KR20200145583A - Urethanescontaining monofunctional and bifunctional aromatic amines - Google Patents

Abstract

The present invention relates to a high-functional urethane resin production method, a nanocomposite using the same, and a production method thereof. The high-functional urethane resin production method comprises: a 3-aminoalkyl trialkoxysilane production step; a hydroxy-terminated alkyl polydimethyl siloxane production step; an isocyanateterminated silicone resin production step; a functional group capping step; a reactive organic acid neutralization step; and a chain extension step. According to the present invention, durability and mechanical strength are excellent.

Description

Manufacturing method of high-functional urethane resin and nanocomposite using the same, and manufacturing method thereof {Urethanes-containing monofunctional and bifunctional aromatic amines}

The present invention relates to an eco-friendly high-functional silicone-modified urethane hybrid resin manufacturing method with improved water resistance as well as mechanical properties, heat resistance, and weather resistance without causing environmental pollution, and a nanocomposite using the same and a manufacturing method thereof.

Organic/inorganic hybrid resins combine organic components (organic molecules or low molecular weight polymers, etc.) with inorganic components to obtain the hardness, thermal stability and durability of inorganic materials, as well as flexibility and toughness of organic polymers. The introduced organic component not only significantly changes the mechanical properties of the inorganic material, but also makes it easy to form a film or fiber. In addition, as nano-level phase separation is possible, colorless, transparent, uniform, and even porosity can be arbitrarily adjusted, making it possible to manufacture high-functional organic-inorganic hybrid composite materials with new optical and electrical properties.

Due to these advantages, it is in the spotlight as a promising future technology, such as nanocomposite materials for solar cells, nanocomposites for fuel cells, nanocomposites for secondary batteries, and nanocomposites for coatings.

[0004] In general, a coating agent used as a covering material for the surface finish of a building is a fluid material that is widely applied to the surface of an object to form a thin film layer and protects the surface of the object by drying and curing over time. Not only does it have a function to enhance aesthetics.

Therefore, the coating agent acts as a large factor affecting environmental pollution as well as its own component, as well as the lifetime of the coating layer.

That is, because the polymer resin forming the coating layer is exposed to sunlight, the chain is broken by ultraviolet rays or heat, and thus deterioration of low molecular weight is generated, so that the properties of the coating layer are deteriorated, so that the performance cannot be exhibited. In addition, it has a great influence on environmental pollution due to not only cost but also volatile organic compounds in the coating agent during recoating.

Accordingly, there has been a strong demand for the development of a binder resin having excellent durability such as weather resistance and acid rain in order to reduce the maintenance and repair cost of the coating agent worldwide.

[0008] In accordance with this request, research related to this has been actively conducted in developed countries since the early 1980s, and as a result of this, an attempt to develop an organic/inorganic composite by introducing an inorganic polymer into an organic polymer that has been used before and applying it to a coating agent has been attempted. There was.

[0009] Silicone resins are known to have excellent properties in terms of flexibility, water resistance and heat or oxidation stability because the main chain is composed of -Si-O- bonds made of organic and inorganic compounds.

[0010] In recent years, as various silicone compounds have been developed, application studies using them are also actively made, and more comprehensive studies are being conducted in the field of application of a binder resin of a coating agent.

[0011] In line with this trend, a silicone compound is applied to a coating agent to develop a high-functional, high-value-added coating agent that can maintain coating performance for a long period of time even when exposed to heat or ultraviolet rays, and exhibits high weather resistance and is cheaper than fluororesin or silicone resin in price Attempts to do this have been continuously made.

However, the conventional technology for applying a silicone compound to a paint has a disadvantage that the room temperature curing is very slow, and it is difficult to cure under a humid condition.

In addition, even if the room temperature curing drying properties are partially improved, satisfactory curing performance is not exhibited in the application of heavy anticorrosive paints and general industrial coatings, and weather resistance tends to be relatively insufficient.

Therefore, there is an urgent need to develop an eco-friendly, high-functional silicone modified resin that can improve curability, solvent resistance, dryness, coating hardness and further improve weather resistance.

To solve the above problem, hydroxy-terminated polydimethylsiloxane (hydroxy terminated)

polydimethylsiloxane), isocyanate-terminated silicone resin, diisocyanate, and chain extender. The chemical composition of the silicone-urethane organic/inorganic hybrid resin and the length of the soft segment, etc. It aims to produce an eco-friendly, high-functional silicone-modified urethane hybrid resin and nanocomposite that can supplement heat resistance, chemical resistance, and water resistance while maintaining physical properties such as mechanical strength by changing.

In addition, deterioration of the properties of the silicone-modified urethane hybrid resin due to changes in the external environment such as humidity and sunlight should not be caused.

Finally, since it is easy to contact the human body when applied as a binder resin of the coating agent, toxic substances or harmful components should not migrate when contacted.

Therefore, the eco-friendly high-functionality silicone-modified urethane hybrid resin and nanocomposite of the present invention should be completely cured so that unreacted compounds should not occur, and should have excellent water resistance, chemical resistance, durability, and mechanical strength, and when commercialized It is long and easy to handle, and is suitable for use as a coating agent for both industrial and home use. It is a solvent-free type and should not emit volatile organic compounds or harmful components to the human body.

An aromatic solvent such as benzene, toluene, and xylene in a reactor equipped with a thermometer and agitator, dropping equipment, and a reflux condenser under nitrogen supply. solvent) 30-50 parts by weight, dirhodium octacarbonyl, tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbony, rhodium tribromide, rhodium tribromide 001 to 01 parts by weight of a rhodium catalyst such as trihydrate (RhCl3·3H2O) and potassium oxide, rubidium oxide, lithium hydroxide, potassium hydroxide, sodium hydrochloride Triethoxy silane or triethoxysilane while stirring at a speed of 20 to 50 rpm by dropwise adding 001 to 01 parts by weight of metal oxide such as sodium hydroxide and maintaining the reaction temperature at 100 to 130°C 20 to 50 parts by weight of trialkoxysilane such as (triethoxy silane) and 2-propen-1-amine, or 3-butene-1-amine 5-20 parts by weight of an alkene amine mixture such as -amine) and 4-pentene-1-amine are added dropwise over 1 hour, and after the reaction is finished, rotating under reduced pressure A step of preparing 3-aminoalkyl trialkoxysilane prepared by removing unreacted substances and solvents with a rotary evaporator and then vacuum drying at a vacuum of 05 to 07 torr and a temperature of 20 to 40°C;

Hydrogen-terminated polydimethyl having 30 to 50 parts by weight of distilled aromatic solvent and 10 to 30 parts by weight of a weight average molecular weight of 1,000 to 3,000 in a reactor equipped with a thermometer and agitator, condensing condenser, dropping equipment under nitrogen supply Siloxane (hydrogen terminatedpolydimethylsiloxane) and 0001 to 01 parts by weight of a metal-vinyl silane complex catalyst were added and stirred at a speed of 20 to 50 rpm, while maintaining the reactor temperature at 70 to 75°C and 10 to 20 weights Negative 2-propen-1-ol, 3-butene-1-ol, 4-penten-1-ol (4-penten-1-ol) ol) is added dropwise for 1 hour to complete the dropwise addition, raise the temperature of the reactor to 90~95℃ for further reaction for 1~2 hours, remove unreacted substances using a reduced pressure rotary evaporator, and then vacuum for 24~48 hours. Hydrooxy-terminated alkyl polydimethyl siloxane (hydroxy-terminated alkyl polydimethyl siloxane) prepared by drying a manufacturing step; [0022] 30 to 50 parts by weight of distilled in a reactor equipped with a thermometer, agitator, condensing condenser, and dropping equipment A polar solvent such as tetrahydrofurane, methylene chloride, 1,2-chloroethane, and 20 to 40 parts by weight of the hydrooxy-terminated alkylpolydimethylsiloxane production step The hydrooxy-terminated alkylpolydimethylsiloxane prepared in was added and stirred at a rate of 20 to 50 rpm, and 20 to 50 parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate (1 ,4-phenyl diisocyanate), diisocyanato dicyclohexyl methane (4,4'-diisocyanato dicyclo-hexyl methane), toliene diisocyanate, diphenyl methane di Diisocyanate such as isocyanate (diphenyl methane diisocyanate) and 05 to 50 parts by weight of dibutyl tin diacetate or dibutyl tin dilaulate

(dibutyl tin dilaurate), dibutyl tin maleate, dioctyl tindiacetate, 1,4-diazo[2,2,2]-bicyclo-octane (1,4 Condensation catalysts such as -diazo[2,2,2]-bicyclo-octane)

A mixture of (polycondensation catalyst) dissolved in 20 to 50 parts by weight of a polar solvent is added dropwise into the reactor for 30 to 60 minutes, and then the reaction is continued for 2 to 4 hours to complete the reaction, and then the solvent is removed with a vacuum rotary evaporator. An isocyanate-terminated silicone resin prepared by vacuum drying at a vacuum of ~07torr and a temperature of 20~40℃;

In a reactor equipped with a thermometer and a stirrer, a condensing condenser under nitrogen supply, 55 to 95 parts by weight of polyetherdiol or polyesterdiol, polydiol such as polycarbonatediol, and

5 to 25 parts by weight of the isocyanate-terminated silicone resin obtained in the manufacturing step of the isocyanate-terminated silicone resin was added, and 5 to 20 parts by weight of hydroxyacetic acid was added while maintaining the temperature of the reactor at 70 to 90°C. acid) B, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid, 2, Add reactive organic acid such as 2-bis (hydroxymethyl) propionic acid [2,2-bis (hydroxy methyl) propionic acid] and stir at a speed of 20 to 50 rpm for 1 to 4 hours, and 60 to 80 Parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane (4,4'-diisocyanatodi cyclohexylmethane) , Tolyene diisocyanate (tolylene diisocyanate), diphenyl methane diisocyanate (diphenyl methanediisocyanate) and diisocyanates such as 0001 to 005 parts by weight of dibutyl tindiacetate or dibutyl tin dilaurate , Dibutyl tin maleate, dioctyl tin diacetate, 1,4-diazo[2,2,2]-bicyclo-octane (1,4-diazo[2 , A silicon-modified urethane hybrid prepolymer prepared by adding a condensation catalyst such as ,2,2]-bicyclooctane) and raising the reaction temperature to 100 to 120°C for 6 to 12 hours;

The reaction product obtained in the silicone-modified urethane hybrid prepolymer production step lowers the reaction temperature to 40 ~ 60 ℃, and 5 ~ 20 parts by weight of the 3-aminoalkyl trialkoxysilane produced in the 3-aminoalkyl trialkoxysilane production step And reacting for 1 to 3 hours to cap the isocyanate group (-NCO); and 5 to 20 weight of the reaction product prepared in the functional group capping step 1,000-2,000 by adding functional nano-fillers such as photo catalyst, nano-silver, activated nano-carbon, and nano-clay with negative 20-80 nm particle size. A nanocomposite forming step of stirring at rpm and dispersing with ultrasonic waves;

To the mixture obtained in the nanocomposite forming step, 5 to 10 parts by weight of a tertiary amine neutralizing agent such as trimethyl amine or triethyl amine is added and reacted at 40 to 60° C. for 1 to 2 hours. Neutralizing a reactive organic acid;

A dispersion step of dispersing while dropwise adding the reaction product generated in the neutralization step to distilled water stirred at a speed of 800-1,500 rpm;

By adding a chain extender such as 1 to 5 parts by weight of methylene diamine, ethylenediamine, or hexamethylenediamine to the dispersion produced in the dispersion step 800~ A chain expansion step of stirring for 1 to 2 hours at a speed of 1,500 rpm; Then, 55 to 95 parts by weight of polydiol, 5 to 25 parts by weight of isocyanate-terminated silicone resin, 5 to 20 parts by weight of reactive organic acid, 60 to 80 parts by weight of diisocyanate, 0001 to 005 parts by weight of condensation catalyst, 5 to 20 The production of an eco-friendly high-functional silicone-modified urethane hybrid resin composed of parts by weight of 3-aminoalkyl trialkoxysilane, 5 to 20 parts by weight of functional nanofillers, 5 to 10 parts by weight of neutralizing agent and 1 to 5 parts by weight of chain extender was completed.

As described above, the eco-friendly high-functional silicone-modified urethane hybrid resin and nanocomposite of the present invention are completely cured and do not generate unreacted compounds, and are excellent in water resistance, chemical resistance, durability, and mechanical strength. It can be used and has the advantage of not emitting volatile organic compounds or harmful components to the human body.

1 is an exemplary diagram of an exemplary embodiment of the present invention.
Figure 2 is an exemplary view of the reaction equipment of the present invention.

The method of manufacturing an eco-friendly high-functional silicone-modified urethane hybrid resin and nanocomposite according to the present invention will be examined in more detail, and examples according to the method will be described as follows.

In a reactor equipped with a thermometer and agitator, dropping equipment, and a condensing condenser under nitrogen supply, aromatic solvents such as benzene, toluene, and xylene are used. solvent) 30-50 parts by weight, dirhodium octacarbonyl, tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbony, rhodium tribromide, rhodium tribromide 001 to 01 parts by weight of a rhodium catalyst such as trihydrate (RhCl3·3H2O) and potassium oxide, rubidium oxide, lithium hydroxide, potassium hydroxide, sodium hydrochloride 20 to 50 parts by weight of triethoxy silane while stirring at a speed of 20 to 50 rpm by dropwise addition of 001 to 01 parts by weight of a metal oxide such as sodium hydroxide and maintaining the reaction temperature at 100 to 130°C 20 to 50 parts by weight of trialkoxysilane such as triethoxy silane and 2-propen-1-amine, or 3-butene-1-amine ( 5-20 parts by weight of an alkene amine mixture such as 3-butene-1-amine), 4-pentene-1-amine is added dropwise over 1 hour.

After the reaction is over, the unreacted material and the solvent are removed with a rotary evaporator, and then 3-aminoalkyl trialkoxysilane prepared by vacuum drying at a temperature of 20 to 40°C and a vacuum of 05 to 07 torr (3- aminoalkyl trialkoxysilane) production step; [0034] In a reactor equipped with a thermometer, agitator, condensing condenser, and dropping equipment under nitrogen supply, 30 to 50 parts by weight of distilled aromatic solvent and 10 to 30 parts by weight of a weight average molecular weight of 1,000 to 3,000 Hydrogen terminated polydimethylsiloxane and 0001 to 01 parts by weight of metal-vinyl silane complex catalyst were added and stirred at a speed of 20 to 50 rpm and the reactor temperature was 70 to 75 °C. And 10 to 20 parts by weight of 2-propen-1-ol, 3-butene-1-ol, and 4-penten-1-ol (4-penten-1-ol) was added dropwise over 1 hour.

When the dropwise addition is complete, the temperature of the reactor is raised to 90 to 95°C, reacted for 1 to 2 hours, and then unreacted material is removed using a reduced pressure rotary evaporator, and then hydrooxy prepared by vacuum drying for 24 to 48 hours. -Preparation step of hydroxy-terminated alkyl polydimethyl siloxane;

Thermometer and stirrer, condensing condenser, 30 to 50 parts by weight of distilled tetrahydrofurane or methylene chloride (methylene chloride) in a reactor equipped with dropping equipment, 1,2-chloroethane (1,2-chloroethane ), and the like, and 20 to 40 parts by weight of the hydrooxy-terminated alkylpolydimethylsiloxane prepared in the production step of the hydrooxy-terminated alkylpolydimethylsiloxane, and stirred at a speed of 20 to 50 rpm. Here, 20 to 50 parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate, 4,4'-diisocyanate dicyclohexylmethane (4,4 Diisocyanates such as'-diisocyanato dicyclo-hexyl methane), tolylene diisocyanate, diphenyl methane diisocyanate, and 05-50 parts by weight of dibutyl tin diacetate or diisocyanate. Butyl tin dilaurate, dibutyl tin maleate, dioctyl tindiacetate, 1,4-diazo[2,2,2]-bicyclo- A mixture in which a polycondensation catalyst such as octane (1,4-diazo[2,2,2]-bicyclo-octane) is dissolved in 20 to 50 parts by weight of a polar solvent is added dropwise into the reactor for 30 to 60 minutes. The reaction is continued for 2 to 4 hours.

After the reaction is over, the solvent is removed with a vacuum rotary evaporator, and then isocyanate-terminated silicone resin prepared by vacuum drying at a temperature of 20 to 40° C. and a vacuum of 05 to 07 torr; In a reactor equipped with a thermometer and a stirrer, a condensing condenser under nitrogen supply, 55 to 95 parts by weight of polyetherdiol or polyesterdiol, polydiol such as polycarbonatediol, and 5 to 25 parts by weight of the isocyanate-terminated silicone resin obtained in the manufacturing step of the isocyanate-terminated silicone resin was added, and 5 to 20 parts by weight of hydroxyacetic acid was added while maintaining the temperature of the reactor at 70 to 90°C. acid) B, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid, 2, Add reactive organic acid such as 2-bis (hydroxy methyl) propionic acid [2,2-bis (hydroxy methyl) propionic acid] and stir at a speed of 20 to 50 rpm for 1 to 4 hours.

Here, 60 to 80 parts by weight of hexamethylene diisocyanate (hexamethylene diisocyanate), 1,4-phenyl diisocyanate (1,4-phenyl diisocyanate), 4,4'-diisocyaneto dicyclohexylmethane ( Diisocyanates such as 4,4'-diisocyanatodi cyclohexylmethane), toliene diisocyanate, diphenyl methanediisocyanate and 0001 to 005 parts by weight of dibutyl tindiacetate or dibutyl tin Dibutyl tin dilaurate, dibutyl tin maleate, diocyl tin diacetate, 1,4-diazo[2,2,2]-bicyclo-octane Preparation step of silicone-modified urethane hybrid prepolymer prepared by adding a condensation catalyst such as (1,4-diazo[2,2,2]-bicyclooctane) and raising the reaction temperature to 100~120℃ for 6~12 hours Wow;

[0040] The reaction product obtained in the silicone-modified urethane hybrid prepolymer production step lowers the reaction temperature to 40 to 60° C. and 5 to 20 parts by weight of the 3-aminoalkyl trialkoxysilane produced in the production step of the 3-aminoalkyl trialkoxysilane And reacting for 1 to 3 hours to cap the isocyanate group (-NCO); and 5 to 20 weight of the reaction product prepared in the functional group capping step By introducing functional nano-fillers such as photo catalyst or nano-silver, activated nano-carbon and nano-clay having a negative 20-80 nm particle size A nanocomposite forming step of stirring at 1,000 to 2,000 rpm and dispersing by ultrasonic waves;

To the mixture obtained in the nanocomposite forming step, 5 to 10 parts by weight of a tertiary amine neutralizing agent such as trimethyl amine or triethyl amine is added and reacted at 40 to 60° C. for 1 to 2 hours Reactive organic acid neutralization step; [0043] A dispersion step of dropwise adding the reaction product generated in the neutralization step to distilled water stirred at a speed of 800 to 1500 rpm and dispersing; [0044] 1 to the dispersion produced in the dispersion step Chain expansion step in which a chain extender such as 5 parts by weight of methylene diamine, ethylenediamine, or hexamethylenediamine is added and stirred at a speed of 800-1,500 rpm for 1-2 hours. To; Then, 55 to 95 parts by weight of polydiol, 5 to 25 parts by weight of isocyanate-terminated silicone resin, 5 to 20 parts by weight of reactive organic acid, 60 to 80 parts by weight of diisocyanate, 0001 to 005 parts by weight of condensation catalyst, 5 to 20 The production of an eco-friendly high-functional silicone-modified urethane hybrid resin composed of parts by weight of 3-aminoalkyl trialkoxysilane, 5 to 20 parts by weight of functional nanofillers, 5 to 10 parts by weight of neutralizing agent and 1 to 5 parts by weight of chain extender was completed.

[0045] The polydiol is 55 to 95 parts by weight, and polyether diol, polyester diol, polycarbonate diol, etc. may be used as a main component forming a hard segment of a silicone-modified urethane hybrid resin.

At this time, when the polydiol content is less than 55 parts by weight, the mechanical strength of the silicone-modified urethane hybrid resin formed decreases, and when the content is more than 95 parts by weight, productivity due to the increase in viscosity during the reaction decreases.

[0047] The isocyanate-terminated silicone resin is used in an amount of 5 to 25 parts by weight as a main component forming a soft segment of a silicone-modified urethane hybrid resin.

At this time, when the content of the isocyanate-terminated silicone resin is less than 5 parts by weight, the water resistance of the silicone-modified urethane hybrid resin formed is lower, and when the content is 25 parts by weight or more, the mechanical strength of the product is lowered.

[0049] The reactive organic acid is used to increase water dispersibility, and hydrooxyacetic acid, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulonic acid, 2,2 -5 to 20 parts by weight of bis (hydroxymethyl) propionic acid, etc. are used.

At this time, when the reactive organic acid content is less than 5 parts by weight, the water dispersibility decreases, and when the content is more than 20 parts by weight, the water resistance of the product decreases.

[0051] The diisocyanate is a reactive binder such as hexamethylene diisocyanate, 1,4-phenyl diisocyanate, 4,4'-diisocyanate dicyclohexyl methane, tolyene diisocyanate, diphenyl methane diisocyanate, etc. 60 to 80 parts by weight are used.

At this time, when the diisocyanate content is less than 60 parts by weight, the mechanical strength of the silicone-modified urethane hybrid resin is lowered, and when the content is 80 parts by weight or more, environmental friendliness is lowered.

[0053] The condensation catalyst is a reaction catalyst such as dibutyl tin diacetate or dibutyl tin dilaulate, dibutyl tin maleate, dioctyl tin diacetate, 1,4-diazo[2,2,2]-by Cyclo-octane can be used, and 0001~005 parts by weight are used.

At this time, when the content of the condensation catalyst is less than 0001 parts by weight, the viscosity of the silicone-modified urethane hybrid resin formed is lowered, and when the content is 005 parts by weight or more, the productivity decreases.

The 3-aminoalkyl trialkoxysilane produced in the manufacturing step of the 3-aminoalkyl trialkoxysilane is used in an amount of 5 to 20 parts by weight for capping the isocyanate group.

At this time, when the 3-aminoalkyl trialkoxysilane content is less than 5 parts by weight, the viscosity of the silicone-modified urethane hybrid resin formed is lower, and when the content is 20 parts by weight or more, the economical efficiency is lowered.

The functional nano-filler is used in 5 to 20 parts by weight of the final product is a photocatalyst or nano silver having a particle size of 20 to 80 nm to impart properties such as decomposition of volatile organic compounds, antibacterial properties, release of anions and improvement of tensile strength, Activated nanocarbons and nanoclays are available.

Claims (3)

In a reactor equipped with a thermometer, agitator, dropping equipment and a reflux condenser under nitrogen supply, an aromatic solvent such as benzene, toluene, and xylene 30 ~50 parts by weight and, dirhodium octacarbonyl or tetrarhodium dodecacarbonyl (tetrarhodium)
dodecacarbonyl), hexarhodium hexadecacarbony, rhodium tribromide
001 to 01 parts by weight of a rhodium catalyst such as tribromide), rhodium trichloride trihydrate (RhCl3·3H2O) and potassium oxide, rubidium oxide, lithium hydroxide, potassium hydroxide (potassium hydroxide) 001 to 01 parts by weight of a metal oxide such as sodium hydroxide is added dropwise and stirred at a speed of 20 to 50 rpm, and the reaction temperature is maintained at 100 to 130°C, while triethoxy silane ) And trialkoxysilane such as triethoxy silane and 20 to 50 parts by weight of 2-propen-1-amine or 3-butene-1-amine Reaction by dropwise adding 5 to 20 parts by weight of an alkene amine mixture such as (3-butene-1-amine) and 4-pentene-1-amine over 1 hour After completion, 3-aminoalkyl trialkoxysilane prepared by removing unreacted substances and solvent with a vacuum rotary evaporator and then vacuum drying at a vacuum of 05~07torr and a temperature of 20~40℃. Manufacturing steps;
Under nitrogen supply, in a reactor equipped with a thermometer, agitator, condensing condenser, and dropping equipment, 30 to 50 parts by weight of distilled aromatic solvent and 10 to 30 parts by weight of a hydrogen-terminated polydimethylsiloxane having a weight average molecular weight of 1,000 to 3,000. terminatedpolydimethylsiloxane) and 0001 to 01 parts by weight of a metal-vinyl silane complex catalyst were added and stirred at a speed of 20 to 50 rpm while maintaining the temperature of the reactor at 70 to 75°C, and 10 to 20 parts by weight of 2- Propen-1-ol (2-propen-1-ol), 3-butene-1-ol (3-butene-1-ol), 4-penten-1-ol (4-penten-1-ol) When the dropwise addition is completed by adding dropwise for 1 hour, increase the temperature of the reactor to 90~95℃, react for 1~2 hours, remove unreacted material using a reduced pressure rotary evaporator, and then vacuum dry for 24~48 hours. Hydrooxy-terminated alkyl polydimethylsiloxane (hydroxy-terminated alkyl polydimethyl siloxane) preparation step;
30-50 parts by weight of distilled tetrahydrofuran in a reactor equipped with a thermometer, agitator, condensing condenser, and dropping equipment
(tetrahydrofurane), methylene chloride (methylene chloride), 1,2-chloroethane (1,2-chloroethane), such as polar solvent and 20 to 40 parts by weight of the hydrooxy-terminated alkylpolydimethylsiloxane prepared in the manufacturing step Hydrooxy-terminated alkylpolydimethylsiloxane was added and stirred at a speed of 20 to 50 rpm, and 20 to 50 parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate (1,4- phenyl diisocyanate), 4,4'-diisocyanato dicyclo-hexyl methane (4,4'-diisocyanato dicyclo-hexyl methane), toliene diisocyanate, diphenyl methane diisocyanate, and The same diisocyanate and 05-50 parts by weight of dibutyl tin diacetate or dibutyl tin dilaurate, dibutyl tin maleate, dioctyl tin diacetate (diocyl) tindiacetate), a polycondensation catalyst such as 1,4-diazo[2,2,2]-bicyclo-octane (1,4-diazo[2,2,2]-bicyclo-octane). The mixture dissolved in ~50 parts by weight of a polar solvent is added dropwise into the reactor for 30 to 60 minutes, and then the reaction is continued for 2 to 4 hours to complete the reaction.After the reaction is finished, the solvent is removed with a reduced pressure rotary evaporator, and then vacuum of 05 to 07 torr and 20 An isocyanate-terminated silicone resin prepared by vacuum drying at a temperature of ~40°C;
In a reactor equipped with a thermometer, stirrer, and condensation condenser under nitrogen supply, polydiol such as 55 to 95 parts by weight of polyetherdiol, polyesterdiol, and polycarbonatediol
5 to 25 parts by weight of the isocyanate-terminated silicone resin obtained in the manufacturing step of the isocyanate-terminated silicone resin was added, and 5 to 20 parts by weight of hydroxyacetic acid was added while maintaining the temperature of the reactor at 70 to 90°C. acid) B, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid, 2, Add reactive organic acid such as 2-bis (hydroxymethyl) propionic acid [2,2-bis (hydroxy methyl) propionic acid] and stir at a speed of 20 to 50 rpm for 1 to 4 hours, and 60 to 80 Parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane (4,4'-diisocyanatodi cyclohexylmethane) , Tolyene diisocyanate (tolylene diisocyanate), diphenyl methane diisocyanate (diphenyl methanediisocyanate) such as diisocyanate and 0001 to 005 parts by weight of dibutyl tindiacetate or dibutyl tin dilaurate (dibutyl tin dilaurate) , Dibutyl tin maleate, dioctyl tin diacetate, 1,4-diazo[2,2,2]-bicyclo-octane (1,4-diazo[2 ,2,2]-bicyclooctane)
Silicon modified cow prepared by adding a condensation catalyst as described above and raising the reaction temperature to 100~120℃ for 6~12 hours
Retane hybrid prepolymer (prepolymer) production step; The reaction product obtained in the silicone-modified urethane hybrid prepolymer production step, lower the reaction temperature to 40 ~ 60 ℃, 5-20 parts by weight of the 3-aminoalkyl trialkoxysilane produced in the production step A functional group capping step of capping an isocyanate group (-NCO) by adding 3-aminoalkyl trialkoxysilane and reacting for 1 to 3 hours;
5 to 10 parts by weight of trimethylamine in the reaction product prepared in the functional group capping step
a reactive organic acid neutralization step of adding a tertiary amine neutralizing agent such as (trimethyl amine) or triethyl amine and reacting at 40 to 60° C. for 1 to 2 hours;
A dispersion step of dropwise adding the reaction product generated in the neutralization step to distilled water stirred at a speed of 800 to 1500 rpm and dispersing; 1 to 5 parts by weight of methylene diamine or ethylene to the dispersion produced in the dispersion step An eco-friendly high-functional silicone modification characterized by comprising: a chain extension step in which a chain extender such as diamine or hexamethylenediamine is added and stirred at a speed of 800 to 1500 rpm for 1 to 2 hours. Urethane hybrid resin manufacturing method. 55 to 95 parts by weight of polydiol, 5 to 25 parts by weight of isocyanate-terminated silicone resin, 5 to 20 parts by weight
Reactive organic acid, 60 to 80 parts by weight of diisocyanate, 0001 to 005 parts by weight of condensation catalyst, 5 to 20 parts by weight of 3-aminoalkyl trialkoxysilane, 5 to 20 parts by weight of functional nano-filler, 5 to 10 parts by weight of neutralizing agent and 1 to Eco-friendly, high-functional silicone-modified urethane hybrid resin nanocomposite, characterized by comprising 5 parts by weight of a chain extender. An aromatic solvent such as benzene, toluene, and xylene in a condenser equipped with a thermometer, agitator, dropping equipment and a reflux condenser under nitrogen supply 30 ~50 parts by weight and, dirhodium octacarbonyl or tetrarhodium dodecacarbonyl (tetrarhodium)
dodecacarbonyl), hexarhodium hexadecacarbony, rhodium tribromide
001 to 01 parts by weight of a rhodium catalyst such as tribromide), rhodium trichloride trihydrate (RhCl3·3H2O) and potassium oxide, rubidium oxide, lithium hydroxide, potassium hydroxide (potassium hydroxide) 001 to 01 parts by weight of a metal oxide such as sodium hydroxide is added dropwise and stirred at a speed of 20 to 50 rpm, and the reaction temperature is maintained at 100 to 130°C, while triethoxy silane ) And trialkoxysilane such as triethoxy silane and 20 to 50 parts by weight of 2-propen-1-amine or 3-butene-1-amine Reaction by dropwise adding 5 to 20 parts by weight of an alkene amine mixture such as (3-butene-1-amine) and 4-pentene-1-amine over 1 hour After completion, 3-aminoalkyl trialkoxysilane prepared by removing unreacted substances and solvent with a vacuum rotary evaporator and then vacuum drying at a vacuum of 05~07torr and a temperature of 20~40℃. Manufacturing step; 30 to 50 parts by weight of distilled aromatic solvent in a reactor equipped with a thermometer, agitator, condensing condenser, and dropping equipment under nitrogen supply and
By adding 10 to 30 parts by weight of hydrogen terminated polydimethylsiloxane with a weight average molecular weight of 1,000 to 3,000 and 0001 to 01 parts by weight of a metal-vinyl silane complex catalyst, 20 to While stirring at a speed of 50 rpm, the reactor temperature is maintained at 70 to 75°C, and 10 to 20 parts by weight of 2-propen-1-ol or 3-butene-1-ol -1-ol) and 4-penten-1-ol are added dropwise for 1 hour, and when the dropwise addition is completed, the temperature of the reactor is raised to 90~95℃ for 1~2 hours. A step of preparing a hydroxy-terminated alkyl polydimethyl siloxane prepared by reacting and removing unreacted substances using a vacuum rotary evaporator and then vacuum drying for 24 to 48 hours;
30-50 parts by weight of distilled tetrahydrofuran in a reactor equipped with a thermometer, agitator, condensing condenser, and dropping equipment
(tetrahydrofurane), methylene chloride (methylene chloride), 1,2-chloroethane (1,2-chloroethane), such as polar solvent and 20 to 40 parts by weight of the hydrooxy-terminated alkylpolydimethylsiloxane prepared in the manufacturing step Hydrooxy-terminated alkylpolydimethylsiloxane was added and stirred at a speed of 20 to 50 rpm, and 20 to 50 parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate (1,4- phenyl diisocyanate), 4,4'-diisocyanato dicyclo-hexyl methane (4,4'-diisocyanato dicyclo-hexyl methane), toliene diisocyanate, diphenyl methane diisocyanate, and The same diisocyanate and 05-50 parts by weight of dibutyl tin diacetate or dibutyl tin dilaurate, dibutyl tin maleate, dioctyl tin diacetate ( diocyl tindiacetate), 1,4-diazo[2,2,2]-bicyclo-octane (1,4-diazo[2,2,2]-bicyclo-octane), a polycondensation catalyst such as A mixture dissolved in 20-50 parts by weight of a polar solvent was added dropwise into the reactor for 30-60 minutes.
Next, the reaction is continued for 2 to 4 hours, after the reaction is over, the solvent is removed with a vacuum rotary evaporator, and then isocyanate-terminated silicone resin prepared by vacuum drying at a vacuum of 05 to 07 torr and a temperature of 20 to 40°C ( isocyanateterminated silicone resin) manufacturing step;
In a reactor equipped with a thermometer, stirrer, and condensing condenser under nitrogen supply, polydiol such as 55 to 95 parts by weight of polyetherdiol, polyesterdiol, and polycarbonatediol
5 to 25 parts by weight of the isocyanate-terminated silicone resin obtained in the manufacturing step of the isocyanate-terminated silicone resin was added, and 5 to 20 parts by weight of hydroxyacetic acid was added while maintaining the temperature of the reactor at 70 to 90°C. acid) B, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid, 2, Add reactive organic acid such as 2-bis (hydroxymethyl) propionic acid [2,2-bis (hydroxy methyl) propionic acid] and stir at a speed of 20 to 50 rpm for 1 to 4 hours, and 60 to 80 Parts by weight of hexamethylene diisocyanate, 1,4-phenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane (4,4'-diisocyanatodi cyclohexylmethane) , Tolyene diisocyanate (tolylene diisocyanate), diphenyl methane diisocyanate (diphenyl methanediisocyanate) such as diisocyanate and 0001 to 005 parts by weight of dibutyl tindiacetate (dibutyl tindiacetate) or dibutyl tin dilaurate (dibutyl tin dilaurate) , Dibutyl tin maleate, dioctyl tin diacetate, 1,4-diazo[2,2,2]-bicyclo-octane (1,4-diazo[2 , A silicon-modified urethane hybrid prepolymer prepared by adding a condensation catalyst such as ,2,2]-bicyclooctane) and raising the reaction temperature to 100 to 120°C for 6 to 12 hours;
To the reaction product obtained in the silicone-modified urethane hybrid prepolymer production step, the reaction temperature was lowered to 40 to 60°C, and 5 to 20 parts by weight of the 3-aminoalkyl trialkoxysilane produced in the 3-aminoalkyl trialkoxysilane production step was added. A functional group capping step of capping the isocyanate group (-NCO) by reacting for 1 to 3 hours;
In the reaction product prepared in the functional group capping step, a photo catalyst, nano-silver, or activated nano-carbon having a particle size of 20 to 80 nm in 5 to 20 parts by weight of the reaction product And a nanocomposite forming step of adding a functional nano-filler such as nano-clay, stirring at 1,000 to 2,000 rpm, and dispersing with ultrasonic waves;
Neutralization of reactive organic acids by adding 5 to 10 parts by weight of a tertiary amine neutralizing agent such as trimethyl amine or triethyl amine to the mixture obtained in the nanocomposite formation step and reacting at 40 to 60° C. for 1 to 2 hours A dispersion step of dropping and dispersing the reaction product generated in the neutralization step into distilled water stirred at a speed of 800 to 1500 rpm;
A chain extender such as 1 to 5 parts by weight of methylene diamine, ethylenediamine, or hexamethylenediamine is added to the dispersion produced in the dispersion step at a speed of 800-1,500 rpm. A chain expansion step of stirring for 1 to 2 hours; A method of manufacturing an eco-friendly, high-functional silicone-modified urethane hybrid resin nanocomposite comprising further comprising

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