the above formula, x is an integer having an average value of about 2 to 8, preferably 2 to 4. The hydroxyl number of the polycaprolactone polyol can be about 15 to 600, preferably 200 to 500, and the polycaprolactone can have an average of 2 to 8, preferably 2 to 4 hydroxyl groups. Examples of polycaprolactone polyols that can be used to produce the adduct composition of the present invention include reaction products of caprolactone and polyhydroxyl compounds having an average of 2 to 8 hydroxyl groups. A method for producing this type of polycaprolactone polyol composition is disclosed in U.S. Patent No.
No. 3,169,945, and many such compositions are available on the market. The following table summarizes exemplary polycaprolactone polyols. The first column shows the organic functional polymerization initiator that reacts with caprolactone, and the second column shows the average molecular weight of the polycaprolactone polyol. Knowing the molecular weight of the polymerization initiator and the molecular weight of polycaprolactone, it is possible to easily determine the average number of caprolactone (CPL units) molecules reacted to produce the target compound. That number is the third
Shown in the column.

[Table] Call

[Table] *Average molecular weight of glycol The structures of the compounds in the above table are obvious to those skilled in the art based on the information provided. The preparation of the seventh compound is as follows. Here, the variables r and q are integers, the sum of r+q is an average value of 3.7, and the average molecular weight is 527. The structure of the 20th compound is as follows. Here, the sum of r+q has an average value of 6, and the average molecular weight is 1684. This explanation clarifies the structural formulas of compounds No. 1 to No. 36 above. Although not specifically mentioned above, it is appreciated that other lactone-based polyols can be used in preparing the adduct compositions of the present invention. Examples of other lactone-based polyols derived from beta-propiolactone, delta-valerolactone, jeterenantolactone, etc., including derivatives thereof, such as gamma-methyl-delta-valerolactone, etc. It includes what is done. The polyepoxides used to prepare the adduct compositions of the invention, alone or in admixture, have the formula: It has two or more epoxy groups. The epoxy group can be a terminal epoxy group or an internal epoxy group. The polyepoxide is preferably a cycloaliphatic epoxide. Polyglycidyl epoxides can also be used to prepare the adduct compositions of the present invention. The polyepoxide is reacted with the polycaprolactone polyol described above to form the novel adduct composition of the present invention. Cycloaliphatic epoxide resins suitable for the purposes of this invention are those having an average of two or more epoxy groups per molecule. Examples of suitable cycloaliphatic epoxides are: Formula General formula: Diepoxide of cycloaliphatic ester of dicarboxylic acid represented by. In the above formula R ₁ to R ₁₈ can be the same or different and are therefore hydrogen atoms or generally contain 1 to 9 carbon atoms, and preferably 1 to 3 carbon atoms. Alkyl groups such as methyl, ethyl, n-propyl, n-butyl,
n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl and the like, R being a valence bond or generally containing 1 to 20 carbon atoms, and preferably 4 to 6 carbon atoms. Divalent hydrocarbon groups containing alkylene groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylenemexamethylene, octamethylene, nonamethylene, hexadecamethylene and the like; 1,4-cyclohexane, 1,3-
Cycloaliphatic groups such as cyclohexane, 1,2-cyclohexane and the like. Particularly desirable epoxides within the formula range are those in which R ₁ to R ₁₈ are hydrogen and R is 4 to
It is an alkylene epoxide with 6 carbon atoms. Among the specific diepoxides of cycloaliphatic esters of dicarboxylic acids are: Bis(3,4-epoxycyclohexylmethyl)oxazalate, Bis(3,4-epoxycyclohexylmethyl)adipate, Bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, Bis(3,4-epoxycyclohexylmethyl) Pimelate and similar. Other suitable compounds are described in US Pat. No. 2,750,395. Formula General formula: 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate represented by. In the above formula, R ¹ to R ¹⁸ can be the same or different and are thus the same as defined for R ₁ to R ₁₈ in the formula. Particularly desirable compounds are those in which R ₁ to R ₁₈ are hydrogen. Among the specific compounds falling within the formula:
There are the following compounds. 3,4-epoxycyclohexylmethyl-3,
4-Epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3, 4-Epoxycyclohexyl-methyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4- Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methycyclohexanecarboxylate. Other suitable compounds are, for example, U.S. Pat.
It is described in the specification of No. 2890194. Formula General formula: Diepoxide represented by In the above formulas, the single prime (') sign and the double prime ('') sign for R can be the same or different and represent monovalent substituents such as hydrogen, halogen, i.e. chlorine, bromine, iodine or fluorine. is a monovalent hydrocarbon group or even a U.S. patent no.
A group as defined in 3318822. Particularly desirable compounds are those in which all R's are hydrogen. Other suitable cycloaliphatic epoxides are as follows. and similar. Preferred cycloaliphatic epoxides are as follows. 3,4-epoxycyclohexylmethyl-3,
4-Epoxycyclohexane carboxylate Bis-(3,4-epoxycyclohexylmethyl)adipate 2-(3,4-epoxycyclohexyl-5,
5-spiro-3,4-epoxy)cyclohexane-meth-dioxane Vinylcyclohexene diepoxide or a mixture thereof. Polyglycidyl epoxides suitable for the purposes of this invention include epoxides having a six-membered ring structure, such as diglycidyl esters of phthalic acid, partially hydrogenated phthalic acid, or fully hydrogenated phthalic acid; Diglycidyl esters of hydrophthalic acid are preferred. Representative diglycidyl esters of phthalic acid are listed below. The polyglycidyl type epoxide is preferably a diglycidyl ester of bisphenol A, which is derived from bisphenol A and epichlorohydroline and has the formula: Cresol-novolac epoxy resins are multifunctional solid polymers characterized by low ionic and hydrolyzable chlorine impurities, high chemical resistance and thermal performance. Epoxyphenol novolac resins generally have the following formula: Resins derived from polynuclear phenol-glycidyl ethers generally have the following formula:

[Formula] or

[Formula] Heterocyclic glycidylamine resins that can be included in the present invention are as follows. That is, the following formula is derived from tetraglycidylmethylene dianiline: resins having the formula; resins derived from triglycidyl-p-aminophenol; triazine-based resins; Hydantoin epoxy resin with R'= _CH3 . Mixtures of cycloaliphatic epoxides and polyglycidyl epoxides can also be used to prepare the adduct compositions of the present invention. Preferably, the adducts of the present invention are prepared by reacting at least one polycaprolactone polyol and a polyepoxide in a molar ratio of polycaprolactone polyol to polyepoxide of about 2:1 to about 3:1. Such a range of molar ratios provides about 1 to about 1.5 moles of polycaprolactone polyol for each equivalent of epoxide present in the reaction mixture. The most preferred molar ratio of polycaprolactone polyol to polyepoxide is about 2.5:1. The adducts of the invention are prepared by reacting at least one polycaprolactone polyol with a polyepoxide in the presence of a sulfonic acid catalyst or a derivative thereof. Preferred sulfonic acid catalysts and derivatives thereof are trifluoromethanesulfonic acid (triflic acid) and the general formula: (R _f SO ₃ ) _o M, where R _f has 1 to 18 carbon atoms, preferably 1 -8 fluoroalkyl (preferably perfluoroalkyl), M is ammonium (...NH ₄ ), quaternary ammonium, an amine cation (i.e. protonated amine), or preferably a group 1 to 10 of the periodic table. and monovalent or polyvalent, preferably monovalent to
cations with a valence of 5, where n is an integer equal to the valence of M). Such preferred sulfonic acid catalysts and their derivatives are described in further detail in US Pat. No. 3,842,019. Preferred triflic acid amines that can be used as catalysts in the present invention are: CF ₃ SO ₃ H·N (C ₆ H ₅ ), CF ₃ SO ₃ H·NH ₃ ,
CF ₃ SO ₃ H・CH ₃ NH ₂ , CF ₃ SO ₃ H・(CH ₃ ) ₃ N,
CF ₃ SO ₃ H・C ₂ H ₅ NH ₂ , CF ₃ SO ₃ H・
(C ₂ H ₅ ) ₂ NH, CF ₃ SO ₃ H・(C ₂ H ₅ ) ₃ N,
CF ₃ SO ₃ H・(i−C ₃ H ₇ ) ₂ NH, CF ₃ SO ₃ H・(i−
C ₃ H ₇ ) ₂ N (C ₂ H ₅ ), CF ₃ SO ₃ H・(i-C ₃ H ₇ ) ₂ N
(C ₂ H ₄ OH), CF ₃ SO ₃ H・H ₂ N (C ₂ H ₄ OH),
CF ₃ SO ₃ H・HN (C ₅ H ₈ O), CF ₃ SO ₃ H・H ₂ NC
(CH ₃ ) ₂ CH ₂ OH, CF ₃ SO ₃ H・NH (C ₆ H ₁₁ ),
CF ₃ SO ₃ H・HN (C ₂ H ₄ OH) ₂ , CF ₃ SO ₃・
(CH ₃ ) ₄ N, and mixtures thereof. Preferred metal salts _of sulfonic acids _that can be used as catalysts in the present _{invention are : CF3SO3H} , _C8F17SO3H , _{CF3C6F10SO3H ,}
C ₃ F ₇ SO ₃ H, C ₂ F ₅ SO ₃ H, C ₂ HF ₄ SO ₃ H,
C ₃ F ₇ CHFCF ₂ SO ₃ H, (CF ₃ ) ₂ CHCF ₂ SO ₃ H,
C ₄ F ₇ SO ₃ H, (CF ₃ ) ₂ CF (CF ₂ ) ₄ SO ₃ H,
C ₄ F ₉ CFHCF ₂ SO ₃ H, C ₃ H ₇ CH (CF ₃ ) CF ₂ SO ₃ H,
C ₁₁ F ₂₃ SO ₃ H, C ₅ H ₁₁ CFHCF ₂ SO ₃ H,
C ₇ F ₁₅ CFHCF ₂ SO ₃ H, etc., and mixtures thereof.
Typical examples of the metal cations of the above metal salts are lithium,
Sodium, potassium, magnesium, calcium, strontium, barium, yttrium,
vanadium, manganese, cobalt, nickel,
Metal cations of salts of the following metals: copper, silver, zinc, cadmium, mercury, lead, bismuth, tungsten, lanthanum, neodymium, tin, and gadolinium. Other sulfonic acids and their derivatives can also be used to prepare the adducts of the present invention, including para-toluene sulfonic acid, dinonylnaphthylene sulfonic acid, alkyl sulfonic acids, and the like. The sulfonic acid metal salts used in the present invention can be prepared simply by neutralizing the sulfonic acid precursor with a metal oxide, hydroxide, or carbonate, or a metal salt. Amino and ammonium salts can be produced by neutralizing sulfonic acids with salt-forming primary, secondary or tertiary amines, ammonia or quaternary ammonium hydroxide. These latent forms of sulfonic acid catalysts are activated by heating them in the presence of polycaprolactone polyol and polyepoxide to generate the sulfonic acid in its free acid form and catalyze the opposite. It can be used for. The sulfonic acid catalysts and their derivatives are about
Used in amounts varying from 1 ppm to about 10,000 ppm (from about 0.0001% to about 1.0% by weight based on the total charge of ingredients used to formulate the adduct composition) or even more. be able to. Preferred concentrations of sulfonic acid catalysts and derivatives thereof are from about 5 ppm to about 5000 ppm (from about 0.0005% to about 0.5% by weight based on the total charge of ingredients used to formulate the adduct composition).
over a range of. The most preferred concentration of the sulfonic acid catalyst and its derivatives used in the present invention is about 50 ppm.
to about 4000 ppm (from about 0.005% to about 0.4% by weight, based on the total charge of ingredients used to use the adduct). The most preferred sulfonic acid catalysts and their derivatives useful in preparing the adduct compositions of the present invention include diethylammonium triflylate, trifluoromethanesulfonic acid, ammonium triflate, di-isopropylethyl-ethylammonium triflylate, and Includes di-isopropylammonium triflic acid. Some of these catalysts are commercially available from 3M. The adducts of the present invention combine at least one polycaprolactone polyol and a polyepoxide in the presence of a sulfonic acid catalyst or derivative thereof from about 80°C to about 225°C, preferably from about 100°C to about 200°C, most preferably from about 100°C to about 200°C. The reaction is carried out at a temperature of about 125°C to about 190°C. The reaction proceeds well under an inert atmosphere at substantially atmospheric pressure. However, elevated or subatmospheric pressures can also be used. As known to those skilled in the art, the time required for the reaction to complete is related to the catalyst concentration and the temperature of the reaction mixture. As exemplified in the present invention, the time can vary from one hour or less to about six hours depending on the conditions selected. It is preferred to complete the reaction within as short a time as possible without using excessive amounts of catalyst. It is preferred to complete the reaction in about 5 hours or less, and most preferably in about 2 hours or less. A preferred method of making the adducts of the present invention is to place one or more polycaprolactone polyols in a reactor, and add the polycaprolactone polyols to about
As soon as the polycaprolactone polyol melts by heating to a temperature of 100° C., the sulfonic acid catalyst or derivative thereof is added using nitrogen sparging. The polycaprolactone polyol and catalyst mixture is then heated to a temperature of about 130°C to about 200°C and the polyepoxide is added to the mixture. Under certain reaction conditions, an exotherm may occur, increasing the temperature by about 10°C to 20°C or more. This exotherm was found to be beneficial in promoting the reaction to completion in a short period of time. The reaction is carried out for about 1 to 3 hours or until the oxysilane content is reduced to approximately zero value.
As a variation of this method, all ingredients can be initially placed in the reactor. As yet another variation of the method, vacuum can be used during the 10 to 30 minute vacuum treatment after addition of the catalyst and/or during heating to bring the polycaprolactone polyol into a molten state. During the reaction of the mixture of polycaprolactone polyol(s) and polyepoxide(s),
The equivalent of one hydroxyl group of the polyol reacts with one epoxy group to open the oxirane ring, leaving a hydroxyl group on one oxirane carbon atom and a second oxirane carbon atom with a carbon atom of the polyol. It is believed that at least a large portion of each polycaprolactone polyol molecule reacts with only one epoxy group of the polyepoxide to form an ether linkage. The following equation describes the reaction of 2 moles of polycaprolactone triol with 1 mole of cyclohexane diepoxide: In the above reaction formula, X is -CH ₂ OOC-, -
_Any divalent group that joins two 3,4 _- epoxycyclohexyl nuclei, such as _CH2OOC (CH2) _4COOCH2- or -C( _CH3 ) ₂ . The values of a, b and c are such that the indicated polycaprolactone polyol has an average molecular weight of about 200 to 6000.
Can be any integer including zero. It should be understood that the product structure shown in the above reaction scheme is merely exemplary and that any of the three hydroxyl groups of the caprolactone triol can react to open the oxirane group of the polyepoxide reactant. The above formula is a theoretical norm. However, during the reaction, other longer chain length species may be present in the reaction product as a result of the reaction of the hydroxyl groups of the indicated product with unreacted oxirane groups. Additionally, other reaction mechanisms can account for other long chain components in the reaction product, such as reaction of unreacted polycaprolactone polyol with the ester bonds of the polyepoxide. The presence of these long chain components can result in increased product viscosity and it is desirable to minimize their formation. A high degree of Effective sulfonic acid catalysts and their derivatives promote the production of shorter chain length, lower viscosity products, such as those described in the equation above. The longer the polycaprolactone polyol is in contact with the polyepoxide before the oxirane is consumed, the greater the potential for forming high molecular weight adducts and resulting in a highly viscous product. The sulfonic acid catalysts and their derivatives used in the present invention reduce the oxirane content in the reaction mixture to zero or very low values in a short period of time, producing shorter chain lengths such as those described in the above equation. It is believed that this gives a predominance of solids and therefore a low viscosity adduct. The low oxysilane content means that most of the epoxide groups of the polyepoxide react with the hydroxyl groups of the polycaprolactone polyol to open the oxirane ring.
This shows that an ether bond was formed between the hydroxyl group on one oxirane carbon atom and the second oxirane carbon atom and the carbon atom of the polycaprolactone polyol. Achieving such low oxirane contents in a short time is likely due to the predominance of short chain length, low viscosity, high functionality adducts such as those described in the above equation. A high oxirane content indicates that most of the epoxide groups of the polyepoxide have not reacted with the hydroxyl groups of the polycaproctone polyol. The adducts of the present invention have an oxirane content of about 0.10% or less and a viscosity at 54.5°C of about 3700 centistokes or less, preferably an oxirane content of about 0.05% or less and a viscosity of about 3500 centistokes or less at 54.5°C, most preferably about 0.025 % or less and a viscosity at 54.5°C of less than about 3000 centistokes. Many of the adducts exemplified in this invention have oxirane contents of about 0.025% or less and viscosities at 54.5°C of about 1000 centistokes or less. If desired, the reaction time can be increased to substantially eliminate the oxirane content. The adducts of the present invention prepared from polyglycidyl epoxides have an oxirane content of about 0.10% or more and
It can have a viscosity of about 3700 centistokes or greater at 54.5°C. Such adducts preferably have an oxirane content of about 1.0% or less and a temperature of 54.5°C.
a viscosity of less than about 25,000 centistokes, more preferably an oxirane content of less than 0.5%, and
It has a viscosity of less than about 15,000 centistokes at 54.5°C, most preferably an oxirane content of less than about 0.25% and a viscosity of less than about 10,000 centistokes at 54.5°C. Adducts of the present invention made from a single polycaprolactone polyol can have an oxirane content of greater than about 0.10% and a viscosity of greater than about 3700 centistokes at 54.5°C. Such adducts preferably have an oxirane content of about 0.50% or less and a viscosity of about 20,000 centistokes or less at 54.5°C, more preferably an oxirane content of about 0.25% or less and a viscosity of about 15,000 centistokes or less at 54.5°C, most preferably Preferably, it has an oxirane content of about 0.125% or less and a viscosity at 54.5°C of about 10,000 centistokes or less. The novel adducts of this invention are particularly useful in formulating high solids coating compositions. Such a curable coating composition preferably comprises the polycaprolactone polyol and polyepoxide adduct of the present invention, 1
Includes polyepoxides having two or more epoxy groups per molecule and a catalyst or photoinitiator. Other additives can also be included in the curable high solids coating compositions, such as surfactants, solvents, substituted cycloaliphatic monoepoxide reactive diluents, etc., as described in more detail below. . Any of the polycaprolactone polyol and polyepoxide adducts of this invention are useful in formulating curable high solids coating compositions. The concentration of the adduct in the curable high solids coating composition ranges from about 1 to about 60% of the total weight of the coating composition, depending on the properties desired in the cured composition.
It may range from 5 to 40% by weight, most preferably from 10 to 30% by weight. Preferred polyepoxides having two or more epoxy groups per molecule suitable for reacting with the adducts of the invention are any of the above-mentioned polyepoxides useful for preparing the adducts themselves.
However, other reactive substances such as polyisocyanates and amino-formaldehydes selected from melamine formaldehyde, urea formaldehyde and benzoguanamine formaldehyde can also be reacted with the adducts produced by the process of the invention to form polyurethane coating compositions and Each of the aminoformaldehyde coating compositions can be provided. The polyisocyanates and amino-formaldehydes are well known in the art and no further description is necessary to inform the person skilled in the art what they are. The concentration of polyepoxide or polyisocyanate or aminoformamide in the curable high solids coating composition varies depending on the properties desired in the cured composition, preferably from about 1 to about 95% by weight of the total weight of the coating composition. It can range from 25 to 90% by weight, most preferably from 50 to 80% by weight. Suitable catalysts that can be used in the curable high solids coating composition to cure it include:
It is preferred to include any of the sulfonic acid catalysts or derivatives thereof described above that are useful in preparing the adduct composition itself. The concentration of catalyst in the curable high solids coating composition is about 0.1 per 100 parts by weight of the combination of the polyepoxide and the adduct composition.
and 30 parts by weight. For photocopolymerizable coating compositions, a photopolymerization initiator can be used in place of the above catalyst. Photoinitiators suitable for use in the curable coating compositions include, for example, U.S. Pat. No. 4,231,951;
Any one of the well-known photopolymerization initiators as described in the specifications of No. 4138255 and No. 4058401
Seeds are fine. The above patent specifications are incorporated herein by reference. Preferred photoinitiators, alone or in combination, include triarylsulfonium complex salts as described in U.S. Pat. No. 4,231,951;
Aromatic sulfonium salts or aromatic iodonium salts of halogen-containing complex ions as described in U.S. Pat. No. 4,256,828; aromatic group a elements as described in U.S. Pat. Nos. 4,058,401 and 4,138,255. Onium salts include aromatic onium salts of group a elements such as those described in US Pat. No. 4,069,055. Such salts include FC-508 and
As FC-509 (manufactured by Minnesota Mining and Manufacturing Company), and UVE-
1014 (manufactured by General Electric Company). The photoinitiator is present in an amount of about 100 parts by weight of the combination of polyepoxide and adduct composition.
It is used in conventional amounts such as 0.1 to 30 parts by weight. Preferably, the curable coating composition contains conventional amounts of oils (particularly silicone oils), surfactants such as silicone-alkylene oxide copolymers (e.g. L-5410, available from Union Carbide); silicone oil-containing aliphatic epoxide groups, fluorocarbon surfactants such as FC-171, available from 3M Company, and FC-430, also available from 3M Company; ethanol, propanol, butanol, hexanol, etc. low molecular weight, alcohols; hydroxyl-containing copolymers of ethylenically unsaturated monomers, such as RJ-100, available from Monsanto Chemical; cellosolves, such as butyl cellosolve, available from Union Carbide. ; carbitols such as butyl carbitol; diethylene glycols; commercially available from Union Carbide
Low molecular weight hydroxyl-containing vinyl polymers such as UCAR Solution Vinyl VYES; Formula: (wherein R ₁₁ is alkyl or aryl, n
is an integer from 1 to 6); Examples of these are glycidyl ethers of polyhydric phenols obtained by reacting polyhydric phenols with an excess of chlorohydrin, such as epichlorohydrin. Another example of this kind is e.g.
These include α-olefin epoxide and epoxy novolac described in the specification of No. 3018262. If desired, various conventional non-basic fillers such as silica, talc, glass beads or foams, clays, powders of metals such as aluminum,
Viscosity modifiers, gums, tackifiers, pigments, and the like can also be included in the coating composition, up to about 50% by volume or more (such as zinc oxide). The particular additives or fillers selected do not affect the basic invention. Additionally, the curable coating compositions can be combined with various structural fibers and cured to form useful high strength composites. Structural fibers useful in the curable coating composition include carbon, graphite,
Glass, silicon carbide, poly(benzothiazole),
Includes poly(benzimidazole), poly(benzoxazole), alumina, titania, boron, and aromatic polyamide fibers. These fibers have a tensile strength greater than 100000psi, 2 million
Characterized by a tensile modulus greater than psi and a decomposition temperature greater than 200°C. The fibers are continuous tows (1,000 to 400,000 strands each);
It can be used in the form of woven fabrics, whiskers, cut fibers or random mats. Preferred fibers are carbon fibers, aromatic polyamide fibers such as Kevlar 49 fiber (manufactured by EI Dupont de Nemours, Wilmington, Del.), and silicon carbide fibers. The curable coating composition preferably includes a substituted cycloaliphatic monoepoxide reactive diluent. The substituted cycloaliphatic monoepoxides used in the coating compositions are substituted with alkyl, halogen, carbon, ether, ester or vinyl groups having 1 to 9 carbon atoms. Preferably, the substituted cycloaliphatic monoepoxide is a vinyl-substituted cycloaliphatic monoepoxide, and is preferably selected from one or more of the following: (1) Formula: 4-vinylcyclohexene monoepoxide having the formula (2): norbornene monoepoxide having the formula (3): limonene monoepoxide with. The substituted cycloaliphatic monoepoxide acts as a reactive diluent that cures into the final coating product, has a significant effect on lowering the viscosity, does not volatilize during the curing operation, and is cured quickly. Don't slow down. The substituted cycloaliphatic monoepoxide is present in the curable coating composition in an amount of about 0.1 to about 95% by weight;
Preferably it is used in an amount of about 1 to about 60% by weight, most preferably about 3 to about 30% by weight. In preparing the coating composition, the ingredients are mixed according to conventional procedures used in the production of inks, paints, and coating compositions. Since these procedures are well known to those skilled in the art, there is no need to discuss them further in this case. However, when photoinitiators are incorporated into coating compositions, it is necessary to mix or blend the curable coating formulation under a "safe light" such as a yellow light source to avoid or minimize photocopolymerization. It should be noted that there is. The coating composition may also contain an organic solvent as an optional ingredient. Any conventional solvent used in the coating industry may be used, preferably at a concentration of up to 30% by weight, based on the total weight of the coating composition. Suitable solvents are acetone, methylene chloride, and any solvent that does not significantly react with the coating components. Although it is possible to use large amounts of solvent, using large amounts is practically
This negates the benefits of high solids curable paints, which are considered 100% solids paint systems. Solvents are generally added in small amounts that have been shown to improve flow properties during application of coating compositions to substrates. The curable coating composition is applied as a wet film to a suitable surface or substrate by conventional means such as rolling or spraying. Curing of the curable coating composition can be accomplished by heating the wet coating at a temperature of about 100°C to about 200°C for a period of about 1 minute to about 2 hours or more. Curing can also be carried out by photopolymerization of the coating composition. Photopolymerization occurs by exposing the composition to any radiation source that emits actinic radiation at wavelengths within the ultraviolet and visible spectral regions. Preferred radiation sources include mercury,
Includes xenon, carbon arc and tungsten filament lamps, sunlight, etc. This exposure depends on the amount of the particular polymerizable material and the photoinitiator used, and also on the radiation source and distance from the source and the thickness of the coating to be cured.
It can range from less than seconds to 10 minutes or more. The composition can also be polymerized by exposure to electron beam irradiation. Generally speaking, the required radiation dose ranges from less than 1 megarad to 100 megarads or more. Generally speaking, the rate of polymerization increases with increasing amounts of photoinitiator for a given exposure or irradiation. The polymerization rate also increases with increasing light intensity or electron radiation dose. Curing or photopolymerization of the coating composition is triggered (trig-
gered) reaction. Once the decomposition of the photoinitiator to the cationic catalyst is initiated by exposure to the radiation source, the curing or photopolymerization reaction proceeds and continues even after the radiation source is removed. The use of thermal energy during or after exposure to a radiation source, ie, thermal postcure, generally accelerates the curing reaction, and even mild temperature increases can greatly accelerate the curing rate. The cured coating compositions can be useful in bicycle, can, appliance and office machine finishes, coil coatings, house siding finishes, general metal finishes, and the like. The compositions can also be used as adhesives, printing inks, foundry and molding compounds, potting and encapsulating compounds, caulking and sealing compounds, impregnating and coating compounds, and the like. The photocopolymerizable compositions are suitable for use with metals, due to their excellent impact resistance, abrasion resistance and adhesion properties.
It is particularly suitable for various applications in the field of protective coatings and printing on rigid, elastic and flexible substrates such as plastics, rubber, glass, paper, wood and ceramics. The low viscosity adduct of polycaprolactone polyol and polyepoxide produced in the following examples was evaluated by the following procedure: Oxirane content: 1400 ml of CP grade acetic acid
and 1800 ml of reagent grade chlorobenzene.
99% tetraethylammonium bromide 350g
Tetraphethylammonium bromide reagent was prepared by dissolving 1% crystal violet indicator in acetic acid and then adding 1.0 ml of 1% crystal violet indicator. The reagent was mixed well and neutralized to a blue-green color. 70-72 in about 2000ml of CP grade acetic acid
Dissolve 30ml of perchloric acid, then 100% acetic anhydride
A 0.1N perchloric acid anhydrous standard solution in acetic acid was prepared by adding ml and diluting to 3500 ml using CP grade acetic acid. Standardization was against 0.7-0.8 g of potassium acid phthalate dissolved in 50 ml of acetic acid using Crystal Violet reagent. Tetraethylammonium bromide reagent using a graduated cylinder
100 ml was placed in each of two 250 ml wide-mouth Erlenmeyer flasks. Approximately 0.7-0.8 g of adduct product, weighed to the nearest mg, was added to each flask and mixed thoroughly. The contents of the flask were immediately titrated with an anhydrous 0.1N perchloric acid standard solution in acetic acid until the blue-green end point stabilized for 2 minutes, and the percent oxirane was calculated as follows: (A)(N ) (1.6) / Grams of sample = Weight % of oxirane (where A is the number of ml of perchloric acid anhydrous standard titrant solution in acetic acid, N is the perchloric acid anhydride standard titrant solution in acetic acid to normality) ). Viscosity (centistokes): Measured at specific temperatures with a calibrated capillary viscometer with the required centistoke range. Viscosity (centipoise): Measured with a Bruckfield viscometer at ambient temperature. Hydroxyl number: CP class phthalic anhydride 111-116g
A phthalic anhydride-imidazole-pyridine reagent was prepared by weighing and placing in a one-coat amber bottle and then adding 700 ml of pyridine from which the phthalic anhydride had been evaporated. The contents of the bottle were mixed vigorously to completely dissolve, then 16-18 g of CP grade imidazole was added and carefully swirled to dissolve. 25 ml of the phthalic anhydride-imidazole-pyridine reagent was pipetted into a heat-resistant pressure bottle, and then a calculated amount of the adduct product, weighed to an accuracy of 0.1 mg, was added to several bottles using a hypodermic syringe or other suitable device. (some bottles were saved for empty measurements). The bottles were stoppered and swirled until the sample was completely dissolved in the reagent. Each bottle was then placed in a water bath maintained at 98±2° C. for 30 minutes and then cooled to ambient temperature. Add 50 ml of redistilled pyridine to each bottle and after 2 minutes approx. 0.5 ml of a 1.0% solution of phenolphthalein in pyridine.
was added. The contents of the bottle were titrated with 0.5N sodium hydroxide standard solution until the pink end point stabilized for at least 15 seconds, and the hydroxyl number was calculated by the following formula: (B-A)(N)(56.1)/gram of sample. Number = Hydroxyl number (mg of KOH/g of sample) (where A is the number of ml of standard sodium hydroxide titration solution required for the sample, and B is the number of standard sodium hydroxide titration solutions required for the blank sample) titration solution
ml and N is the normality of sodium hydroxide). Acid value: A solution containing 1200 ml of isopropanol, 200 ml of water and 150 ml of methylene chloride was prepared. To a 250 ml Erlenmeyer flask was added 50 ml of the above solution and a 10 g sample of the adduct product weighed to an accuracy of 0.1 mg. Swirl the contents to completely dissolve, add 1.0-1.5 ml of 1.0% phenolphthalein solution in methanol,
Swirl to dissolve. the contents of the flask,
It was titrated to a pink end point with an alcoholic solution of 0.02N potassium hydroxide for small acid values and then with an alcoholic solution of 0.1N sodium hydroxide for large acid values. Acid value was calculated as follows: (A) (N) (56.1)/grams of sample = acid value (mg of KOH/
g) (where A is the number of ml of potassium hydroxide titration solution required for the sample and N is the normality of potassium hydroxide in alcohol). Water Content: Union Carbide Corporation Laboratory Manual Specification Method (Union Carbide
Corporatin Laboratory Manual
Specification Method) 31-29W1-4 (1955
Determination of the concentration of any water in the adduct product by titration using a sulfur dioxide-iodine reagent, as described in more detail in 2003, March 2, 2007). Color, Gardner color number: ASTM D1544−68 (1974
Measurement of the color of clear liquid adduct composition solutions as described in The coating compositions prepared in the following examples were evaluated by the following procedure: Solvent resistance (double-acting acetone rub): Consists of rubbing the coating surface back and forth with manual pressure with a cheesecloth impregnated with acetone. Determination of the resistance of cured coatings to attack by acetone. A single "double acetone rub" refers to the back and forth rubbing of an acetone-soaked cheesecloth over the coating surface with hand pressure. The effect that a certain number of double-acting acetone rubs had on the coating surface was indicated by the number in brackets after the number of double-acting acetone rubs. The grading system for evaluating acetone resistance for a given number of double-acting acetone rubs is as follows: Number after and within the number of rubs (1) No change in appearance of the paint. (2) Scratched surfaces. (3) Cloudy, scratched and some paint removed. (4) Destruction of paint appearance. (5) Approximately half of the paint was removed. Pencil hardness: The hardness value of the pencil increases,
A pencil lead of one type was pressed against the coating surface in a strictly defined manner as described in ASTM-D-3363-74 until the coating surface was scratched. The hardness of the surface was considered the grade of the hardest pencil that could not just scratch the coating surface. Here are the pencil leads in order from softest to hardest: 6B, 5B, 4B, 3B, 2B, B,
HB, F, H, 2H, 3H, 4H, 5H, 6H,
7H, 8H, and 9H. Crosshatch adhesion: A grid pattern was created in the coating film to the substrate by 10 cuts in each direction, and a pressure-sensitive adhesive tape was applied over the grid pattern and then removed. Adhesion, ASTM
- D-3359-78 was evaluated by comparison with the description and explanation more fully detailed. Surface Impact Resistance (Gardner Impact): A measure of the ability of a cured coating to resist failure by falling weights. A Gardner impact tester model IG-1120 using an 8 pound arrow was used to test the cast and then cured coatings on steel panels. The arrow was raised to a predetermined height in inches and then dropped onto the painted side of the painted steel panel. The product of inches and pounds, in inches-points, that was absorbed into the coating without breaking was recorded as the coating surface impact resistance. Backside Impact Resistance (Gardner Impact): A measure of the ability of a cured coating to resist fracture by falling weights. A Gardner impact tester model IG-1120 using an 8 pound arrow was used to test the cast and then cured coatings on steel panels. The arrow was raised to a predetermined height in inches and then dropped onto the unpainted side of the painted steel panel. The product of inches and pounds, expressed in inches, that is absorbed into the coating without breaking is recorded as the coating backside impact resistance. Water immersion resistance: The penetration of a cured coating into water for a specified time and at a specified temperature. After removal from the water, the hydrolysis resistance of the cured coatings was determined by the pencil hardness test and crosshatch adhesion test described above. Water resistance was determined by comparing the results obtained with the results of the same test performed on cured coatings that were not immersed in water. The following examples illustrate the invention:
It is not intended to limit the scope of the invention. The following symbols, terms, and abbreviations used in the examples described below have the meanings given below: mg: milligram °C: degree Celsius: degree Fahrenheit cc: cubic centimeter Epoxide: Union Carbide Corporation as ERL-4221 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate commercially available from. Epoxide: Bis(3,4-
Epoxycyclohexylmethyl) adipate. Epoxide: Vinyl cyclohexene diepoxide commercially available from Union Carbide as ERL-4206. Epoxide: has an equivalent weight of 185-192, and
Diglycidyl ether of bisphenol A, commercially available from Shell Chemical Company as EPON828. Epoxide: 4-vinycyclohexene monoepoxide. Epoxide: Viking Chemical
Limonene, commercially available from Chemical)
Monoepoxide. Melamine: A 20% by weight solution of a modified melamine resin in isobutanol, commercially available as Cymel 325 from American Cyanamide Company. Polyol: Polycaprolactone diol having an average molecular weight of 530 and an average hydroxyl number of 212, commercially available as TONE-0200 from Union Carbide. Polyol: Polycaprolactone diol having an average molecular weight of 830 and an average hydroxyl number of 135, commercially available as TONE-0210 from Union Carbide. Polyol: Polycaprolactone tridiol having an average molecular weight of 540 and an average hydroxyl number of 310, commercially available as TONE-0305 from Union Carbide. Polyol: Polycaprolactone triol having an average molecular weight of 300 and an average hydroxyl number of 560, commercially available as TONE-0301 from Union Carbide. Polyol: Polycaprolactone triol having an average molecular weight of 900 and an average hydroxyl number of 187, commercially available as TONE-0310 from Union Carbide. Polyol: dihydroxyl-functional polyol prepared by reacting 63 mol% caprolactone, 19 mol% diethylene glycol and 18 mol% adipic acid at elevated temperature; average molecular weight
3066, with an average hydroxyl number of 36.6, and D
-737 from Union Carbide. Catalyst: An aqueous solution of 60% by weight diethylammonium triflylate and 40% by weight of a 50/50 mixture of water and butyl carbitol, commercially available as FC-520 from 3M Company. Catalyst: An aqueous solution containing 60% by weight of trifluoromethanesulfonic acid (triflic acid), commercially available from 3M Company as FC-24Aq. Catalyst: stannous caprylate (stan-nons)
octoate). Catalyst: A 60% by weight solution of catalyst material in isopropanol having an acid number of 130-140 and a specific gravity of 0.960 and commercially available from American Cyanamide Company as Cycat 4040. Photoinitiator: Triarylsulfonium hexafluoro having a specific gravity of 1.33 at 23°C and a Bruckfield viscosity of 40,000 to 60,000 centipoise (#4 spindle at 6 rpm, 23°C) and commercially available from 3M Company as FC-508. Phosphate solution. Photoinitiator: Triarylsulfonium hexafluoroantimony salt solution having a specific gravity of 1.39 at 25°C and a Bruckfield viscosity of 74 centipoise and commercially available from General Electric Company as UVE-1014. Surfactant: Structural formula below: and is commercially available from Union Carbide Company as L-5410. Solvent: Methyl Isobutyl Ketone Polyol Adduct: Product prepared in Example 2 containing a tetrafunctional polyol adduct and having the properties described in Example 2 below. Polyol adduct: The product prepared in Example 13 containing a hexafunctional polyol adduct and having the properties described in Example 13 below. Polyol adduct: The product prepared in Example 15 containing a hexafunctional polyol adduct and having the properties described in Example 15 below Polyol adduct: The product containing a hexafunctional polyol adduct and having the properties described in Example 15 below. The product produced in Example 17, having the properties described in Example 17. Polyol adduct: the product prepared in Example 20 containing a mixture of hexafunctional polyol adduct, pentafunctional polyol adduct and tetrafunctional polyol adduct and having the properties described in Example 20 below. . The figures and data will be converted as follows. 1 pound = 453g 1 inch = 2.54 cm 1 mil = 1 inch x 1/1000 = 0.00254 cm °C = (〓-32) x 5/9 Comparative Example A Washed with refluxing acetone in advance and dried with nitrogen
617.4 pounds of polyol and 282.6 pounds of epoxide (2/1 molar ratio) were added to a 100 gallon glass lined autoclave (G101). The autoclave contents were mixed for 15 minutes at ambient temperature, then 61 g of catalyst was added to the autoclave, and the autoclave contents were then mixed for 1 hour at ambient temperature. Mixing is possible with two-blade and three-blade
This was done by alternating a total of four sets of Glascote impellers onto a single eccentric shaft operated at 114 rpm. The contents of the autoclave were then heated with continuous stirring to a temperature of 170°C and kept at this temperature for 27 hours. The reaction temperature was controlled by circulating tempered ethylene glycol into the autoclave jacket and high purity nitrogen was used to remove air and/or moisture from the autoclave. Samples were taken at intervals and analyzed for oxirane content (%) and viscosity. Total
After 3 hours to a 27 hour heating period, the oxirane content was determined to be 2.07% and the viscosity at 130° was 14.097 centistokes. After 5 hours for a total heating period of 27 hours, the oxirane content was 14.7
% and the viscosity at 130° was 16.735 centistokes. After 7 hours for a total heating period of 27 hours, the oxirane content was determined to be 1.16% and the viscosity at 130° was 18.340 centistokes. After 10 hours to a total heating period of 27 hours, the oxirane content was determined to be 0.93% and the viscosity at 130° was 19.956 centistokes. After 14.5 hours for a total heating period of 27 hours, the oxirane content was determined to be 0.73% and 130
The viscosity was 20.792 centistokes. 27
At the end of the heating period for hours, the oxirane content is
It was determined to be 0.51% and the viscosity at 130〓 was
It was 21.850 centistokes. After cooling to a temperature of 80° C., the contents of the autoclave were then collected as a residual product, which upon analysis was found to have the following properties: Oxirane Content 0.51% Viscosity at 130〓 21850 Centistoke Hydroxyl Number 339 mg KOH/g Color, Gardner Scale ~1 Comparative Example A shows the high viscosity product obtained when carrying out the technique described in U.S. Pat. No. 3,896,303. This is to explain. Comparative Example B In a 2 liter, 4 neck, round bottom reaction flask equipped with a nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer, 450 g (1.5 moles) of polyol,
540g (1.0mol) polyol and epoxide
274g (1.0 mol) (molar ratio is 1.5:1:
1) was added. The contents of the reaction flask were heated to a temperature of 100 °C with continuous stirring;
After that, 0.19g of catalyst (0.015g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were then heated to 150 ml with continuous stirring.
Heat to a temperature of °C and keep at this temperature for 6.5 hours.
A nitrogen blanket was maintained throughout the reaction period. Samples were taken at intervals and analyzed for oxirane content (%). After 2 hours to a total heating period of 6.5 hours, the oxirane content was 1.94
%. After 3 hours for a total heating period of 6.5 hours, the oxirane content was determined to be 0.63%. After 5 hours of heating for a total of 6.5 hours,
Oxirane content was determined to be 0.18%.
At the end of the 6.5 hour heating period, the oxirane content was determined to be 0.106%. Then 50℃
After cooling to a temperature of , the contents of the reaction flask were collected as a residual product (yellow liquid), which upon analysis was found to have the following properties: Oxirane Content 0.106% Viscosity at 54.5°C 3790 Centistoke Hydroxyl Number 333 mg KOH/g Color, Gardner Scale ~3.5 Comparative Example B illustrates the product obtained when carrying out the technique described in U.S. Pat. No. 4,045,474 (See Example 2 of this patent). A comparison with Example 14 of the present invention showed that the product of Example 14 was prepared in a much shorter time and had significantly lower viscosity and oxirane content than the product of Comparative Example B. Comparative Example C Pre-cleaned with refluxing acetone and dried with nitrogen
To a 100 gallon glass-lined autoclave (G101) was added 302 pounds of polyol, 385 pounds of polyol, and 195 pounds of epoxide (molar ratio of 1.5:1:1, respectively). While continuously stirring the contents of the autoclave
Heating to a temperature of 110℃, then 61.3g of catalyst
was added to the autoclave. Agitation was provided by a 15-inch three-blade Glascote impeller operated at 114 rpm. The contents of the autoclave were then heated to a temperature of 150 °C with continuous stirring;
It was kept at this temperature for 22.5 hours. The reaction temperature was controlled by circulating tempered ethylene glycol into the autoclave jacket and a slight air purge was maintained throughout the reaction. Total 22.5
After heating period of 7.25 hours, catalyst 61.3g
was further added to the autoclave. During the remaining reaction period, the oxirane content was monitored to confirm the reduction in epoxide content and degree of reactivity.
At the end of the 22.5 hour heating period, the oxirane content was determined to be 0.30%. Then, after cooling to a temperature of 80° C., the contents of the autoclave were taken as overproduct, which was found to have the following properties: Oxirane content 0.30% Viscosity at 54.5°C 3250 centistoke Hydroxyl number 345 mg KOH/g Color, Gardner scale 2.5 Water content 0.02% Comparative Example C is the product obtained by carrying out the technique described in U.S. Pat. No. 4,045,474 This is to explain. Long reaction times are required to achieve the final low oxirane content. Comparative Example D 450 g (1.5 moles) of polyol, 450 g (1.5 moles) of polyol, were placed in a 2 liter, 4-neck, round-bottom reaction flask equipped with a nitrogen inlet and outlet, a mechanical stirrer, a heating mantle, and a thermometer.
540 g (1.0 mol) of polyol and 274 g (1.0 mol) of epoxide (molar ratio of 1.5:
1:1) was added. The contents of the reaction flask were heated to a temperature of 100° C. with continuous stirring, after which 0.19 g of catalyst (0.015% by weight based on the total charge) was added to the reaction flask. The contents of the reaction flask were then heated to 150 °C with continuous stirring.
and kept at this temperature for 13 hours. A nitrogen blanket was maintained throughout the reaction period. Samples were taken at intervals and analyzed for oxirane content (%). After 7 hours for a total heating period of 13 hours, the oxirane content was determined to be 1.36%. 10 to 13 hours total heating period
After an hour, the oxirane content was determined to be 0.30%. After 1 hour for a total heating period of 13 hours, the oxirane content was determined to be 0.16%. 13
At the end of the heating period for hours, the oxirane content is
It was determined to be 0.12%. After cooling to a temperature of 50° C., the contents of the reaction flask were then collected as a residual product, which was found to have the following properties. Oxirane content 0.12% Viscosity at 54.5°C 3713 centistokes Hydroxyl number 338 mg KOH/g Comparative Example D describes the product obtained when carrying out the technique described in U.S. Pat. No. 4,045,474 (this patent (See Example 2).
A comparison with Example 14 of the present invention showed that the product of Example 14 was prepared in a much shorter time and had significantly lower viscosity and oxirane content than the product of Comparative Example D. Comparative Example E 2444 g (8.15 moles) of polyol and 744 g (2.72 moles) of epoxide (molar ratio of 3 :1) was added. The contents of the reaction flask were heated to a temperature of 100 °C with continuous stirring;
Then 0.239g of catalyst (0.0075 for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were then heated to 150 ml with continuous stirring.
It was heated to a temperature of °C and kept at this temperature for 148.75 hours. A nitrogen blanket was maintained throughout the reaction period. When the temperature reaches 150℃, the catalyst
An additional 0.239 g (0.0075% by weight of total charge) was added to the reaction flask. Samples were taken at intervals and analyzed for oxirane content (%) and viscosity. Up to a total heating period of 148.75 hours
After 21.5 hours, the oxirane content was determined to be 1.97% and the viscosity at 54.5°C was 792 centistokes. 38.75 for a total heating period of 148.75 hours
After hours, the oxirane content was determined to be 1.29% and the viscosity at 54.5°C was 1652 centistokes. After 46.25 hours of a total heating period of 148.75 hours, the oxirane content was determined to be 1.18% and the viscosity at 54.5° C. was 2667 centistokes, after 90.25 hours of a total heating period of 148.75 hours.
The oxirane content was determined to be 0.5%,
The viscosity at 54.5°C was 9560 centistokes.
After 136.25 hours for a total heating period of 148.75 hours, the oxirane content was determined to be 0.12% and 54.5
The viscosity at °C was 26.176 centistokes.
At the end of the 148.75 hour heating period, the oxirane content was determined to be 0.06% and the viscosity was 31.848 centistokes. After cooling to a temperature of 50° C., the contents of the reaction flask were then collected as a residual product, which upon analysis was found to have the following properties: Oxirane Content 0.06% Viscosity at 54.5°C 31848 Centistoke Hydroxyl Number 314 mg KOH/g Color, Gardner Scale 5.0 Comparative Example E describes the product obtained when carrying out the comparative technique described in U.S. Pat. No. 4,045,474 (See the comparative example in this patent). Example 1 1.325 g (2.5 moles) of polyol is placed in a 2 liter, 4 neck, round bottom reaction flask equipped with a nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer.
was added. The polyol is heated to a temperature of 140° C. with continuous stirring and nitrogen sparge;
Thereafter, 274 g (1.0 mole) of epoxide and 0.63 g (0.04% by weight of total charge) of catalyst were added to the reaction flask. The contents of the reaction flask were kept at a temperature of 140-145°C for 3 hours with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%). After 2 hours for a total heating period of 3 hours, the oxirane content was determined to be 0.04%. At the end of the 3 hour heating period, the oxirane content was determined to be 0.03% and the reaction was complete. After cooling to ambient temperature, the contents of the reaction flask were then collected as a residual product, which upon analysis showed, on average, a residue containing primarily a mixture of tetrafunctional polyol adduct and unreacted difunctional polyol. The product was found to have the following properties. Oxirane content 0.03% Viscosity at 54.5°C 531 centistokes Hydroxyl number 156.9 mg KOH/g Acid number 0.22 mg KOH/g Example 2 Four 2 liters with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 2.075 g (2.5 moles) of polyol in a round-necked reaction flask
was added. The polyol is heated to a temperature of 140° C. with continuous stirring and nitrogen sparge;
Thereafter, 274 g (1.0 mole) of epoxide and 0.63 g (0.027% by weight of total charge) of catalyst were added to the reaction flask. The contents of the reaction flask were kept at a temperature of 140-150°C for 5 hours with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and the oxirane content (%)
was analyzed. After 1 hour up to a total heating period of 5 hours at a temperature of 140 °C, the oxirane content was
It was determined to be 1.03%. After 2.5 hours to a total heating period of 5 hours at a temperature of 150° C., the oxirane content was determined to be 0.08%. After 4.0 hours at a temperature of 145° C. for a total heating period of 5 hours, the oxirane content was determined to be 0.02%. 5
At the end of the heating period for hours, the oxirane content is
It was determined to be 0.01% and the reaction was complete.
After cooling to room temperature, the contents of the reaction flask were then collected as a residual product (soft grayish white solid) and analyzed to reveal, on average, the tetrafunctional polyol adduct and unreacted dihydrogen. The residue product, which mainly contains a mixture with functional polyols, was found to have the following properties. Oxirane content 0.01% (zero) Viscosity at 54.5°C 931 centistokes Hydroxyl number 114 mgKOH/g Acid number 0.23 mgKOH/g Water content 0.08% Example 3 Nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 2775 g (9.25 moles) of polyol in a 2 liter four-neck round-bottom reaction flask with
was added. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
Thereafter, 1.89 g of catalyst (0.05% by weight based on the total charge) was added to the reaction flask. The contents of the reaction flask were then vacuum stripped at 100° C. for 10 minutes to also remove volatiles such as water in the catalyst. After breaking the vacuum, the nitrogen sparge was again applied and the contents of the reaction flask were heated to 140 °C with continuous stirring.
Heated to ℃. At a temperature of 140℃, epoxide
1014 g (3.70 moles) was added to the reaction flask.
While continuously stirring the contents of the reaction flask.
The temperature was kept at 140-170°C for 2 hours. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Take samples at intervals,
Analyzed for oxirane content (%). At the end of the 2 hour heating period, the oxirane content is
It was determined to be 0.036% and the reaction appeared to be complete. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adducts and unreacted trifunctional polyols. The product was found to have the following properties. Oxirane content 0.036% Viscosity at 54.5°C 5423 centistokes Hydroxyl number 413 mgKOH/g Acid number 0.36 mgKOH/g Water content 0.00% Example 4 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 2775 g (9.25 moles) of polyol in a 2 liter four neck round bottom reaction flask
was added. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
Thereafter, 1.89 g of catalyst (0.05% by weight based on the total charge) was added to the reaction flask. The contents of the reaction flask were heated to a temperature of 140° C. with continuous stirring, after which 1014 g (3.7 moles) of epoxide were added to the reaction flask. Bring the contents of the reaction flask to a temperature of 165 °C with continuous stirring for 3.5
It kept time. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped).
Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 3.5 hour heating period, the oxirane content was determined to be 0.04% and the reaction appeared complete. Then, after cooling to room temperature, the contents of the reaction flask were collected as a residual product,
Analysis has shown that, on average, the residual product containing primarily a mixture of hexafunctional polyol adduct and unreacted trifunctional polyol has the following properties: Oxirane content 0.04% Viscosity at 54.5°C 5488 centistokes Hydroxyl number 371 mgKOH/g Acid number 0.26 mgKOH/g Water content 0.00% Example 5 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 335.4 g (1.118 moles) of polyol was added to a 2 liter, 4 neck, round bottom reaction flask. With continuous stirring and nitrogen sparging, the polyol was heated to a temperature of 110°C, after which 0.375 g (0.075% by weight of total charge) of catalyst was added to the reaction flask. The contents of the reaction flask were heated to 140 mL with continuous stirring.
Heating to a temperature of °C, then the epoxide
164.6 g (0.447 mole) was added to the reaction flask. The contents of the reaction flask were kept at a temperature of 160-170°C for 1 hour with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content. At the end of the 1 hour heating period, the oxirane content was 0.01
% and the reaction appeared to be complete. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adducts and unreacted trifunctional polyols. The product was found to have the following properties. Oxirane content 0.01% Viscosity at 54.5°C 3244 centistokes Hydroxyl number 383 mgKOH/g Acid number 0.34 mgKOH/g Water content 0.00% Example 6 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 420.0 g (1.40 moles) of polyol in a 2 liter four neck round bottom reaction flask.
was added. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
After that, 0.374g of catalyst (0.075g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were heated with continuous stirring to a temperature of 140°C, after which 78.4 g of epoxide (0.56
mol) was added to the reaction flask. The contents of the reaction flask were kept at a temperature of 160-170°C for 1 hour with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen strolling was stopped). Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 1 hour heating period, the oxirane content was determined to be 0.04% and the reaction appeared complete. Then,
After cooling to room temperature, the contents of the reaction flask were collected as a residual product, and analysis revealed that, on average,
The residual product, which mainly contains a mixture of hexafunctional polyol adduct and unreacted trifunctional polyol, was found to have the following properties. Oxirane content 0.04% Viscosity at 54.5°C 1162 centistokes Hydroxyl number 457 mgKOH/g Acid number 0.23 mgKOH/g Water content 0.00% Example 7 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 420 g (1.40 moles) of polyol in a 1 liter four-neck round-bottom reaction flask.
was added. This polyol is heated to a temperature of 100°C while continuously stirring and sparging with nitrogen;
After that, 0.40g of catalyst (0.080g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were then cooled to room temperature and allowed to rise to room temperature for 4 hours.
I kept it for days. The contents of the reaction flask were then heated with continuous stirring to a temperature of 100-110<0>C, after which 78.4 g (0.56 mol) of epoxide was added to the reaction flask. Following 2-3 minutes after adding the epoxide to the reaction flask, the system
The fever reached a temperature of 160℃. The contents of the reaction flask were kept at a temperature of 160° C. for 45 minutes with continuous stirring. Nitrogen sparging was continued throughout the reaction period. Samples were taken at intervals and analyzed for oxirane content. At the end of the 45 minute heating period, the oxirane content was determined to be 0.02% and the reaction was complete. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adducts and unreacted trifunctional polyols. The product was found to have the following properties. Oxirane content 0.02% Viscosity at 54.5°C 986 centistokes Hydroxyl number 416 mgKOH/g Acid number 3.83 mgKOH/g Water content 0.75% Example 8 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 420 g (1.40 moles) of polyol in a 1 liter four-neck round-bottom reaction flask.
and 78.4 g (0.56 mol) of epoxide were added. While continuously stirring and sparging with nitrogen, heat the contents of the reaction flask to a temperature of 100 °C;
After that, 0.40g of catalyst (0.080g for the total charge)
% by weight) was added to the reaction flask. System is 185℃
The system is then heated to a temperature of 160-170℃.
was cooled to a temperature of The contents of the reaction flask were kept at a temperature of 160-170°C for 30 minutes with continuous stirring. Nitrogen sparging was continued throughout the reaction period. Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 30 minute heating period, the oxirane content was determined to be 0.00% and the reaction was complete. The contents of the reaction flask are then collected as a residual product, and analysis reveals that, on average, the residual product contains primarily a mixture of hexafunctional polyol adduct and unreacted trifunctional polyol with the following properties: It was found that it has Oxirane content 0.00% Viscosity at 54.5°C 925 centistokes Hydroxyl number 415 mgKOH/g Acid number 5.61 mgKOH/g Water content 0.71% Example 9 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 630 g (0.70 moles) of polyol in a 2 liter four neck round bottom reaction flask.
was added. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
After that, 0.374g of catalyst (0.056g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were heated with continuous stirring to a temperature of 140°C, after which 39.2 g of epoxide (0.28
mol) was added to the reaction flask. The contents of the reaction flask were kept at a temperature of 160-170°C for 5 hours with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 5 hour heating period, the oxirane content was determined to be 0.00% and the reaction appeared complete. Then,
After cooling to room temperature, the contents of the reaction flask were collected as a residual product, and analysis revealed that, on average, the residual product mainly contained a mixture of hexafunctional polyol adduct and unreacted trifunctional polyol. It was found that it has the following properties. Oxirane content 0.00% Viscosity at 54.5°C 504 centistokes Hydroxyl number 178 mgKOH/g Acid number 0.19 mgKOH/g Water content 0.00% Example 10 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 300 g (1.0 mole) of polyol was added to a 2 liter, 4 neck, round bottom reaction flask. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
After that, 0.278g of catalyst (0.075g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were heated to a temperature of 140° C. with continuous stirring, after which 70 g (0.50 mole) of epoxide was added to the reaction flask. Bring the contents of the reaction flask to a temperature of 160 °C with continuous stirring for 2.5
It kept time. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped).
Samples were taken at intervals and analyzed for oxirane content. At the end of the 2.5 hour heating period,
The oxirane content was determined to be 0.00% and the reaction appeared complete. After cooling to ambient temperature, the contents of the reaction flask were then collected as a residual product, and analysis showed that, on average, the residual product containing primarily hexafunctional polyol adducts had the following properties: Ta. Oxirane content 0.00% Viscosity at 54.5°C 1506 centistokes Hydroxyl number 445.6 mgKOH/g Acid number 0.18 mgKOH/g Water content 0.00% Example 11 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 360 g (0.667 mol) of polyol in a 2 liter four-neck round-bottom reaction flask.
was added. This polyol is heated to a temperature of 100° C. with continuous stirring and nitrogen sparging;
After that, 0.305g of catalyst (0.075g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were heated with continuous stirring to a temperature of 140°C, after which 46.6 g of epoxide
(0.333 mol) was added to the reaction flask. The contents of the reaction flask were kept at a temperature of 165° C. for 4.5 hours with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 4.5 hour heating period, the oxirane content was determined to be 0.00% and the reaction appeared complete. After cooling to ambient temperature, the contents of the reaction flask were then collected as a residual product, and analysis showed that, on average, the residual product containing primarily hexafunctional polyol adducts had the following properties: Ta. Oxirane content 0.00% Viscosity at 54.5°C 657 centistokes Hydroxyl number 276 mgKOH/g Acid number 0.16 mgKOH/g Water content 0.00% Example 12 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 360 g (0.40 moles) of polyol in a 2 liter four neck round bottom reaction flask.
was added. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
After that, 0.291g of catalyst (0.075g for the total charge)
% by weight) was added to the reaction flask. The contents of the reaction flask were heated to a temperature of 140° C. with continuous stirring, after which 28 g (0.20 mole) of epoxide was added to the reaction flask. Bring the contents of the reaction flask to a temperature of 165 °C with continuous stirring for 3.5
It kept time. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped).
Samples were taken at intervals and analyzed for oxirane content. At the end of the 3.5 hour heating period,
The oxirane content was determined to be 0.00% and the reaction appeared complete. After cooling to room temperature, the contents of the reaction flask were then collected as a residual product, and analysis showed that, on average, the residual product containing primarily hexafunctional polyol adducts had the following properties: Ta. Oxirane content 0.00% Viscosity at 54.5°C 646 centistokes Hydroxyl number 176.4 mgKOH/g Acid number 0.17 mgKOH/g Water content 0.00% Example 13 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 2775 g (9.25 moles) of polyol in a 2 liter four-neck round-bottom reaction flask.
was added. The polyol is heated to a temperature of 100°C with continuous stirring and nitrogen sparging;
Thereafter, 1.89 g of catalyst (0.05% by weight based on the total charge) was added to the reaction flask. The contents of the reaction flask were then vacuum stripped at 100° C. for 10 minutes to remove any volatiles such as water in the catalyst. After the vacuum was broken, the nitrogen sparge was again applied and the contents of the reaction flask were heated to 140° C. with continuous stirring. At a temperature of 140°C, 1014 g (3.7 moles) of epoxide was added to the reaction flask. The contents of the reaction flask were kept at a temperature of 140° C. for 3.5 hours with continuous stirring. Furthermore, the contents of the reaction flask were heated to 155 °C with continuous stirring.
The temperature was kept at ~157 °C for 3.5 hours. The contents of the reaction flask were also maintained at a temperature of 160° C. for 1 hour with continuous stirring. A nitrogen blanket was maintained throughout these reactions (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 1 hour heating period at a temperature of 160° C., the oxirane content was determined to be 0.035% and the reaction appeared to be complete. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adducts and unreacted trifunctional polyols. The product was found to have the following properties. Oxirane content 0.035% Viscosity at 54.5°C 5429 centistokes Hydroxyl number 370.6 mgKOH/g Acid number 0.16 mgKOH/g Water content 0.00% Example 14 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer In a 2 liter four neck round bottom reaction flask, 250 g (1.5 moles) of polyol,
Polyol 540g (1.0mol), epoxide 274
(1.0 mol) and 3.8 g (0.30% by weight based on the total charge) of catalyst were added. The contents of the reaction flask were heated with continuous stirring to a temperature of 150-155°C and held at this temperature for 2.5 hours. A nitrogen blanket was maintained throughout the reaction period. Samples were taken at intervals and analyzed for oxirane content (%). Before heating the contents of the reaction flask, the initial oxirane content is 2.46%
(Logic value: 2.53%). After 1.5 hours for a total heating period of 2.5 hours, the oxirane content was determined to be 0.015%. The oxirane content of 0.015% appears to be almost zero.
This is because the first or second drop of titrant (approximately
This is because the indicator changes color at 0.10cc). As a comparison, the initial oxirane content measurement of 0.46% required 14.95 cc of titrant to change the indicator color. After 2.0 hours for a total heating period of 2.5 hours, the oxirane content was again measured at the same zero value. Therefore, the reaction of oxirane with hydroxyl groups was confirmed to be complete after 1.5 or less hours at a temperature of 150°C to 155°C. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adducts and unreacted trifunctional polyols. The product was found to have the following properties. Oxirane content 0.015% (zero) Viscosity at 54.5°C 2911 centistokes Hydroxyl number 325 mgKOH/g Acid number 0.69 mgKOH/g Water content 0.00% Comparison with Comparative Examples B and D shows that the product of this example is It was prepared in a much shorter time than the products of Comparative Examples B and D and had a significantly lower viscosity and oxirane content. Example 15 450 g (1.5 mole) polyol and 540 g (1.0 mole) polyol were added to a 2 liter, 4 neck, round bottom reaction flask equipped with a nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer. This polyol was heated to a temperature of 140°C with continuous stirring, and then 274 g (1.0 mol) of epoxide
and 0.63 g of catalyst (0.05% by weight based on total charge) were added to the reaction flask. The contents of the reaction flask were maintained at a temperature of 140°C to 145°C for 4 hours with continuous stirring. A nitrogen blanket was maintained throughout the reaction period. Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 4 hour heating period, the oxirane content was determined to be 0.04% and the reaction appeared complete. Then, after cooling to room temperature, the contents of the reaction flask were collected as a residual product,
Analysis has shown that, on average, the residual product containing primarily a mixture of hexafunctional polyol adduct and unreacted trifunctional polyol has the following properties: Oxirane content 0.04% Viscosity at 54.5°C 2864 centistokes Hydroxyl number 344.7 mg KOH/g Acid number 0.19 mg KOH/g Example 16 Four 2 liters with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 766.4 g (0.25 moles) of polyol in a round-necked reaction flask.
was added. This polyol is heated with continuous stirring to a temperature of 110-120°C, then 27.4 g (0.10 mol) of epoxide and 0.40 g of catalyst
(0.050% by weight of total charge) was added to the reaction flask. The contents of the reaction flask were then heated to a temperature of 170° C. for 0.5 hour with continuous stirring. A nitrogen blanket was maintained throughout the reaction period. When the temperature reached approximately 140°C to 150°C, an exotherm of 10°C to 20°C was observed. At the end of the 0.5 hour heating period, the oxirane content was determined to be 0.00% and the reaction was complete. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adduct and unreacted difunctional polyol. The product was found to have the following properties. Oxirane content 0.00% Viscosity at 130㎓ 4306 centistokes Hydroxyl number 39.2 mg KOH/g Acid number 0.72 mg KOH/g Example 17 Four 2 liters with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 450 g (1.5 moles) of polyol and 540 g (1.0 mole) of polyol were added to a round-necked, round-bottom reaction flask.
These polyols were heated to a temperature of 100°C with continuous stirring and nitrogen sparging, and then
1.26 g of catalyst (0.09% by weight based on total charge) was added to the reaction flask. With continuous stirring and nitrogen sparging, the polyol and catalyst are further heated to a temperature of 140°C, then the epoxide
377 g (1.0 mole) was added to the reaction flask.
The contents of the reaction flask were then heated with continuous stirring to a temperature of 170°C to 175°C and kept at this temperature for 22 hours. A nitrogen blanket was maintained throughout the reaction period after addition of the epoxide (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content. After 3 hours for a total heating period of 22 hours, the oxirane content was determined to be 1.88%. At the end of the 22 hour heating period, the oxirane content was determined to be 0.40% and the reaction was complete. After cooling to room temperature, the contents of the reaction flask were then collected as a residual product, and analysis revealed a residue containing, on average, a mixture of hexafunctional polyol adduct and unreacted trifunctional polyol. The product was found to have the following properties. Oxirane content 0.40% Viscosity at 54.5°C 6500 centistokes Hydroxyl number 280 mg KOH/g Acid number 0.23 mg KOH/g The above procedure was repeated at higher reaction temperature and higher catalyst concentration as follows. 450 g (1.5 moles) of polyol and 540 g of polyol in a 2 liter, 4-neck, round-bottom reaction flask equipped with a nitrogen inlet and outlet, mechanical stirrer, heating mantle, and thermometer.
(1.0 mol) was added. With continuous stirring and nitrogen sparging, these polyols were heated to a temperature of 100° C., after which 4.11 g (0.3% by weight, based on the total charge) of catalyst were added to the reaction flask.
While continuously stirring and sparging with nitrogen, the polyol and catalyst are further heated to a temperature of 140°C;
Then, 377 g (1.0 mole) of epoxide was added to the reaction flask. The contents of the reaction flask were then heated with continuous stirring to a temperature of 177°C and held at this temperature for 1 hour. A nitrogen blanket was maintained throughout the reaction period after epoxide addition at 140°C (nitrogen sparge was stopped).
At the end of the 1 hour heating period, the oxirane content was determined to be 0.04% and the reaction was complete. After cooling to room temperature, the contents of the reaction flask were then collected as a residual product, and analysis revealed a residual product containing, on average, a mixture of primarily hexafunctional polyol adducts and unreacted trifunctional polyols. It turns out that objects have the following properties. Oxirane content 0.04% Viscosity at 54.5°C 4478 centistokes Hydroxyl number 304.5 mgKOH/g Acid number 0.56 mgKOH/g Water content 0.04% Example 18 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 1350 g (4.5 moles) of polyol in a 2 liter four-neck round-bottom reaction flask.
and 1620 g (3.0 mol) of polyol were added. With continuous stirring and nitrogen sparging, these polyols were heated to a temperature of 100° C., after which 1.89 g of catalyst (0.05% by weight based on the total charge) were added to the reaction flask. The contents of the reaction flask were then vacuum stripped at 100° C. for 10 minutes to remove any volatiles such as water in the catalyst. After releasing the vacuum, perform nitrogen sparging again.
While continuously stirring the contents of the reaction flask.
Heated to 140°C. Epoxide at temperature 140℃
822 g (3 moles) was added to the reaction flask. 146 while continuously stirring the contents of the reaction flask.
The temperature was kept at ~164°C for 2.75 hours. A nitrogen bracket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 2.75 hour heating period, the oxirane content is
It was determined to be 0.02% and the reaction appeared to be complete. After cooling to ambient temperature, the contents of the reaction flask are then collected as a residual product, which upon analysis shows, on average, to contain primarily a mixture of hexafunctional polyol adducts and unreacted trifunctional polyols. The product was found to have the following properties. Oxirane content 0.02% Viscosity at 54.5°C 2410 centistokes Hydroxyl number 329 mgKOH/g Acid number 0.48 mgKOH/g Water content 0.10% Example 19 Equipped with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 1350 g (4.5 moles) of polyol in a 2 liter four neck round bottom reaction flask.
and 1620 g (3.0 mol) of polyol were added. With continuous stirring and nitrogen sparging, these polyols were heated to a temperature of 100° C., after which 1.89 g of catalyst (0.05% by weight based on the total charge) were added to the reaction flask. The contents of the reaction flask were vacuum stripped at 100° C. for 10 minutes to remove any volatiles such as water in the catalyst. After the vacuum was broken, the nitrogen sparge was again applied and the contents of the reaction flask were heated to 140° C. with continuous stirring. 822g of epoxide (3
mol) was added to the reaction flask. The contents of the reaction flask were kept at a temperature of 140°C to 210°C for 2.5 hours with continuous stirring. A nitrogen bracket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%). At the end of the 2.5 hour heating period, the oxirane content was determined to be 0.02% and the reaction appeared complete. After cooling to room temperature, the contents of the reaction flask are then collected as a residual product, and analysis shows that, on average, the residual product mainly contains a mixture of hexafunctional polyol adduct and unreacted polyol. It was found that it has the following properties. Oxirane content 0.02% Viscosity at 54.5°C 2252 centistokes Hydroxyl number 310 mg KOH/g Acid number 0.27 mg KOH/g Example 20 2 liter four-necked vessel with nitrogen inlet and outlet, mechanical stirrer, heating mantle and thermometer 632 g (0.76 moles) of polyol in a round bottom reaction flask;
540 g (1.0 mol) of polyol and polyol
450 g (1.5 mol) was added. These polyols are mixed with continuous stirring and nitrogen sparging.
Heat to a temperature of 140℃, then epoxide
274 g (1.0 mole) and 0.63 g (0.033% by weight of total charge) of catalyst were added to the reaction flask. The contents of the reaction flask were maintained at a temperature of 145°C to 155°C for 4 hours with continuous stirring. A nitrogen blanket was maintained throughout the reaction period (nitrogen sparge was stopped). Samples were taken at intervals and analyzed for oxirane content (%).
After 1 hour to a total heating period of 4 hours at a temperature of 155°C, the oxirane content was determined to be 0.97%. After 1.5 hours to a total heating period of 4 hours at a temperature of 150° C., the oxirane content was determined to be 0.26%. After 3.0 hours for a total heating period of 4 hours at a temperature of 150 °C, the oxirane content was 0.05
%. At the end of the 4 hour heating period, the oxirane content was determined to be 0.01% and the reaction was complete. After cooling to room temperature, the contents of the reaction flask were then collected as a residual product and analyzed to show that, on average, the hexafunctional polyol adduct, unreacted trifunctional polyol, and unreacted difunctional polyol were It was found that the residual product, which mainly contains a mixture of: Oxirane content 0.01% Viscosity at 54.5°C 614 centistokes Hydroxyl number 267 mgKOH/g Acid number 0.15 mgKOH/g Water content 0.02% Examples 21-32 Epoxide, epoxide,
The polyol adduct, polyol adduct, polyol adduct, polyol adduct, catalyst and surfactant were added in various specific combinations in the amounts specified for each example in the table below.
The contents of the bottle were thoroughly mixed by simple stirring at a temperature of 40°C to 50°C until homogeneous.

The mixed preparation was then applied to Bonderite 37 treated steel panels using a No. 20 wire-wound rod and cured for 20 minutes at 121.1° C. in an injected air oven. One Bonderite 37 treated steel panel coated with the specific blend formulation was prepared for each example. Bonderite 37 of Examples 27-32 Cured films on treated steel panels were prepared from the mixed formulations of Examples 21-26, respectively. Coating thickness ranged from about 0.85 mil to about 1.1 mil. After cooling to ambient temperature, the cured coatings were tested for the properties indicated in the table and the results of such tests are shown in the table.

[Table] In addition, the cured coating film was immersed in water at room temperature for 4 days. After 3.5 hours to a total soak period of 4 days, the cured coating had 100% crosshatch adhesion and 4H pencil hardness (other than the cured coating of Example 27, which had a 2H pencil hardness). ). At the end of the 4 day soaking period, Example 28,
Cured coatings of 29, 30 and 31 had 100% crosshatch adhesion density and 4H pencil hardness.
At the end of the 4 day soak period, the cured coating of Example 27 had a crosshatch adhesion of 50% and a 2H pencil hardness. Examples 33-38 Epoxide, photoinitiator, surfactant, and polyol adduct were added to a brown bottle under a yellow light source in the amounts specified for each example in the table below. The contents of the bottle were thoroughly mixed by simple stirring at ambient temperature until homogeneous. The viscosity of the product mixture prepared in each example was then measured on a Brookfield viscometer (centipoise) at 25°C. The viscosity results are shown in the table.

Table: The mixed preparation was then applied to a Bonderite 37 treated steel panel using a No. 20 wire-wound rod at a speed of 30 feet/minute under a mercury lamp ultraviolet light source at 100 watts/inch medium pressure. Cured in one pass. One Bonderite 37 treated steel panel coated with a specific blend formulation for each example.
They were prepared one by one. Cured coatings on Bonderite 37 of Examples 36, 37, and 38 were prepared from the mixed formulations of Examples 33, 34, and 35, respectively. Coating thickness ranged from about 0.85 mil to about 0.95 mil. The cured coatings were tested for the properties indicated in the table and the results of such tests are shown in the table.

【table】

[Table] The table shows the function of polyol adducts as modifiers to improve the flexibility of cured coatings.
The impact strength of the cured coatings shows a significant improvement as the concentration of polyol adduct increases in the coating preparation. Examples 39-54 Epoxide, epoxide, photoinitiator, photoinitiator, surfactant, polyol adduct, and polyol adduct were added to each example in the table below in a brown glass bottle under a yellow light source. They were added in specific amounts and in various specific combinations. The contents of the bottle were thoroughly mixed by simple stirring at ambient temperature until homogeneous.

Table: The mixed preparation was then applied to a Bonderite 37 treated steel panel using a No. 20 wire-wound rod and applied at a speed of 30 feet/minute under a 100 watts/inch medium pressure mercury lamp ultraviolet light source. Oxidation was carried out in one pass. One Bonderite 37 treated steel panel coated with a specific blend formulation for each example.
They were prepared one by one. Bonderite of Examples 47-54
37 Cured coatings on treated steel panels were prepared from the mixed formulations of Examples 39-46, respectively. Coating thickness ranged from about 0.85 mil to about 1.1 mil. The cured coatings were tested for the properties indicated in the table for three days after UV exposure and the results of such tests are shown in the table.

TABLE Examples 55-76 Examples 55-76 illustrate the utility of low viscosity adducts of polycaprolactane polyol and polyepoxide in melamine (urea-formaldehyde) crosslinking systems. Glass bottles, melamine, polyol adducts, polyol adducts,
Polyol adducts, polyol adducts, catalysts, surfactants, and solvents were added in various specific combinations in the amounts specified for each example in the table below. The contents of the bottle were thoroughly mixed by simple stirring at 40°C to 50°C until homogeneous.

Table: The mixed formulation was then applied to Bonderite 37 treated steel panels using a No. 60 wire-wound rod. The wet film was air dried for approximately 5-10 minutes and cured for 30 minutes at 130°C in an injected air oven. Some specific tests in the table below were further cured for an additional 20 minutes at 170°C in an injected air oven. Bonderite 37 coated with a specific blend formulation Bonderite 37 treated steel panels of Examples 66-76 were prepared, one for each example Bonderite 37 coatings on steel panels were coated with the blend preparations of Examples 55-65 Each was prepared from Coating thickness ranged from about 0.85 mil to about 1.1 mil. After cooling to room temperature, the hard and slow coatings were tested for the properties shown in the table and the results of such tests are shown in the table.

[Table] Examples 77-96 Epoxide, epoxide, epoxide, photoinitiator, photoinitiator, surfactant, polyol adduct, polyol adduct, and polyol adduct in a brown glass bottle under a yellow light source were added in various specific combinations in the amounts specified for each example in the table. The contents of the bottle were mixed thoroughly at ambient temperature by simple stirring until homogeneous.

[Table] Addition
The mixed preparation was then applied to Bonderite 37 treated steel panels using a No. 20 wire-wound rod and applied in one pass at a rate of 10 feet/minute under a 300 watt/inch medium pressure mercury lamp ultraviolet light source. hardened with. One Bonderite 37 treated steel panel coated with the specific blend formulation was prepared for each example. Bonderite 37 of Examples 87-96
Cured coatings on treated steel panels were prepared from the mixed formulations of Examples 77-86. The coating thickness ranged from about 0.85 mil to about 1.1 mil. All coatings were hard and tack-free immediately after UV exposure.
The cured coatings were tested for the properties indicated in the table and the results of such tests are shown in the table.

【table】

Claims (1)

[Claims] 1. At least one polycaprolactone polyol and a polyepoxide having two or more epoxy groups per molecule are heated at 80°C to 225°C in the presence of a sulfonic acid catalyst or a derivative thereof. at temperature, the polycaprolactone polyol,
a polyepoxide and a sulfonic acid catalyst or derivative thereof in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the polyepoxide to provide an oxirane content of 0.10% or less, and to produce a highly viscous product; A process for producing a low viscosity adduct of polycaprolactone polyol and polyepoxide, characterized in that the reaction is carried out for a time of 6 hours or less, which is sufficiently short to minimize the formation of polycaprolactone polyol and polyepoxide. 2. The method according to claim 1, wherein the polycaprolactone polyol is a polycaprolactone triol. 3. The method according to claim 1, wherein the polycaprolactone polyol is polycaprolactone diol. 4. The method according to claim 1, wherein the polycaprolactone polyol is a mixture of polycaprolactone triol and polycaprolactone diol. 5. The method according to claim 1, wherein the polyepoxide having two or more epoxy groups per molecule is a cycloaliphatic epoxide. 6 Cycloaliphatic epoxide has the formula: (In the formula, R ₁ to R ₁₈ may be the same or different,
and hydrogen or an alkyl group, generally having 1 to 9 carbon atoms; R is a valence bond or a divalent hydrocarbon group, generally having 1 to 20 carbon atoms) The method according to claim 5, comprising: 7 Cycloaliphatic epoxide has the formula: (In the formula, R ¹ to R ¹⁸ may be the same or different,
and hydrogen or an alkyl group having generally 1 to 9 carbon atoms. 8 Cycloaliphatic epoxide has the formula: (In the formula, R′ group and R″ group may be the same or different,
and is a monovalent substituent or a monovalent hydrocarbon group). 9. The method according to claim 5, wherein the cycloaliphatic epoxide is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. 10. The method according to claim 5, wherein the cycloaliphatic epoxide is bis(3,4-epoxycyclohexylmethyl)adipate. 11. The method according to claim 5, wherein the cycloaliphatic epoxide is vinylcyclohexene diepoxide. 12. The method according to claim 1, wherein the polyepoxide having two or more epoxy groups per molecule is polyglycidyl epoxide. 13. The method according to claim 12, wherein the polyglycidyl epoxide is diglycidyl ether of bisphenol A. 14. The method according to claim 1, wherein the polyepoxide having two or more epoxy groups per molecule is a mixture of a cycloaliphatic epoxide and a polyglycidyl epoxide. 15. The method of claim 1, wherein the polycaprolactone polyol and the polyepoxide having two or more epoxy groups per molecule are present in a molar ratio of polycaprolactone polyol to polyepoxide of 2:1 to 3:1. 16 The sulfonic acid catalyst or its derivative has the formula: (R _f SO ₃ ) _o M where R _f is fluoroalkyl having 1 to 18 carbon atoms and M is an ammonium cation, a quaternary ammonium cation or an amine. cations of metals of the Periodic Table of Metals, Groups B, Subgroups B, and B of the Periodic Table of Metals.
a cation of a metal selected from the B subgroup and the lanthanide and actinide series, where n is M
2. The method of claim 1, wherein the valence is an integer equal to the valence of . 17 Claim 1 in which the sulfonic acid catalyst or its derivative is trifluoromethanesulfonic acid
The method described in Section 6. 18. The method according to claim 16, wherein the sulfonic acid catalyst or its derivative is diethylammonium triflylate. 19. The method of claim 1, wherein the sulfonic acid catalyst or derivative thereof is present in an amount of 0.0001% to 1.0% by weight, based on the total charge of components. 20 Adduct of polycaprolactone polyol and polyepoxide at 54.4℃ (130〓)
The method of claim 1 having a viscosity of 3700 centistokes or less.