KR101510399B1 - Manufacturing method for waterborne flame-retarding hybrid resin and coating compositions thereof - Google Patents
Manufacturing method for waterborne flame-retarding hybrid resin and coating compositions thereof Download PDFInfo
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- KR101510399B1 KR101510399B1 KR20140065572A KR20140065572A KR101510399B1 KR 101510399 B1 KR101510399 B1 KR 101510399B1 KR 20140065572 A KR20140065572 A KR 20140065572A KR 20140065572 A KR20140065572 A KR 20140065572A KR 101510399 B1 KR101510399 B1 KR 101510399B1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention relates to a coating composition which is excellent in chemical resistance, water resistance, abrasion resistance, impact resistance and excellent adhesion strength, and has excellent cleaning performance upon adhering a contaminant to a coating film. Particularly, Soluble flame retardant hybrid resin and a coating composition for a concrete floor using the same.
Description
The present invention relates to a method for producing a water-soluble flame retardant hybrid resin and a coating material composition using the same, and more specifically to a method for producing a water-based flame-retardant hybrid resin, which exhibits high adhesion strength to a concrete surface and improves durability by improving the water- Flame retardant hybrid resin that can prevent flame spread and toxic gas generation when a fire occurs, and an eco-friendly coating composition prepared by the method.
In the case of the underground parking lot floor of the construction structure, the surface treatment method is applied to apply the thermosetting polymer resin in order to prevent the appearance of the aesthetic exterior and the dust caused by the damage of the concrete surface due to the running of the vehicle.
However, the coating material containing an organic resin such as the above-mentioned thermosetting resin as a main component is excellent in adhesiveness and mechanical strength. On the other hand, when moisture contained in the concrete rises due to heat pressure, the coating material is saponified by alkali hydrolysis There is a side effect that the finish material peels off due to occurrence of a phenomenon, and a cosmetic problem occurs due to yellowing due to ultraviolet rays and the like.
Especially, in recent years, problems of environmental pollution have been highlighted on a global level, and the need for environmentally friendly materials in the field of construction materials has become stronger in Korea, and a lot of research and development is proceeding. In order to cope with environmental problems, aqueous or water-soluble paints and finishing materials are distributed in the market. However, the application of the paints and finishing materials to the field is very weak due to the low mechanical strength as compared with the conventional solvent type paints.
It shows high adhesion strength by chemical reaction with concrete structure. It shows watertightness by reinforcing the surface of concrete and shows the surface strength and chemical resistance of high hardness. It shows mechanical strength equal to or higher than that of oil based material. It is urgent to develop an environmentally friendly water-soluble flame retardant hybrid coating material that can easily clean adhered contaminants by using water and soapy water when the floating contaminants adhere to the finish material and prevent flame diffusion and toxic gas generation in the event of a fire. to be.
The object of the present invention is to provide a method for producing a water-soluble flame retardant hybrid resin by using an inorganic reactive group (methoxy, ethoxy, acetoxy) of an organic functional silane coupling agent as a coupling agent do.
In addition, the present invention relates to a method for producing a silane coupling agent by hydrolyzing a silane coupling agent under an acid catalyst to prepare a first silane compound, hydrolyzing the silane coupling agent under another acid catalyst to prepare a second silane compound, Soluble flame retardant hybrid resin having high adhesion strength and excellent water resistance and cleaning function.
Another object of the present invention is to provide a method for producing a water-soluble flame retardant hybrid resin having an excellent cleaning effect and a high adhesion strength by using an alkali metal organosiliconate.
Another object of the present invention is to provide a water-soluble flame retardant hybrid resin which imparts flame retardancy by reacting a polyalkoxysiloxane with a silane coupling agent which is a reactive inorganic crosslinking agent.
In order to achieve the above object, the present invention provides a method for producing a silane coupling agent, comprising the steps of: (A) hydrolyzing a silane coupling agent in an acid catalyst in a pH range of 3 to 4 to obtain a first silane compound; (B) hydrolyzing the silane coupling agent in an acid catalyst different from the catalyst used in the step (A) in a pH range of 3 to 4 to obtain a second silane compound; (C) adding the second silane compound to the first silane compound and stirring to obtain a composite silane stirring mixture; (D) grafting an alkali metal organic silicate to the complex silane stirring mixture to obtain a grafted polymer; And (E) adding a polyalkoxysiloxane compound to the graft polymer and reacting the resultant to obtain a water-soluble flame retardant hybrid resin.
The present invention also provides a coating composition for a concrete floor finish, which comprises a water-soluble flame retardant hybrid resin prepared by the above-mentioned method as an active ingredient.
Hereinafter, the method for producing the water-soluble flame retardant hybrid resin of the present invention and the coating composition for floor finishing using the same will be described in detail.
(A) hydrolyzing a silane coupling agent in an acid catalyst in a pH range of 3 to 4 to obtain a first silane compound
This step is a step of hydrolyzing the silane coupling agent while maintaining the pH in the range of 3 to 4 using an acid catalyst to obtain the first silane compound. The first silane compound obtained in this step is a " hydrolyzed silane compound " which is a silane compound containing a silanol group (Si-OH) obtained by hydrolyzing a silane coupling agent.
The silane coupling agent is a material showing the form of R-Si (OR ') n, and R is a functional group chemically bonding with an organic material such as various synthetic resins, and includes an amino group (-NH 2 ), an epoxy group, OR 'represents a methoxy group capable of being hydrolyzed by a functional group that is chemically bonded to glass, metal, and inorganic materials. Examples of the organic group include, but are not limited to, an acryl group, a vinyl group, a mercapto group, include H 2 SiOH): CH 3 O -: -), ethoxy group (ethoxyl group), silanol group (silanol group C 2 H 5 O . Alkoxy (OR ') n forms a silanol of R-Si (OH) n which can form a film through hydrolysis reaction and forms an organic film of siloxane on the surface.
The present invention is preferably used as a silane coupling agent, such as? -Glycidoxy propyl trimethoxy silane,? -Glycidoxy propyl methyl diethoxy silane,? -Glycidoxy propyl trimethoxy silane, (3-aminopropyltriethoxysilane), vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane (hereinafter referred to as " 3-methacryloxypropyltrimethoxysilane " One or more selected from the group can be used.
In the present invention, the silane coupling agent is hydrolyzed in the pH range of 3 to 4 to prepare the first silane compound. If the pH is less than 3, the effect of promoting hydrolysis is insufficient, and when the pH becomes 4 or more, There is a problem that the silane compound gels due to the decomposition reaction.
At this time, it is preferable to use at least one acid selected from the group consisting of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, borax and phosphoric acid as the acid catalyst for maintaining the pH in the range of 3 to 4.
In this step, preferably, 50 to 100 parts by weight of purified water and acetic acid as an acid catalyst are added to 100 parts by weight of the silane coupling agent and the solution is adjusted to pH 3 to 4 at a rate of 20 min / ml. The first silane compound can be obtained by stirring at 100 rpm for 3 hours while maintaining the temperature at 90 to 110 ° C.
(B) hydrolyzing the silane coupling agent in the range of pH 3 to 4 under an acid catalyst to obtain a second silane compound
This step is a step of hydrolyzing a silane coupling agent in a pH range of 3 to 4 by using an acid catalyst different from the acid catalyst used in the step (A) to obtain a second silane compound. The second silane compound obtained in this step is also a " hydrolyzed silane compound " and is a silane compound containing a silanol group (Si-OH) obtained by hydrolyzing a silane coupling agent.
Thus, in this step, a second silane compound is obtained by using an acid catalyst different from that in the step (A), and this second silane compound is a silane compound for increasing the adhesion strength and corresponds to a silane compound which migrates .
That is, the present invention uses the two kinds of silane compounds obtained in steps (A) and (B), respectively. Thus, the storage stability of the resin is secured, and the water resistance, chemical resistance, And a colloidal state in which silica particles of several hundred nm to several 탆 do not generate phase separation in the inorganic resin while preventing agglomeration of the silane through stable dispersion of the silane compound can be obtained .
The silane coupling method in this step is not particularly limited as long as γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl methyl diethoxy silane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane. One or more selected can be used.
The acid catalyst of this step may be at least one selected from the group consisting of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, borax and phosphoric acid. It is important to do. Preferably, 100 parts by weight of boric acid, 80 parts by weight of borax and 200 parts by weight of purified water are reacted with stirring at 70 rpm for 1 hour, for example, using a mixture of boric acid and borax (also referred to herein as a "boric acid compound" It is recommended to use the one produced.
In this step, a boric acid compound, which is an acid catalyst different from the acid catalyst used in the step (A), is added dropwise to 100 parts by weight of the silane coupling agent in a proportion of 50 to 100 parts by weight, At a rate of 20 ml / min, and then reacted at a rate of 100 rpm for 3 hours while reacting at a reaction temperature of 90 to 110 ° C to react to produce a second silane compound.
(C) adding the second silane compound to the first silane compound and stirring to obtain a composite silane stirring mixture
In this step, the second silane compound prepared in step (B) is added to the first silane compound prepared in step (A) and stirred to obtain a composite silane stirring mixture.
Herein, the composite silane stirring mixture is obtained by migrating the first silane compound and the second silane compound. When the hybridization of the thermoplastic or thermosetting resin and the inorganic materials is performed by stabilizing the dispersion of the silane, the electrical properties and the chemical resistance, Physical strength such as abrasion resistance and impact resistance can be improved.
At this time, preferably, 50 parts by weight of the second silane compound obtained in the step (B) is added to 100 parts by weight of the first silane compound obtained in the step (A), and then the mixture is homogenized for 30 minutes to 1 hour The reaction is carried out while stirring with an ultrasonic wave. At this time, it is preferable that the temperature maintains a temperature generated in the course of the reaction.
(D) grafting an alkali metal organosiliconate to the complex silane stirring mixture to obtain a graft polymer
In this step, an alkali metal organic silicate is graft-polymerized to the composite silane stirring mixture prepared in the step (C) to produce a graft polymer.
Herein, the first silane compound in the complex silane stirring mixture corresponds to a substance which stems from the graft polymerization reaction. The addition of the alkali metal organosiliconate to the complex silane stirring compound in the graft polymerization in this step is intended to suppress the homogeneous intermolecular crosslinking and maximize the crosslinking reaction between the dissimilar resins to increase the dispersing efficiency.
When the composite silane stirring mixture and the alkali metal organosiliconate form a graft polymer, a high-density polymer material is produced, and voids are not formed on the surface of the cured product when the concrete is applied to the concrete, thereby significantly reducing cracks . As a result, the grafted polymer of the present step can exhibit a complex synergistic effect of the physical properties of the inorganic resin by attaching the silane having enhanced water resistance, abrasion resistance, and impact resistance.
At this time, the alkali metal organosiliconate has the effect of easily cleaning various contaminants deposited on the coating film by using water or soapy water and improving the adhesion strength, and preferably sodium methylsiliconate, potassium methylsiliconate, sodium Ethyl silicoate, and potassium methyl silicoate.
In this step, preferably, 50 parts by weight of an alkali metal organic silicate is dropped into 100 parts by weight of the composite silane stirring mixture of the step (C), and the mixture is stirred at 100 rpm for 2 hours while maintaining the temperature within the range of 90 to 110 ° C A graft polymer can be obtained.
(E) adding a polyalkoxysiloxane compound to the graft polymerizate and reacting to obtain a water-soluble flame retardant hybrid resin
This step is a step of adding a polyalkoxysiloxane compound to the graft polymer of step (D) to obtain a water-soluble flame retardant hybrid resin. As described above, the water-soluble flame retardant hybrid resin having maximized flame retardancy can be obtained by adding a polyalkoxysiloxane compound to the graft polymerizate and reacting the same.
In this step, preferably, 2 to 10 parts by weight of the polyalkoxysiloxane compound is added dropwise to 100 parts by weight of the graft polymer in the step (D), and the mixture is stirred at a temperature of 20 to 25 ° C for 7 hours at a speed of 100 rpm, A hybrid resin can be obtained.
At this time, the polyalkoxysiloxane compound is preferably a polyalkoxysiloxane compound obtained by reacting the first silane compound obtained in the step (A) with a polyalkoxysiloxane. As described above, the present invention can provide a polyalkoxysiloxane compound capable of imparting flame retardancy and improving surface hardness by reacting a polyalkoxysiloxane with a first silane compound which is a hydrolyzed silane compound, And the resultant is reacted to obtain a water-soluble flame retardant hybrid resin.
At this time, the polyalkoxysiloxane compound may be prepared by, for example, dropping 2 to 10 parts by weight of a polyalkoxysiloxane to 100 parts by weight of the first silane compound at a rate of 20 min / ml, The polyalkoxysiloxane compound obtained by stirring at a speed of 100 rpm can be used.
At this time, the polyalkoxysiloxane may preferably be at least one of polyethoxysiloxane and polymethoxysiloxane. More preferably, the tetraalkoxysilane monomer content and the alcohol content are each 0.5% by weight or less, the silica conversion concentration is 53% by weight or more, but the weight average molecular weight is 600 to 3,000 and the viscosity is 10 to 1,000 cps at 25 캜. It is preferable to use a polyalkoxysiloxane.
The present invention can use the water-soluble flame retardant hybrid resin thus prepared in a floor finish composition, for example, as a coating composition for a concrete floor surface finish.
The coating composition for floor surface finishing of concrete according to the present invention shows high adhesion strength to the concrete surface and the durability is improved due to increase of the watertightness of the concrete surface and the hardness and function of the applied surface are improved, so that pollutants can be easily cleaned. Diffusion prevention and toxic gas generation can be suppressed.
The present invention is characterized in that the silane coupling agent is separately hydrolyzed to separately synthesize the first silane compound and the second silane compound for improving the adhesion strength, the second silane compound is added dropwise to the first silane compound, , The water-soluble flame retardant hybrid resin prepared according to the present invention has an effect of not only an aqueous pollution source but also an oil pollution source that is washed with water, soapy water or alcohol even when adhering to the surface of the coating film. And the water resistance of the surface and the water tightness of the concrete surface are greatly improved.
Further, since the water-soluble flame retardant hybrid resin of the present invention uses alkali metal organosiliconate, it has excellent resistance to ultraviolet rays and chemical resistance as compared with conventional organic paints, and is integrated by chemical bonding due to the characteristics of materials having the same properties as concrete It has an effect of suppressing lifting of the coating film due to the excellent adhesion strength.
In addition, the present invention can produce a water-soluble flame retardant hybrid resin having improved compatibility of a polymer by graft-polymerizing the hydrolyzed silane compound and the alkali metal organosiliconate.
In addition, the present invention can produce a water-soluble flame retardant hybrid resin that maximizes flame retardance and further improves surface hardness by reacting a hydrolyzed silane compound with a polyalkoxysiloxane.
Further, the present invention is environmentally friendly since it does not use toxic substances harmful to human body.
Fig. 1 is a comparative test result of flame retardancy by inducing a torch flame.
FIG. 2 shows the results of a comparative experiment showing the difference in toxic gas generation after the fire evolution.
Fig. 3 shows the results of a comparison test of the cleaning property of the modified magic contamination area. (A: Example 1, B: Comparative Example 2)
Fig. 4 shows the results of a comparative test for cleaning the oil-based magic contamination site. (A: Example 2, B: Comparative Example 2)
5 shows the chemical resistance comparison test results. (For each chemical treatment, the left side is the result of Comparative Example 2, and the right side is the result of Example 2)
6 shows the results of the vulcanization modification experiment (A: Example 1, B: Comparative Example 2)
7 is a result of the adhesion strength test. The above drawing shows a state immediately after dropping water on the coating film, and the following figure shows the results after 24 hours. (A: Example 2, B: Comparative Example 2)
Hereinafter, the inorganic resin composition according to a preferred embodiment of the present invention will be described step by step, but the present invention is not limited to the following examples. Accordingly, it is obvious that those skilled in the art can variously change the present invention without departing from the technical idea of the present invention.
Example 1: Preparation of water-soluble flame retardant hybrid resin
(1) Preparation of first silane compound
To 100 parts by weight of? -glycidoxypropyltrimethoxysilane, 100 parts by weight of purified water was added dropwise at a rate of 20 ml / min with adding acetic acid to maintain the pH within the range of 3 to 4, And the mixture was stirred at 100 rpm for 3 hours to prepare a first silane compound.
(2) Preparation of the second silane compound
To 100 parts by weight of? -glycidoxypropyltrimethoxysilane, 10 parts by weight of a boric acid compound and 60 parts by weight of purified water were stirred at 100 rpm for 3 hours while heating at a reaction temperature of 100 占 폚 to prepare a second silane compound.
The boric acid compound was prepared by adding boric acid (100 parts by weight), borax (80 parts) and purified water (200 parts by weight) to the reactor sequentially and stirring at 70 rpm for 1 hour.
(3) Preparation of composite silane stirring mixture
50 parts by weight of the second silane compound was added to 100 parts by weight of the first silane compound at a constant rate and then stirred with a homogenizer or ultrasonic wave for 30 minutes to 1 hour while maintaining the reaction temperature to prepare a composite silane stirring mixture Respectively.
(4) Preparation of Grafted Polymer
50 parts by weight of silicate (OFS 6788) manufactured by Dow Corning Inc. was added dropwise to 100 parts by weight of the composite silane admixture, and the mixture was stirred at 100 rpm for 2 hours while maintaining the temperature in the range of 90 to 110 占 폚 to prepare a graft polymer Resin).
(5) Preparation of water-soluble flame retardant hybrid resin
Five parts by weight of the polyalkoxysiloxane compound was added dropwise to 100 parts by weight of the graft polymerized product and then stirred at 20 to 25 ° C for 5 hours at a speed of 100 rpm to prepare a water-soluble flame retardant hybrid resin.
The polyalkoxysiloxane compound was obtained by dropping 10 parts by weight of polyalkoxysiloxane into 100 parts by weight of the first silane compound at a rate of 20 min / ml and stirring the mixture at 20 to 25 ° C for 7 hours at 100 rpm A polyalkoxysiloxane compound was used.
Example 2: Preparation of water-soluble flame retardant hybrid resin
(1) Preparation of first silane compound
To 100 parts by weight of? -glycidoxypropyltrimethoxysilane, 100 parts by weight of purified water was added dropwise at a rate of 20 ml / min with adding acetic acid to maintain the pH within the range of 3 to 4, And the mixture was stirred at 100 rpm for 3 hours to prepare a first silane compound.
(2) Preparation of the second silane compound
To 100 parts by weight of? -glycidoxypropyltrimethoxysilane, 5 parts by weight of a boric acid compound and 60 parts by weight of purified water were stirred at 100 rpm for 3 hours while heating at a reaction temperature of 100 占 폚 to prepare a second silane compound.
The boric acid compound was prepared by adding boric acid (100 parts by weight), borax (80 parts) and purified water (200 parts by weight) to the reactor sequentially and stirring at 70 rpm for 1 hour.
(3) Preparation of composite silane stirring mixture
50 parts by weight of the second silane compound was added to 100 parts by weight of the first silane compound at a constant rate and then stirred with a homogenizer or ultrasonic wave for 30 minutes to 1 hour while maintaining the reaction temperature to prepare a composite silane stirring mixture Respectively.
(4) Preparation of Grafted Polymer
50 parts by weight of silicate (OFS 6788) manufactured by Dow Corning Inc. was added dropwise to 100 parts by weight of the composite silane admixture, and the mixture was stirred at 100 rpm for 2 hours while maintaining the temperature in the range of 90 to 110 占 폚 to prepare a graft polymer Resin).
(5) Preparation of water-soluble flame retardant hybrid resin
Five parts by weight of the polyalkoxysiloxane compound was added dropwise to 100 parts by weight of the graft polymerized product and then stirred at 20 to 25 ° C for 5 hours at a speed of 100 rpm to prepare a water-soluble flame retardant hybrid resin.
The polyalkoxysiloxane compound was obtained by dropping 10 parts by weight of polyalkoxysiloxane into 100 parts by weight of the first silane compound at a rate of 20 min / ml and stirring the mixture at 20 to 25 ° C for 7 hours at 100 rpm A polyalkoxysiloxane compound was used.
Comparative Example 1: Preparation of epoxy resin-based flooring composition
A known solvent-free epoxy floor coating composition containing epoxy resin, reactive diluent, curing agent, pigment and additives was prepared (see Laid-Open Patent Publication No. 2001-0060091).
Comparative Example 2: Production of inorganic resin
Glycidoxypropyltrimethoxysilane was hydrolyzed in the absence of acid treatment. To 100 parts by weight of the hydrolyzed? -Glycidoxypropyltrimethoxysilane, 50 parts by weight of microsilica, 5 parts by weight of a surfactant And 100 parts by weight of purified water were added and stirred to prepare an inorganic resin.
Experimental Example 1: Flammability test
In this experiment, the flame retardancy of the resins of Example 1 and Comparative Example 1 was compared.
Seven days after the resins of Example 1 and Comparative Example 1 were applied to the mortar bottom plate, ignition was induced at a close distance by using a torch on the substrate having the coated film, and then the degree of combustion was examined And the results are shown in Table 1 and FIG.
As shown in Table 1 and FIG. 1, in the case of Example 1, induction of a torch fire resulted in partial burning of the flame and only a slight burning, whereas Comparative Example 1 showed a very violent reaction and fast burning Flame rapidity character, indicating that the flame spreads rapidly.
Experimental Example 2: Generation of toxic gas after ignition interruption in the torch
In this experiment, the degree of toxic gas evolution after the fire evolution was compared with Example 1 and Comparative Example 1 after the progress of Experimental Example 1. The results are shown in Table 2 and FIG.
As shown in Table 2 and FIG. 2, in the case of Example 1, when the torch was turned off, the flame disappeared and the flame was hardly generated and almost no smoke was generated. On the other hand, in Comparative Example 1, It was confirmed that dark smoke was generated in the black color.
Experimental Example 3: by water Mercury Magic Cleanliness exam
In order to compare the performance of the resins of Example 1 and Comparative Example 2, experiments were conducted to compare the cleaning properties of water-based magic contamination sites. However, as the resin of Example 1, the graft polymer of step (4) was used.
After the water base paint was coated on the mortar base plate and dried, the resin of each of the above Examples and Comparative Example 2 was coated on the mortar base plate, and after seven days had elapsed, the surface of the base was coated with water magic, Table 3 shows the difference in the cleaning property due to water at the point of time after the elapse of day.
Comparative Example 2
However, traces of contamination induction are severely left behind.
As shown in Table 3 and FIG. 3, the resin of Example 1 was found to have a cleansing function that exhibited the property that the entire portion causing the contamination by water magic floated into water when water was dropped, while the resin of Comparative Example 2 It was confirmed that some parts were cleaned but there was a sign of severe contamination.
Experimental Example 4: by soapy water Yusung Magic Cleanliness exam
In order to compare the performances of the resins of Example 2 and Comparative Example 2, experiments were carried out to compare the cleaning properties of the oil-contaminated areas with soapy water. However, as the resin of Example 2, the graft polymer of step (4) was used.
After the water base paint was coated on the mortar base plate and dried, the resin of each of Example 2 and Comparative Example 2 was coated on the mortar base plate, and the surface of the base was polished with oil magic Table 3 shows the difference in cleaning property by soap water after 30 days.
As shown in Table 4 and FIG. 4, in Example 2, the pollution-causing portion was cleaned by wiping soapy water with a soapy water irrespective of age, whereas in Comparative Example 2, It was confirmed that the cleaning performance was very poor at the site where the contamination was induced by the magic.
Experimental Example 5: Chemical resistance comparison experiment
In this experiment, the chemical resistance of the resins of Example 2 and Comparative Example 2 was confirmed. However, as the resin of Example 2, the graft polymer of step (4) was used.
Example 2 and Comparative Example 2, a resin in accordance with ASTM D 1308-2 Test Method after 7 days Dry H 2 SO 4 (50%) , HNO 3 (20%), HCL (20%), H 3 To each solution of PO 4 (50%) The chemical resistance test was carried out for 7 days. The results are shown in Table 5 below.
Almost no discoloration
Severe discoloration
As shown in Table 5 and FIG. 5, it was confirmed that almost no discoloration was observed in the case of Example 2, whereas in Comparative Example 2, the resistance to each drug was weak and the discoloration was very severe.
Experimental Example 6: Denudation Comparative experiment
In the present experiment, the flame retardancy of the resins of Example 1 and Comparative Example 2 was confirmed. However, as the resin of Example 1, the graft polymer of step (4) was used.
The resin of Example 1 and Comparative Example 2 was applied to a white tile and left exposed to the outside for 3 months, and the difference in yellowing phenomenon was compared and confirmed.
As shown in Table 6 and FIG. 6, slight discoloration was observed in Example 2, but discoloration in Comparative Example 2 was very severe.
Experimental Example 7: Water resistance experiment
In this experiment, the water resistance of the resin of Example 2 and Comparative Example 2 was confirmed. However, as the resin of Example 2, the graft polymer of step (4) was used.
The resin of Example 2 and Comparative Example 2 was coated on a mortar base plate, cured at room temperature for 7 days, and water was dropped thereon for 24 hours to check whether the film was damaged or not.
As shown in Table 7 and FIG. 7, in the case of Example 2, the contact angle of water was maintained and no damage occurred on the surface. On the other hand, in Comparative Example 2, surface roughness and floating were observed.
Experimental Example 8: Bond strength test
In this experiment, the adhesion strengths of the resins of Example 2 and Comparative Example 2 were tested. However, as the resin of Example 2, the graft polymer of step (4) was used.
The resin of Example 2 and Comparative Example 2 was applied to the mortar base plate and the adhesion strength was measured according to the KS F 4937 test standard at the time when 14 days passed. The results are shown in Table 8 below.
As shown in Table 8, in both of Example 2 and Comparative Example 2, all of the mortar base plates were found to be broken. Thus, it was found that the water-soluble flame retardant hybrid resin of the present invention exhibited a high adhesive strength to such an extent that it would break the matrix.
Claims (9)
(B) hydrolyzing the silane coupling agent in an acid catalyst different from the catalyst used in the step (A) in a pH range of 3 to 4 to obtain a second silane compound;
(C) adding the second silane compound to the first silane compound and stirring to obtain a composite silane stirring mixture;
(D) grafting an alkali metal organic silicate to the complex silane stirring mixture to obtain a grafted polymer; And
(E) adding a polyalkoxysiloxane compound to the graft polymerizate and reacting to obtain a water-soluble flame retardant hybrid resin,
The silane coupling agent,
glycidoxy propyl trimethoxy silane,? -glycidoxy propyl methyl diethoxy silane, methyl trimethoxy silane,? -glycidoxy propyl trimethoxy silane,? -glycidoxy propyl trimethoxy silane,? -glycidoxy propyl trimethoxy silane, At least one member selected from the group consisting of 3-aminopropyltriethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane,
The alkali metal organosiliconate may be,
At least one member selected from the group consisting of sodium methyl silicate, potassium methyl silicate, sodium ethyl silicate and potassium methyl silicate,
The polyalkoxysiloxane compound,
Wherein the polyalkoxysilane compound is a polyalkoxysiloxane compound obtained by reacting the first silane compound with at least one polyalkoxysiloxane of polyethoxysiloxane or polymethoxysiloxane.
The polyalkoxysiloxane may be,
Wherein the tetraalkoxysilane monomer content and the alcohol content are each 0.5 wt% or less, the silica conversion concentration is 53 wt% or more, but the weight average molecular weight is 600 to 3,000 and the viscosity is 10 to 1,000 cps at 25 캜. A method for producing a hybrid resin.
Wherein the acid catalyst is at least one selected from the group consisting of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, borax and phosphoric acid.
Wherein the acid catalyst in step (B) is a mixture of boric acid and borax.
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| KR101706625B1 (en) * | 2016-02-02 | 2017-02-16 | 현정환 | The construction method of finishig concrete floor for enhancing durability, no-noise, no-pollution |
| KR102084204B1 (en) * | 2019-07-12 | 2020-04-24 | (주)에콘스 | A flame retardant Styrofoam board, Manufacturing method thereof and EPS heat insulator for the building outer wall |
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| KR20100040531A (en) * | 2008-10-10 | 2010-04-20 | 주식회사 현대화이바 | Developmental composite material of the environmental friendly flame-retardant, high temperature, impact improvement for the rubber modified epoxy resin |
| KR20120010768A (en) * | 2010-07-27 | 2012-02-06 | 주식회사 젠트로 | Functional paint composition and manufacturing method for the same |
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| KR20100040531A (en) * | 2008-10-10 | 2010-04-20 | 주식회사 현대화이바 | Developmental composite material of the environmental friendly flame-retardant, high temperature, impact improvement for the rubber modified epoxy resin |
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