KR101254942B1 - Composition for air-drying polyurethane modified vinylester resin and method of preparing the same - Google Patents

Abstract

The present invention aims to provide an air-drying polyurethane-modified vinyl ester resin composition and a method for producing the same. Specifically, the vinyl ester resin has excellent corrosion resistance, high strength, and toughness, and high elongation and low polyurethane resin. Resin as well as shrinkage as well as the advantage of hardening in the contact with the air as a resin that provides a resin suitable for corrosion-resistant FRP, strong acid or alkali handling equipment.
More specifically, the present invention provides a polyurethane-modified vinyl ester resin composition comprising a copolymer of a polyurethane resin and a vinyl ester resin to which an air drying function is imparted, and a method of manufacturing the same.
The air-drying polyurethane-modified vinyl ester resin composition according to the present invention comprises 10 to 50 parts by weight of a polyurethane resin imparted with air drying properties (a) and 10 to 50 parts by weight of a vinyl ester resin (b). It consists of 20 to 50 parts by weight of a reactive diluent and, if necessary, comprises 0.1 to 5 parts by weight of a curing accelerator, 0.01 to 0.1 parts by weight of a curing accelerator, and 0.01 to 0.1 parts by weight of a polymerization inhibitor.
The air-drying polyurethane-modified vinyl ester resin composition according to the present invention is in contact with air while simultaneously meeting the advantages of high corrosion resistance, high strength, and toughness of vinyl ester resin, and elongation and low shrinkage of polyurethane system. Edo hardening has the advantage that it has the effect of providing a resin composite suitable for the equipment for handling corrosion resistant FRP, strong acid or alkali with improved physical properties.

Description

Air dried polyurethane modified vinyl ester resin composition and preparation method thereof {Composition for air-drying polyurethane modified vinylester resin and method of preparing the same}

The present invention relates to polyurethane modified vinyl ester resin compositions for molding such as FRP containers and pipes that require high strength and high corrosion resistance, and also to air-curable polyurethane modified vinyl ester resin compositions which can be cured even when exposed to air. It relates to a manufacturing method.

Vinyl ester resins are usually prepared by reacting unsaturated mono carboxylic acids with epoxy resins so that resins containing vinyl ester residues are provided.

These vinyl ester resins exhibit excellent physical properties in corrosion resistance, heat resistance, etc., and are excellent in toughness as a matrix, impregnated with glass fibers, and excellent in adhesion to fiber reinforced plastics such as corrosion tanks and anticorrosive linings. (fiber reinforced plastics) It is widely used as a molded product.

Typical applications for corrosion resistant FRP include, for example: (1) General chemical industry: storage tanks, reactors, pipes, tact, tank covers, linings, transport tanks, electrolytic tank covers, waste gas treatment lines, filtration equipment. (2) Steel industry: pickling tank covers, hoods, scrubber towers, absorption towers, flush tank covers, ducts, stacks, scrubbers, waste treatment equipment, floor linings. (3) Non-steel industry: electrolytic baths such as copper, nickel, gold, silver and manganese, electrode plates, electrolyte baths, flush baths, waste baths, pipelines, ducts, stacks, demisters, cooling tower units and floor linings. (4) Paper and pulp industry: bleach tanks, cleaning liquid tanks, cleaning towers, absorption towers, linings, chlorine dioxide generators, waste gas pipes, ducts, hoods, fans. (5) Textile industry: bleaching tanks, raw material tanks, neutralizing tanks, flushing tanks, hoods, wastewater pipes, other tact, fans, linings. (6) Food / pharmaceutical industry: storage tanks, transportation tanks, various product conditioning tanks, pure water tanks, pipe linings. (7) Spa industry: transport pipes, water tanks, septic tanks, tile membranes. (8) Anti-pollution: desulfurization unit, desulfurization unit, waste water treatment unit, dust treatment unit, various ventilation system. (9) Others: Widely used in various industrial fields such as marine equipment parts, agricultural equipment, tank lorry, containers, sewers and agricultural drainage lines.

As described above, the vinyl ester resin is widely used as a molded product of fiber reinforced plastics, but the vinyl ester resin is in the manufacturing process of the molded product due to a problem of hardening (uncured, etc.) when exposed to air. The production process tends to be complicated, such as attaching vinyl for air blocking in the curing process.

As a prior art related to vinyl ester resin manufacturing technology, for example, disclosed in Korea Patent Publication No. 10-2000-0061812 condensation polymerization of epoxy resin composition and bisphenol-A and then condensation polymerization of monomer having an unsaturated group. Korean Patent Laid-Open Publication No. 2003-0097392 discloses a composition of a flame retardant vinyl ester resin and a method for producing the same, and hydroxyalkyl acrylate or methacrylate dicarboxylic acid ester is disclosed in US Pat. No. 3,367,992. The Dow Chemical Company, U.S. Patent 4,786,693, discloses a urethane modified epoxy composition (The Dow Chemical Company) containing oxazolidi or thiazolininone.

Although the above prior arts improve the functional or physical properties of vinyl ester resins, such as imparting flame retardancy and improving mechanical properties, as described above, there is disclosed a solution to a problem of curing failure when the vinyl ester resin is exposed to air. no.

The present invention solves the above problems by proposing an air-drying polyurethane-modified vinyl ester resin composition.

The present invention aims to provide an air-drying polyurethane-modified vinyl ester resin composition and a method for preparing the same, and more specifically, not only hardening the part in contact with air while maintaining high strength and high corrosion resistance. An object of the present invention is to provide an air-drying polyurethane-modified vinyl ester resin composition and a method for producing the same, which solve the problem of product defects due to poor curing.

The air-drying polyurethane-modified vinyl ester resin composition according to the present invention as a solution for achieving the above object is 10 to 50 parts by weight of polyurethane resin, 10 to 50 parts by weight of vinyl ester resin, reactive diluent with air drying properties It consists of 20 to 50 parts by weight, if necessary, characterized in that consisting of 0.1 to 5 parts by weight of the curing accelerator, 0.01 to 0.1 parts by weight of the curing bath accelerator, 0.01 to 0.1 parts by weight of the polymerization inhibitor.

The air-drying polyurethane resin is prepared by a urethane reaction of an oligomer glycol and an isocyanate prepared by condensation polymerization of an alcohol and a basic acid in which at least one air-driable component is present among alcohols and basic acids, or Or it is produced by the urethane reaction of the alcohol and isocyanate which is a component which can be air dried.

Examples of the alcohol component that can be air dried include silanol, trimethylethyl propane diallyl ether (TMPDE), glycol group PG, and PEG, and one or more selected from them. Do.

In addition, the base acid components that can be air dried include vegetable fatty acid soybean fatty acid, coconut fatty acid, castor oil fatty acid, palm oil fatty acid, linseed oil fatty acid, aromatic saturated basic acid tetrabromo phthalic anhydride, tetrachloro phthalic anhydride, and anhydrous acid ( Chlorendic acid), an alicyclic saturated polybasic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 1,2-hexahydrophthalic anhydride, 1,4-cyclohexanecarboxylic acid, and at least one selected from these, In order to increase air drying property, it is preferable to select at least one from castor oil fatty acid, linseed oil fatty acid, tetrabromophthalic anhydride, and tetrahydrophthalic anhydride, and from the viewpoint of mechanical properties, from linseed oil fatty acid and tetrahydrophthalic anhydride, It is more preferable to select one or more.

In addition, the isocyanate is an aromatic diisocyanate compound such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), tetramethyl xylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated methane diisocyanate ( Aliphatic diisocyanate compounds such as H12MDI), norbornene diisocyanate and alicyclic compounds such as hexamethylene diisocyanate (HDI), dimer diisocyanate, and the like, and may be selected from TDI, IPDI, H12MDI and HDI.

In addition, the vinyl ester resin may be produced by a well-known conventional technique, a monomer having a reactive unsaturated group after addition polymerization of an epoxy resin (trade name YD-128, Kukdo Chemical Co., Ltd.) and bisphenol-A. For example, acrylic acid, methacrylic acid, or the like, to produce a vinyl ester resin.

The polyurethane-modified vinyl ester resin composition according to the present invention is dissolved in a reactive diluent, which is a conventional radical polymerizable unsaturated monomer, in a polyurethane-modified vinyl ester resin, and a liquid polyurethane-modified vinyl having a solid content of 60% and a weight average molecular weight of 4,000 to 5,500. It is characterized in that it is provided as an ester resin, consisting of a curing accelerator, a curing bath accelerator, a polymerization inhibitor and the like as necessary.

Examples of the reactive diluent include styrene, methyl acrylate, methyl methacrylate, butyl acrylate, ethyl hexaacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, and butyl methacryl. The rate etc. can be illustrated and it is more preferable to select from styrene, methyl methacrylate, and 2-hydroxyethyl methacrylate.

As a hardening accelerator, it uses together 1 type (s) or 2 or more types chosen from naphthenates, such as a cobalt of naphthenate, copper natthenate, and barium nitrate, an octenate such as cobalt, octenate, manganese octaneate, zinc octenate, and vanadium octenate. It can be used, The compounding quantity is 0.1-5 weight part, Preferably it exists in the range of 0.5-3 weight part.

Curing accelerators include aniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N , N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluitine, diethylenetriamine, N, N-substituted aniline, N, N-substituted-p-toluidine, 4- (N, N, such as pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline Amine such as substituted amino) benzaldehyde may be used as a curing accelerator, and curing accelerators may be used alone or in combination of two or more thereof, preferably 0.01 to 0.1 parts by weight, and blended in a range of 0.01 to 0.05 parts by weight. It is more preferable to do.

Examples of the polymerization inhibitor include trihydrobenzene, trihydroquinone, 1,4-naphthoquinone, parabenzoquinone, hydroquinone, toluhydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2, One or two or more kinds selected from 6-di-tert-butyl-4-methylphenol can be used, preferably 0.01 to 0.1 parts by weight, and more preferably 0.01 to 0.05 parts by weight.

In addition, the method for preparing the air-drying polyurethane-modified vinyl ester resin composition according to the present invention includes the steps of (a) preparing a polyurethane resin to which the air-drying function is imparted, and (b) preparing a vinyl ester resin; (c) copolymerizing the resin obtained in steps (a) and (b) and (d) adding a reactive diluent, if necessary (e) a curing accelerator, a curing accelerator, and polymerization. Characterized in that it comprises a step of blending the inhibitor.

In the step (a) of preparing a polyurethane resin provided with air drying property, a condensation polymerization method of (a-1) alcohol and basic acid in which one or more air-driable components are present in alcohol and basic acid is carried out by a condensation polymerization reaction. Prepared by the urethane reaction of the prepared oligomer glycol and isocyanate or (a-2) by the urethane reaction of alcohol and isocyanate which is a component that can be air dried, the vinyl ester resin of step (b) The manufacturing step consists of preparing a vinyl ester resin by a well-known conventional technique, for example, by addition polymerization of epoxy resin (trade name YD-128, Kukdo Chemical Co., Ltd.) and bisphenol-A and then reactive. It comprises a step of producing a vinyl ester resin by addition polymerization of a monomer having an unsaturated group, for example acrylic acid or methacrylic acid.

In addition, the step (c) consists of copolymerizing 10 to 50 parts by weight of the polyurethane resin prepared in step (a) and 10 to 50 parts by weight of the vinyl ester resin prepared in step (b).

The air-drying polyurethane-modified vinyl ester resin composition according to the present invention is in contact with air while simultaneously meeting the advantages of high corrosion resistance, high strength, and toughness of the vinyl ester resin and high elongation and low shrinkage of the polyurethane system. It also has the advantage of hardening, which not only shows the effect of providing resin composites suitable for equipments with improved corrosion resistance FRP, strong acid or alkali, but also prevents problems of hardening due to air contact in the manufacturing process of resin composites. The solution has the advantage of providing a good resin composite with improved quality and solving the complexity of the manufacturing process.

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

All parts by weight and percentages used in the present invention are expressed in weight unless otherwise specified.

A. Air Drying  Functional Oligomer glycol  Produce

Example A-1

152.14 parts by weight of tetrahydrophthalic anhydride (THPAn), 214 parts by weight of TMPDE80 (trade name of PERSTORP, 79 to 85% by weight of diaryl ether), and 76.09 parts by weight of propylene glycol (PG) were added to a 2-liter four-necked flask. After installing a thermometer, a column, and a nitrogen inlet tube, the temperature was raised to 120 to 130 ° C. in a nitrogen atmosphere, and the temperature was raised to 220 ° C. at a rate of 20 ° C./hr after a 1 hour holding reaction. The reaction was carried out while maintaining the temperature at 220 ° C and cooled to an acid value of 1.0 mgKOH / g or less to prepare an oligomer glycol.

Example A-2

The oligomer glycol was manufactured under the same conditions as in Example A-1, except that THPAn of Example A-1 was replaced with 166.13 parts by weight of isophthalic acid (IPA).

Example A-3

An oligomer glycol was prepared under the same conditions as in Example A-1, except that TMPDE80 of Example A-1 was replaced with 280 parts by weight of flax fatty acid.

<Example A-4>

<Example A-1> except that TMPDE80 of <Example A-1> was used by replacing 250 parts by weight of DI-10 (trade name of Siltech Co., Ltd., silanol having a weight average molecular weight of 990) with <Example A-1> The oligomer glycol was prepared under the same conditions as the above.

B. air Drying  Granted Polyurethane resin  Produce

Example B-1

500 parts by weight of the oligomer glycol prepared in <Example A-1> was placed in a 2-liter four-necked flask, and a thermometer and a nitrogen inlet tube were installed, followed by toluene diisocyanate (TDI, 2,4-di 346 parts by weight of a mixture of 80% by weight of isocyanate toluene and 20% by weight of 2,6-diisocyanate toluene) was added over 2 to 2.5 hours. At this time, the flask internal temperature was maintained at 60 ~ 65 ℃. When TDI was completed, the reaction was carried out at 65 ° C. for 1 hour, and the temperature was raised to 75 ° C. at a rate of 20 ° C./hr. The polyurethane resin was prepared by reacting NCO% until it reached 10 ± 0.5% while maintaining the temperature at 75 ° C.

Example B-2

Polyurethane resin was prepared under the same conditions as in <Example B-1>, using the oligomer glycol prepared in <Example A-2>.

Example B-3

Polyurethane resin was prepared under the same conditions as in <Example B-1>, using the oligomer glycol prepared in <Example A-3>.

Example B-4

Polyurethane resin was prepared under the same conditions as in <Example B-1>, using the oligomer glycol prepared in <Example A-4>.

C. Vinyl ester resin  Produce

Example C

400 parts by weight of YD-128 (Epoxy Resin, Kukdo Chemical Co., Ltd.) and 60 parts by weight of bisphenol-A were placed in a 2-liter four-necked flask, and a thermometer and a nitrogen inlet tube were installed. . When the temperature was raised to 150 ° C, samples were taken at 15 minute intervals. The sample was spot-tested with 1 N aqueous potassium permanganate solution to observe the color change. Confirming that there was no color change, the reactor temperature was cooled to 100 ° C. or lower, and 140 parts by weight of acrylic acid and 0.1 part by weight of toluenehydroquinone were added. The temperature was maintained at 120 ° C. while uniformly stirring in the reaction system to prepare a vinyl ester resin having an acid value of 10 mgKOH / g or less.

D. Air Drying  Polyurethane modified Vinyl ester resin  Produce

Example D-1

After inserting 420 parts by weight of the vinyl ester resin prepared in <Example C> and 180 parts by weight of the polyurethane resin prepared in <Example B-1> at a 2-liter four-necked flask, a thermometer and a nitrogen inlet tube were installed. It was made to react, heating up gradually to 65 degreeC in nitrogen atmosphere. When it heated up to 65 degreeC, it heated up to 75 degreeC at the speed | rate of 20 degreeC / hr after carrying out reaction, maintaining for 1 hour. The copolymerization was maintained at 75 ° C. until NCO% became zero. When NCO% reached 0, 400 parts by weight of styrene was added to prepare a liquid polyurethane-modified vinyl ester resin having a solid content of 60% and a weight average molecular weight of 4,500.

Example D-2

Liquid polyurethane modified vinyl ester resin having a solid content of 60% and a weight average molecular weight of 4,800 was prepared under the same conditions as in <Example D-1>, using the polyurethane resin prepared in <Example B-2>. It was.

Example D-3

Liquid polyurethane-modified vinyl ester resin having a solid content of 60% and a weight average molecular weight of 4,000 was prepared under the same conditions as in <Example D-1>, using the polyurethane resin prepared in <Example B-3>. It was.

Example D-4

Liquid polyurethane modified vinyl ester resin having a solid content of 60% and a weight average molecular weight of 5,500 was prepared under the same conditions as in <Example D-1>, using the polyurethane resin prepared in Example B-4. It was.

<Comparative Example>

600 parts by weight of vinyl ester resin and 400 parts by weight of styrene prepared in <Example C> were added to a 2-liter four-necked flask to prepare a liquid vinyl ester resin having a solid content of 60% and a weight average molecular weight of 1,700.

Physical property test results comparing the liquid resins prepared in Examples and Comparative Examples are shown in the following [Table 1].

As can be seen from Table 1, the polyurethane-modified vinyl ester resin prepared according to the present invention can be seen that not only the curing is carried out in air but also excellent mechanical properties compared to the vinyl ester resin of the comparative example.

Claims (14)

delete 10-50 parts by weight of air-dried polyurethane resin prepared by reacting an oligomer glycol prepared by reacting an air-dryable alcohol with a basic acid capable of air drying and an isocyanate with urethane, and a vinyl ester resin 10-50 weight Air-dried polyurethane-modified vinyl ester resin composition, characterized in that consisting of 20 to 50 parts by weight and reactive diluent.
[In the above, the air-dryable alcohol is selected from one or more from trimethylol propylene ether (Pri Methylol Propane Diallyl Ether), PG, PEG and silanol (Silianol),
The base acids which can be air dried are soybean fatty acid, coconut fatty acid, castor oil fatty acid, palm oil fatty acid, linseed oil fatty acid, trabromophthalic anhydride, tetrachloro phthalic anhydride, Chlordic acid, tetrahydrophthalic anhydride, methyltetrahydro At least one is selected from phthalic anhydride, 1,2-hexahydrophthalic anhydride and 1,4-cyclohexanecarboxylic acid.] The air-dried polyurethane-modified vinyl ester resin composition according to claim 2, wherein the polyurethane resin to which the air-drying property is imparted is produced by urethane reaction of an alcohol and an isocyanate which is an air-driable component.
[In the above, alcohol which can be air dried is One or more selected from Tri Methylol Propane Diallyl Ether, PG, PEG and Silanol.] The air-dried polyurethane-modified vinyl ester resin according to claim 2 or 3, further comprising 0.1 to 5 parts by weight of a curing accelerator, 0.01 to 0.1 parts by weight of a curing accelerator and 0.01 to 0.1 parts by weight of an polymerization inhibitor. Composition. delete delete The isocyanate according to claim 2 or 3, wherein the isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), tetramethylxylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated methane diisocyanate. Air-drying polyurethane resin composition, characterized in that at least one selected from the group consisting of (H12MDI), norbornene diisocyanate hexamethylene diisocyanate (HDI) and dimer diisocyanate. The air-drying polyurethane-modified vinyl ester resin composition according to claim 2 or 3, wherein the air-drying polyurethane-modified vinyl ester resin has a weight average molecular weight of 4,000 to 5,500. delete (a) reacting an air-drying alcohol with a base acid capable of air drying to react urethane oligomer glycol with an isocyanate to produce a polyurethane resin given air drying property,
(b) preparing a vinyl ester resin,
(c) copolymerizing with the resin obtained in steps (a) and (b); and
(D) a method for producing an air-drying polyurethane modified vinyl ester resin composition comprising the step of blending a reactive diluent.
[In the above, the air-dryable alcohol is selected from one or more from trimethylol propylene ether (Pri Methylol Propane Diallyl Ether), PG, PEG and silanol (Silianol),
The base acids which can be air dried are soybean fatty acid, coconut fatty acid, castor oil fatty acid, palm oil fatty acid, linseed oil fatty acid, trabromophthalic anhydride, tetrachloro phthalic anhydride, Chlordic acid, tetrahydrophthalic anhydride, methyltetrahydro At least one is selected from phthalic anhydride, 1,2-hexahydrophthalic anhydride and 1,4-cyclohexanecarboxylic acid.] 11. The air-drying polyurethane-modified vinyl ester resin according to claim 10, wherein step (a) produces a polyurethane resin imparted with a drying function by a urethane reaction of an alcohol and an isocyanate which is an air drying component. Method of Preparation of the Composition.
[In the above, the air-dryable alcohol is selected from one or more from Tri Methylol Propane Diallyl Ether, PG, PEG, and silanol.] 12. The polyurethane-modified vinyl ester resin composition according to claim 10 or 11, wherein step (c) is copolymerized into 10 to 50 parts by weight of the air-dried polyurethane resin and 10 to 50 parts by weight of the vinyl ester resin. Manufacturing method. delete delete