JP2001172338A - Graft polymerized functional polyurethane and method for synthesizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel graft polymerized functional polyurethane comprising a high molecular compound prepared by bonding functional monomers to a polyurethane as a main chain by graft polymerization, having not only the properties of the polyurethane but also those of the side chain block polymers introduced by the graft polymerization which include hydrophilicity, lipophilicity, water repellency, and water and oil repellency depending on the functional monomers for preparing the side chains. SOLUTION: (1) One or more diols having one or more intramolecular double bonds are reacted with (2) the other diols for functionally modifying the properties of a main chain and (3) diisocyanate to synthesize a polyurethane. The functional monomers having vinyl groups for the side chains are bonded to the polyurethane for the main chain by graft polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel multifunctional polyurethane, which comprises a polymer having polyurethane as a main chain and various functional monomers bonded to the main chain by graft polymerization. It has both properties and properties of the side chain block polymer introduced by graft polymerization, and has specific functions such as hydrophilicity, lipophilicity, water repellency, water repellency and oil repellency depending on the type of functional monomer constituting the side chain. The present invention relates to a functional grafted polyurethane that can be provided and a method for synthesizing the same.

[0002]

2. Description of the Related Art As is well known, polyurethane has the property of exhibiting rubber elasticity, and further has abrasion resistance, oxidation resistance, oil resistance, and the like.
It has excellent properties such as aging resistance, and its coating film has high strength and flexibility, so paints, fibers,
Widely used for various applications such as foam, packing, adhesives. In recent years, it has also been used for new applications such as semiconductors, transparent conductive films, and photosensitive materials.

[0003]

SUMMARY OF THE INVENTION The present inventors have filed patent applications for various functional grafted polyurethanes in Japanese Patent Application Nos. 10-55438 and 10-122559. A polyurethane synthesized by the reaction of a diol having at least one double bond or more with a diisocyanate in the molecule is used as a main chain, and a functional monomer having a vinyl group is bonded to the main chain by graft polymerization to form a side chain. A functional grafted polyurethane having the characteristics of a polyurethane main chain and the characteristics of a graft-polymerized side chain compound has been proposed, which can be used in a variety of unprecedented applications. In this application, the content of using a hydrogenated polybutadiene diol, a polycarbonate diol, a polyester diol, or the like as a diol not grafted is also described. However, the properties of the polyurethane forming the main chain depend on the combination of the structure of the diisocyanate, the structure of the diol having a double bond in the molecule (the diol to be grafted), and the structure of the non-grafted diol. In JP-A-10-55438 and JP-A-10-122559, a non-grafted diol is used in combination for the purpose of adjusting the ratio of vinyl groups in the main chain, and has a structure relatively similar to the grafted diol. The properties of the main-chain polyurethane were somewhat similar. Therefore, the present inventors have changed the properties of the main chain polyurethane to an unconventional type by replacing the non-grafted diol with a composition having a specific structure and properties which have not existed in the past. Also expect.

[0004]

Means for Solving the Problems In view of the above, the inventors of the present invention have made intensive studies and have arrived at the present invention. That is, in a combination of a diisocyanate which is a basic component of a polyurethane forming a main chain, a diol having a double bond (to be graft-polymerized), and a diol having no double bond, it is specified as a diol having no double bond. It is an object of the present invention to modify the properties of the main-chain polyurethane by using a compound having the following structure. The subsequent grafting process is described in Japanese Patent Application Nos. 10-55438 and 10-1225.
It is the same as No. 59. The functional grafted polyurethane of the present invention thus obtained differs from the conventional polyurethane in the properties of the main chain polyurethane, and the resulting grafted polyurethane is also disclosed in Japanese Patent Application Nos. 10-55438 and 10-55438. Applications in other fields that were not recognized in -122559 are expected.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The functional grafted polyurethane according to the present invention will be described in detail below.

The diisocyanate used in the present invention is not particularly limited. For example, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, methylene diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate Aliphatic diisocyanates such as dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,
Examples include aromatic diisocyanates such as 4-methylenediphenyl diisocyanate, naphthalenediisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate.

The diol having a double bond used in the present invention may be any diol having at least one double bond in the molecule, and may be an internal olefin type diol. As a better diol having a double bond according to the present invention, there is a diol having at least one vinyl group in the molecule, and among these diols, in particular, a polybutadiene diol having a terminal (side chain) vinyl group Is preferred. Examples of the most preferred polybutadiene diol include

Embedded image Can be mentioned.

In the synthesis reaction of the main chain polyurethane, for example, the above 4,4-methylenediphenyl diisocyanate is reacted with the above polybutadiene diol in combination with a diol having no double bond. The role of the unreacted diol is firstly to improve the properties of the main chain, and secondly to adjust the proportion of vinyl groups in the main chain. As the diol having no double bond,

Embedded image The commonly known as both the terminal alcohol-modified silicone oil structure, the R -CH ₂ -, CH ₂ C
H ₂ —, —CH ₂ CH ₂ CH ₂ —, and n is 10 to 10.
For example, "BY16-848" manufactured by Toray Silicone Co., Ltd. and "TSF-4751" manufactured by GE Toshiba Silicone Co., Ltd. The main-chain polyurethane obtained by reacting with diisocyanate and polybutadiene diol is used as a non-diol, while retaining the rubber elasticity, abrasion resistance, oxidation resistance, oil resistance, and aging resistance of the conventional polyurethane. In addition, slip properties, anti-adhesion properties, and releasability are imparted as new properties.

Further, as other diols having no double bond,

Embedded image Where n is 5
The main chain polyurethane obtained by using such polyethylene glycol as a diol having no double bond in the present invention and reacting with diisocyanate and polybutadiene diol is a rubber of a conventional polyurethane. While maintaining elasticity, abrasion resistance, oxidation resistance, oil resistance, aging resistance, etc., affinity to water is additionally provided as a new property.

In addition, when synthesizing a polyurethane, an excess amount of diisocyanate is added to the diol component to synthesize a polyurethane. After reacting under a certain condition, HO- (CH ₂ ) _n OH (n = You may make it add the low molecular diol represented by 2-10). This low molecular weight diol is rich in reactivity and can make the resulting polyurethane a higher molecular weight. For example, when butanediol (n = 4) or the like is added, it reacts with the isocyanate group at the end of the polyurethane, and for example, a polyurethane having a molecular weight of about 4000 can be increased to a high molecular weight of about 12,000. In this case, for example, ethylenediamine (H ₂ NCH ₂ CH ₂ N) is used instead of butanediol.
By using H ₂ ) or the like, the polyurethane can be hardened and strengthened in addition to the extension of the main chain.

The solvent used for synthesizing the polyurethane may be any solvent that is generally used for synthesizing polyurethane, and examples thereof include toluene and N, N-dimethylacetamide. In addition, other synthesis conditions may be performed under the conditions when a polyurethane is generally synthesized.

The polyurethane (or prepolymer) thus obtained has a molecular weight of about 2,000 to 500,000 and has double bonds (preferably vinyl groups) at appropriate intervals in the main chain. Various functional monomers are bonded to the double bond (vinyl group or the like) in the polyurethane by graft polymerization. The functional monomer is added to the polyurethane, for example, azobisisobutyronitrile (AIBN) or the like. Azo, peroxides such as benzoyl peroxide (BPO), and radical initiators such as ammonium persulfate,
The graft polymerization is carried out in a state of being dissolved in an appropriate solvent such as dioxane, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and the like. In this case, a functional polyurethane having two different functions can be synthesized by two-step synthesis in which the first monomer is graft-polymerized and then the second monomer is graft-polymerized. For example, a polyurethane obtained by alternately graft-polymerizing a hydrophilic monomer and a water-repellent monomer has a novel performance, and may be able to develop a new use.

One of the features of the present invention is that it is possible to obtain various functional polyurethanes having different functions depending on the type of the functional monomer to be graft-polymerized as described above. Can also be given specific performance, so that it can be applied to a large number of previously unattainable applications.

The functional monomers to be graft-polymerized in the present invention are disclosed in Japanese Patent Application Nos.
It is the same as −122559.

The first functional monomer is a hydrophilic monomer, and examples thereof include:

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image A functional grafted polyurethane having a hydrophilic segment in which these monomers are bonded to a main chain polyurethane by graft polymerization as a side chain has water retention.
further,

Embedded image

Embedded image Graft polymerized type has antithrombotic properties,

Embedded image Has a similar effect. Also,

Embedded image The type obtained by graft-polymerizing is capable of bonding to an inorganic substance by the OH related to the terminal phosphoric acid, and thus can be applied to tooth adhesion.

The second functional monomer is a lipophilic (hydrophobic) monomer, and examples thereof include:

Embedded image A functional grafted polyurethane having a lipophilic segment in which the monomer is bonded to a main chain polyurethane by graft polymerization as a side chain has oil retaining properties. Such lipophilic (hydrophobic) monomers include, in addition to the above monomers,

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image There are various monomers such as styrene, alkyl styrene, acrylonitrile, alkyl vinyl ether, vinyl acetate, vinyl chloride, ethylene, propylene, etc., which are azo compounds such as AIBN, BPO
With an initiator such as an organic peroxide such as an organic peroxide, potassium persulfate, or an inorganic peroxide such as ammonium persulfate, a solution polymerization, an emulsion polymerization, and a suspension polymerization method are used to graft-polymerize the monomer to be surface-grafted. Depending on the type, a grafted urethane composition having various properties having different surface hardness, surface elasticity, and lipophilic-hydrophilic balance is prepared. Also, by graft-polymerizing two or three types of lipophilic monomers simultaneously, a grafted polyurethane composition having a slightly different surface lipophilic state can be obtained while being a single graft compound.

The third functional monomer is a water-repellent monomer.

Embedded image There is. In general, silicone compounds have the property of repelling water, but are fragile, such as easily breaking when subjected to an external force such as pulling, and have extremely low strength. However, the functional grafted polyurethane of the present invention obtained by graft-polymerizing the water-repellent monomer to the side chain has flexibility, transparency, high strength, and is soluble in a solvent that dissolves ordinary polyurethane. Therefore, it has an excellent effect not found in the conventional water repellent. When the contact angle is measured using this water repellent, it is about 120 to 160 °.

The fourth functional monomer is a water- and oil-repellent monomer.

Embedded image There is. Other water- and oil-repellent monomers include

Embedded image

Embedded image

Embedded image

Embedded image There are various monomers such as tetrafluoroethylene, vinylidene fluoride, vinyl fluoride, ethylene trifluoride and the like, which are azo compounds such as AIBN and organic peroxides such as BPO. It is graft-polymerized by an initiator such as an inorganic peroxide such as potassium persulfate or ammonium persulfate by a solution polymerization, emulsion polymerization or suspension polymerization method. Generally, fluorine compounds have water and oil repellency,
When this is sprayed on clothes or the like, the coated portion generally becomes rough and the flexibility of the material such as clothes is impaired. In addition, there is almost no solvent that dissolves the fluorine compound, and it dissolves only in a highly toxic solvent such as a chlorine-based solvent,
It has the disadvantage that its handling is difficult. However, the functional grafted polyurethane of the present invention in which the water- and oil-repellent monomer is graft-polymerized to the side chain has a flexibility and a high strength because the polyurethane itself has high strength.
Film formation becomes possible, and furthermore, since it is dissolved in a solvent that dissolves ordinary polyurethane, it can also be used for applications as a paint. In addition, since the function of water and oil repellency does not attach dirt, not only water repellency but also a function of preventing dirt can be imparted to the target object.Furthermore, the adhesion to the base material is high, so it can be applied to various materials. Can be applied. When used as a tube utilizing film formability, an anti-thrombotic artificial blood vessel can be obtained by applying it as an artificial blood vessel due to the anti-adhesion property. Furthermore, it can be used for various electronic parts by utilizing the stain prevention property. The contact angle for determining the water repellency may be about 130 to 170 ° depending on the surface shape.

Any other monomer may be used as the functional monomer.

Embedded image After grafting a monomer having an ionic structure in the polyurethane, followed by an anti-thrombotic agent such as heparin R-SO ₃ ^- Na ⁺
A compound having a structure of (R is a polysaccharide) is reacted to obtain an antithrombotic grafted polyurethane. Also,

Embedded image After grafting the monomer of the above onto polyurethane, the epoxide group is opened with water, alcohol or amine to leave a functional epoxide, and then amine, alcohol,
By reacting with water or the like, a reactive polyurethane can be obtained, and can be used, for example, as an adhesive polyurethane.

In the case of grafting in the present invention, two or more monomers can be grafted. As a first example, a hydrophilic monomer and a lipophilic monomer are simultaneously grafted, and a graft compound having both hydrophilicity and lipophilicity in a side chain is obtained. The form is a case where a compound having a hydrophilic side chain and a lipophilic side chain is formed at random, and as a second form, a hydrophilic monomer and a lipophilic monomer are alternately or blocked on one side chain. In the case of forming a copolymerized compound, examples of the hydrophilic monomer used include

Embedded image

Embedded image

Embedded image And the invention includes those described as hydrophilic monomers, while examples of lipophilic monomers include

Embedded image

Embedded image And those described as lipophilic monomers in the present invention. The graft compound thus obtained has both lipophilic and hydrophilic properties. Examples of its use include antifouling paints for preventing the attachment of marine organisms, and various new applications including application to ship bottom paints. Applications are expected.

As another example, as described above,

Embedded image Although it was stated that the grafted product had antithrombotic properties, it was obtained when both the lipophilic monomer such as butyl acrylate and methyl methacrylate and the monomer A were grafted. The graft compound increases the surface hydrophobicity due to the introduction of lipophilicity, has more antithrombotic properties and better blood compatibility than a single graft.

The MPC obtained by reacting the above-mentioned alcohol-modified silicone oil at both ends into the polyurethane main chain and graft-polymerizing the MPC to the side chain.
The grafted polyurethane has a property of preventing adhesion of marine organisms due to surface water retention, which is a property of side chain MPC, in addition to the properties of the main chain such as anti-adhesion property, release property, and slip property. However, for example, a great effect can be expected by using it as an antifouling paint in equipment using seawater as cooling water or a paint selected for various ships.

In the functional grafted polyurethane of the present invention, the ratio of the polyurethane constituting the main chain and the block polymer introduced by the graft polymerization constituting the side chain is 95: 5 to 5:95, If the proportion of the side chain is smaller than this range (the proportion of the main chain is large), the function of the introduced side chain will not be sufficiently exhibited, and only the properties of the main chain, that is, the polyurethane will be exhibited. Conversely, if the proportion of the side chain is larger than this range (the proportion of the main chain is small), the properties of the main chain, that is, polyurethane, are impaired, and only the properties of the side chain, that is, the homopolymer composed of functional monomers, are lost. It will appear.

As described above, the functional grafted polyurethane having a side chain obtained by bonding a functional monomer to the polyurethane constituting the main chain by graft polymerization has been described. It is described below.

The surface grafting of polyurethane refers to grafting at the molecular level to the surface of the polyurethane, in short, without impairing the various properties of the polyurethane, and only the surface of the grafted material. It is not a kind of polyurethane surface treatment, but unlike general surface treatment, the surface treatment according to the present invention is chemically bonded to the polyurethane surface by reaction, No peeling or separation occurs. That is, it is not a mixture (laminate) but a reaction product (integral). In addition, by performing such a reaction, the problem that the substance introduced into the side chain cannot sufficiently exhibit the function when the proportion of the main chain described in [0023] is large is also solved.

The method for synthesizing the surface-grafted polyurethane will be described in further detail. The method comprises the following first to fifth steps. The first step, synthesis of polyurethane, is the same as described above. The synthesis of the grafted polyurethane, which is the second step, is almost the same as described above, but in this case, a monomer having both a vinyl group and an epoxy group is graft-polymerized. At this time, the reaction or grafting percentage must be controlled to a low level to avoid cross-linking between the polyurethanes. A typical example of the monomer used in the second step is

Embedded image Glycidyl methacrylate represented by In the third step, the epoxy group introduced into the grafted polyurethane is ring-opened and a hydroxyl group is introduced into the molecule. The substance used at this time is a compound having both an amino group and a hydroxyl group in the molecule. So, as an example,

Embedded image And the like. In this reaction, there is no problem even if a large excess of amine is used to completely open the epoxy group. In the fourth step, the polyurethane obtained in the third step is formed into a film. Specifically, it is melted once and poured onto a glass plate to form a casting film. This film has a state in which a single molecule of a hydroxyl group protrudes from the surface. In the fifth step, the film-like polyurethane obtained in the fourth step is subjected to surface grafting, and is immersed in a solvent in which a functional monomer and a polymerization initiator are dissolved, and graft-polymerized. That is, a functional monomer having a vinyl group is bonded to a hydroxyl group present on the film surface by graft polymerization to extend the side chain. For example, when grafting a water-soluble monomer, a polymerization initiator such as Ce (IV) may be dissolved in water together with the monomer, and the above-mentioned film-like polyurethane may be immersed in the graft polymerization.
Further, graft copolymerization using two kinds of monomers can also be performed.

As described above, the surface-grafted polyurethane has an unprecedented characteristic to the main-chain polyurethane, and the surface-grafted substance is bonded in a very thin state at the molecular level. The surface texture is an unprecedented epoch-making material in which the properties of the grafted substance can be surely and fully exhibited, and materials using alcohol-modified silicone oil at both ends, alkanediol or polyethylene glycol are mainly used. The new properties added to the chain, such as anti-adhesion properties, peelability, slip properties, and affinity for water, are added, and many more effective applications such as antifouling paints and ship bottom paints can be expected.

[0028]

[Example 1] [1] Synthesis of polyurethane main chain "G2000" (Atactic butadiene oligomer: manufactured by Nippon Soda, molecular weight 2000)

Embedded image “X-22-160AS” (both terminal alcohol-modified silicone oil: manufactured by Shin-Etsu Chemical, molecular weight 1600)

Embedded image MDI (4,4-methylenediphenyl diisocyanate)

Embedded image BD (butanediol)

Embedded image “G2000” 56.0 in a 500 ml four-necked flask
g, “X-22-160AS” 18.9 g, N, N-dimethylacetamide / toluene = 1/4 mixed solvent 120
ml was added thereto and dissolved by applying ultrasonic waves for 2 hours. afterwards,
A condenser tube with a ball and a stirrer were attached, and MDI (molecular weight: 2) dissolved in 60 ml of the mixed solvent in a dry nitrogen stream.
50.3) 20.0 g was added with stirring, the temperature was raised to 70 to 75 ° C. in an oil bath, and 1
Allowed to react for hours. Thereafter, 3.78 g of BD (molecular weight 90) dissolved in 20 ml of N, N-dimethylacetamide was added dropwise over 10 minutes, the temperature was raised to 105 to 115 ° C, and the reaction was carried out for 1 hour. 5 minutes after the temperature rise, the mixed solvent 20
ml of di-n-butyltin dilaurate (molecular weight 6
32) 0.56 g was added over 10 minutes. After allowing to cool to room temperature, the mixture was poured into a large amount of methanol, and the precipitate was washed three times with methanol and dried under vacuum for 1 hour. A white elastic massive polyurethane was obtained. I of the obtained polyurethane
R is shown in FIG.

[2] Grafting reaction of polyurethane Glycidyl methacrylate

Embedded image A 100-ml eggplant-shaped flask was filled with the materials having the following composition dissolved therein, and the atmosphere was replaced with nitrogen gas. 3.0 g of the polyurethane synthesized in the above [1] 3.0 g of glycidyl methacrylate 4.0 ml AIBN 0.04 g of dioxane 30.0 ml The mixture was shaken at 70 ° C. for 3.5 hours in a warm bath and allowed to react. The stopper was stoppered and the reaction was poured into excess methanol. Washed three times with methanol and vacuum dried for 1 hour. As a result, a white elastic granular glycidyl methacrylate-grafted polyurethane was obtained. FIG. 2 shows the IR of the obtained glycidyl methacrylate-grafted polyurethane.

[Example 2] [1] Synthesis of polyurethane main chain "PEG1000" (polyethylene glycol: manufactured by Nacalai Task, molecular weight 1000) "G200" was placed in a 300 ml four-necked flask.
0 ", 28.0 g," PEG1000 ", 6.0 g, and dioxane, 60 ml, were added and dissolved by applying ultrasonic waves for 1 hour (" PEG1000 "was vacuum-dried at 80 ° C for 1 hour, dehydrated and used). Thereafter, a cooling tube with a ball and a stirrer were attached, and dioxane was 30 m in a dry nitrogen stream.
10.0 g of MDI (molecular weight 250.3) dissolved in 1
While stirring, and raise the temperature to 70-75 in an oil bath.
C. and the reaction was carried out for 1 hour with vigorous stirring. Thereafter, BD (molecular weight 90) dissolved in 10 ml of dioxane
1.8 g was added dropwise over 10 minutes, and the temperature was adjusted to 105 to 115.
After raising the temperature to 0 ° C., the reaction was carried out for 1 hour. Five minutes after the temperature was raised, 0.14 g of di-n-butyltin dilaurate (molecular weight: 632) dissolved in 10 ml of dioxane was added over 10 minutes.
After allowing to cool to room temperature, it is poured into a large amount of methanol and
The precipitate was washed with methanol and dried under vacuum for 1 hour.
A white elastic massive polyurethane was obtained. FIG. 3 shows the IR of the obtained polyurethane.

[2] Grafting reaction of polyurethane [2-1] Synthesis of HEMA grafted polyurethane HEMA (hydroxyethyl methacrylate)

Embedded image A 100-ml eggplant-shaped flask was filled with the materials having the following composition dissolved therein, and the atmosphere was replaced with nitrogen gas. The polyurethane synthesized in the above [1] 5.0 g HEMA 4.1 g AIBN 0.30 g dioxane 40.0 g methanol 4.4 g The mixture was shaken in a warm bath at 70 ° C. for 3.5 hours, and reacted at room temperature. After opening the stopper and concentrating the reaction product with an evaporator,
Poured into excess diethyl ether. Washed three times with diethyl ether and dried under vacuum for 30 minutes. As a result, a white elastic massive HEMA-grafted polyurethane was obtained.
FIG. 4 shows the IR of the obtained HEMA-grafted polyurethane.
It was shown to.

[2-2] Synthesis of Glycidyl Methacrylate-Grafted Polyurethane A 100 ml eggplant-shaped flask was charged with the materials having the following composition dissolved therein, and the atmosphere was sufficiently replaced with nitrogen gas and sealed. The polyurethane synthesized in the above [1] 5.0 g glycidyl methacrylate 6.3 g AIBN 0.23 g Dioxane 40.0 g Methanol 4.4 g The mixture was shaken at 70 ° C. for 10 hours in a warm bath and reacted at room temperature. The reaction mixture was poured into excess methanol. Washed three times with methanol and vacuum dried for 1 hour. As a result, a white elastic granular glycidyl methacrylate-grafted polyurethane was obtained. The IR of the obtained glycidyl methacrylate-grafted polyurethane is shown in FIG.

[2-3] Synthesis of silicone-grafted polyurethane "X-24-8201" (water-repellent silicone: manufactured by Shin-Etsu Chemical Co., Ltd.)

Embedded image A 100-ml eggplant-shaped flask was filled with the materials having the following composition dissolved therein, and the atmosphere was replaced with nitrogen gas. 5.0 g of the polyurethane synthesized in the above [1] 5.0 g "X-24-8201" 3.7 g AIBN 0.27 g Dioxane 40.0 g The mixture was shaken in a warm bath at 70 ° C. for 10 hours, reacted, and then cooled to room temperature. The back was opened and the reaction was poured into excess methanol. Washed three times with methanol and vacuum dried for 1 hour. As a result, a white elastic granular silicone-grafted polyurethane was obtained. FIG. 6 shows the IR of the obtained glycidyl methacrylate-grafted polyurethane.

[0034]

As described above, according to the present invention, a polyurethane synthesized using a diol having no double bond as a characteristic modifier is used as a main chain, and various functional monomers are graft-polymerized to the main chain. It is made of a polymer compound that is bonded, and the properties of the main chain polyurethane retain the properties of the conventional polyurethane, and new properties are added.The side chains introduced by graft polymerization Having the characteristics of the block polymer. Therefore, the functionalized grafted polyurethane obtained by the present invention has rubber elasticity, abrasion resistance, oxidation resistance, oil resistance,
In addition to conventional polyurethane properties such as aging resistance, various useful properties and functions are provided depending on the type of diol selected as a property modifier and the type of functional monomer bonded to the side chain. be able to. For example, when a silicone oil modified with both terminals alcohol is used as a diol as a property modifier, slip properties, anti-adhesion properties, releasability and the like are newly imparted. Therefore, it can be used in various fields as a material having an excellent effect that has not been achieved conventionally.

[Brief description of the drawings]

FIG. 1 is an IR chart of a polyurethane synthesized in Example 1 [1] and having a double bond introduced into the molecule.

FIG. 2 is an IR chart of a glycidyl methacrylate-grafted polyurethane synthesized in Example 1 [2].

FIG. 3 is an IR chart of a polyurethane synthesized in Example 2 [1] and having a double bond introduced into the molecule.

FIG. 4 is an IR chart of the HEMA-grafted polyurethane synthesized in Example 2 [2-1].

FIG. 5 is an IR chart of a glycidyl methacrylate-grafted polyurethane synthesized in Example 2 [2-2].

FIG. 6 is an IR chart of the silicone-grafted polyurethane synthesized in Example 2 [2-3].

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F071 AA53 AA77 AA80 AF04 AF26 AF55 AF58 AH12 AH19 BC01 BC07 4J026 AB03 BA02 BA03 BA05 BA06 BA09 BA10 BA11 BA19 BA25 BA29 BA30 BA32 BA39 BA41 BA43 BB01 BB02 BB03 DB02 DB17 DB02 GA01 4J034 CA04 CA15 CB03 CB07 CC03 DA01 DB04 DB07 DG03 DG08 DM01 DP19 HA07 HC03 HC09 HC12 HC13 HC22 HC46 HC64 HC67 HC71 HC73 LA06 LA13 LA32 LA36 QB14 QB15 QB17

Claims (22)

[Claims] 1. Polyurethane synthesized by the reaction of one or more diols having at least one double bond in the molecule, a diol acting as a main chain property modifier, and diisocyanate. And a functional monomer having a vinyl group bonded to the main chain by graft polymerization to form a side chain. 2. The functional grafted polyurethane according to claim 1, wherein the diol has at least one vinyl group in a molecule. 3. The functional grafted polyurethane according to claim 1, wherein the diol is a polybutadiene diol. 4. A diol as a main chain property modifier,
The functionalized grafted polyurethane according to any one of claims 1 to 3, which is a silicone oil modified at both ends with alcohol. 5. A diol as a main chain property modifier,
The functional grafted polyurethane according to any one of claims 1 to 4, which is polyethylene glycol. 6. The functional grafted polyurethane according to claim 1, wherein the functional monomer is a hydrophilic monomer. 7. The functional grafted polyurethane according to claim 6, wherein the functional monomer is at least one of the following monomers. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 8. The method according to claim 1, wherein the functional monomer is a lipophilic monomer, and is obtained by single graft polymerization or binary or ternary graft copolymerization. The functionalized grafted polyurethane of the above. 9. The functional grafted polyurethane according to claim 8, wherein the functional monomer is at least one of the following monomers. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 10. The method according to claim 1, wherein the functional monomer is a mixture of a hydrophilic monomer and a lipophilic monomer.
10. The functional grafted polyurethane according to any one of claims 9 to 9. 11. The functional grafted polyurethane according to claim 10, wherein each of the grafted side chains is formed by random, alternating or block copolymerization of a hydrophilic monomer and a lipophilic monomer. 12. The functional grafted polyurethane according to claim 1, wherein the functional monomer is a water-repellent monomer. 13. The functional grafted polyurethane according to claim 13, wherein the functional monomer is at least one of the following monomers. Embedded image 14. The functional grafted polyurethane according to claim 1, wherein the functional monomer is a water / oil repellent monomer. 15. The functional grafted polyurethane according to claim 14, wherein the functional monomer is at least one of the following monomers. Embedded image Embedded image Embedded image Embedded image Embedded image 16. The functional grafted polyurethane according to claim 1, wherein the functional monomer is at least one of the following monomers. Embedded image Embedded image 17. The method according to claim 1, wherein the ratio of the polyurethane constituting the main chain and the block polymer introduced by graft polymerization constituting the side chain is 95: 5 to 5:95. A functional grafted polyurethane according to any one of the preceding claims. 18. Polyurethane synthesized by the reaction of one or more diols having at least one double bond in the molecule, a diol acting as a main chain property modifier, and diisocyanate. A functional monomer having a vinyl group and an epoxy group is bonded to the main chain by graft polymerization to form a side chain, and a compound having an amino group and a hydroxyl group is reacted with the epoxy group of the side chain to introduce a hydroxyl group. This polyurethane is formed into a film shape, and the functional group having a vinyl group is bonded to the hydroxyl group present on the film surface by graft polymerization to extend the side chain, thereby obtaining a functional graft. Polyurethane. 19. The functional monomer graft-polymerized to a film-like polyurethane is represented by the following formula: The functionalized grafted polyurethane according to claim 18, wherein: 20. A first step of synthesizing a polyurethane by reacting at least one diol having at least one double bond in a molecule, a diol acting as a main chain property modifier, and diisocyanate. A functional step characterized by comprising a second step in which the polyurethane obtained in the first step is used as a main chain, and a functional monomer having a vinyl group is bonded to the main chain by graft polymerization to form a side chain. Synthetic method of grafted polyurethane. 21. A first step of reacting at least one diol having at least one double bond in a molecule, a diol acting as a main chain property modifier, and diisocyanate to synthesize a polyurethane. A second step in which the polyurethane obtained in the first step is used as a main chain, and a functional monomer having a vinyl group and an epoxy group is bonded to the main chain by graft polymerization to form a side chain; A third step of reacting a compound having an amino group and a hydroxyl group with an epoxy group in a side chain of the grafted polyurethane obtained in the step to introduce a hydroxyl group, and a fourth step of forming the polyurethane obtained in the third step into a film. A fifth step of graft-polymerizing the film-like polyurethane obtained in the fourth step by immersing the polyurethane in a solution in which a polymerization initiator and a functional monomer are dissolved; Synthesis of functional grafted polyurethane, characterized by consisting extent. 22. The method for synthesizing a functional grafted polyurethane according to claim 20, wherein the solvent used in the graft polymerization is a mixed solution of dioxane and methyl alcohol.