TW201723084A - Dendritic waterborne polyurethane composition and film formed by dendritic waterborne polyurethane composition - Google Patents

Abstract

The invention provides a dendritic waterborne polyurethane composition and a film formed by dendritic waterborne polyurethane composition. The dendritic waterborne polyurethane composition comprises a dendritic waterborne polyurethane formed by copolymerization of a first monomer containing isocyanate moieties, a second monomer containing at least two hydroxyl moieties, a third monomer containing carboxyl and hydroxyl moieties, and a tertiary amine wherein the first monomer has a structure shown by a general equation: OCN-R1-NCO; the second monomer includes a dendritic polyol and a diol having a structure shown by a general equation: HO-R2-OH; the third monomer has a structure shown by a general equation: HO-R3-OH (R3 contains at least one carboxyl moiety).

Description

Dendritic aqueous polyurethane composition and film comprising the same

The present invention relates to a polyurethane and a film comprising the polyurethane, and more particularly to a dendritic aqueous polyurethane and a film comprising the polyurethane.

Polyurethane has good processing properties and can be applied to fiber processing to improve hand feeling, artificial leather, waterproof and moisture permeable, printing, soft processing of textiles, shrink-proof processing, antistatic processing, and polymer materials, ceramic materials and metals. The surface of the material or the adhesive on the interface of the two heterogeneous materials is widely used in various fields and is a very important polymer material. In the process of polyurethane, a large amount of organic solvent is required. This type of polyurethane product contains the problem of volatile organic compounds (VOCs), and the aqueous polyurethane which replaces the organic solvent with water in the case of environmental awareness. (Waterborne Polyurethane) has attracted attention, but many properties of aqueous polyurethanes are not as good as solvent-based polyurethanes. It is expected to improve the properties by composite materials and molecular design, but the dispersion is still facing challenges.

Usually, the polyurethane itself is oily, it is not easy to be stable and uniformly dispersed in water, and the method of watering the polyurethane is usually, for example, an external emulsification method and an internal emulsification method. External emulsification methods, such as the addition of emulsifiers or surfactants, reduce the surface tension of polyurethane and water, and make polyamines The ester can be uniformly dispersed in water. On the other hand, an internal emulsification method, for example, in the process of synthesizing a polyurethane, a hydrophilic monomer is selected or an ionic group is introduced into the main structure to be dispersed in water, so that, depending on the introduced group, Aqueous polyurethanes can be classified into cationic, anionic and nonionic.

Dendrimer has a three-dimensional dendritic and globular structure. Compared with general polymers, it has the characteristics of low viscosity, high solubility, miscibility and high reactivity. At the same time, its volume and The type can also be specifically controlled during the synthesis process. For example, a dendrimer having a large hydrophobic void space and a hydrophilic nature is designed. Conventional linear polymers have only two terminal functional groups at both ends of the long chain, and the effect of changing the properties by modifying the terminal functional groups is limited. The dendrimer has a large number of functional groups at the end, so modifying the terminal functional group can make a significant change in molecular properties and physical properties, and the glass transition temperature will also be changed.

Therefore, since the dendrimer has the above advantages, it is desirable to improve the water solubility, thermal stability, adhesiveness, film formability, and the like of the polyurethane by the dendritic polyol to form a polyurethane by the design of the molecular structure.

In view of the above-described background of the invention, in order to meet the industrial requirements, one of the objects of the present invention is to provide a dendritic aqueous polyurethane composition and a film comprising the same, which comprise a specific amount in a specific range by a specific amount in the composition. The dendritic aqueous polyurethane having a particle size can improve characteristics such as water solubility, thermal stability, adhesion, and film formability. Further, when the dendritic aqueous polyurethane composition is used, when the film is formed, the film can be provided with good transparency, thermal stability, adhesion, mechanical properties and the like.

In order to achieve the above object, according to an embodiment of the present invention, a dendritic aqueous polyurethane composition comprising: a first monomer containing an isocyanate group, a second monomer having two or more hydroxyl groups, a carboxyl group, and a dendritic aqueous polyurethane obtained by polymerizing a third monomer of a hydroxyl group and a tertiary amine; wherein the first monomer has a structure represented by a general formula OCN-R ₁ -NCO, and the second monomer comprises a dendritic polyol and a diol having a structure represented by the general formula HO-R ₂ -OH, the third monomer having a structure represented by the general formula HO-R ₃ -OH, wherein R ₃ contains a carboxyl group, and the dendritic aqueous polyurethane comprises The structure (D1) or (D2) shown in the chemical formula.

or

Wherein H _n1 ~H _n18 represents a hydrogen atom bonded to a terminal oxygen atom, subscripts n1 to n18 represent the number of a hydrogen atom, not the number of hydrogen atoms, and 3 to 8 of H _n1 to H _n18 are R* Substituted for the group shown, R* has the structure shown by the following formula: , where x/y is 0.1~10.

In one embodiment, R ₁ is a divalent group selected from the group consisting of a linear or branched alkyl group having 2 to 16 carbon atoms and a stretched alkyl group having 3 to 12 carbon atoms in a group or a combination thereof.

In one embodiment, R ₂ is a divalent group selected from the group consisting of a linear or branched alkyl group having 2 to 16 carbon atoms and a stretched alkyl group having 3 to 12 carbon atoms or a combination thereof.

In another embodiment, the second monomer comprises ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol or hexanediol.

In one embodiment, R ₃ is a group of or a combination of a linear or branched alkyl group having 2 to 16 carbon atoms and a ring-shaped alkyl group having 3 to 12 carbon atoms; A divalent group.

Furthermore, in one embodiment, the first monomer is isophorone diisocyanate; the second monomer comprises polytetrahydrofuran and a dendritic polyol; and the third monomer is 2,2-bis(hydroxymethyl) Propionic acid; the tertiary amine is triethylamine; the dendritic polyol has the configuration shown by the following chemical formula:

In one embodiment, the second monomer further comprises a polyester polyol or a polyether polyol. In one embodiment, the polyester polyol is a glycol of adipic acid and a group selected from the group consisting of ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol, and hexanediol or It is obtained by a combination polymerization reaction and has a weight average molecular weight of 500 to 3,000. In one embodiment, the polyether polyol is polytetramethylene ether glycol, polypropylene glycol or polyethylene glycol having a weight average molecular weight of 1000 to 3000.

In one embodiment, the dendritic aqueous polyurethane composition comprises 0.3 to 2.1% by weight of the dendritic polyol in 100% by weight of the dendritic aqueous polyurethane. More preferably, the dendritic aqueous polyurethane composition contains 0.6 to 2.0% by weight of the dendritic polyol in 100% by weight of the dendritic aqueous polyurethane, and the dendritic aqueous polyurethane at this time has a viscosity at 25 ° C. It is 0.2~2100Pa. s, the weight average molecular weight is 180,000 to 260,000. The above dendritic water The polyurethane composition has a network structure, and an average particle diameter of 50 to 150 nm is desirable.

Further, according to another embodiment of the present invention, there is provided a film which is a film comprising the above-described dendritic aqueous polyurethane composition of the present invention.

According to the present invention, it is possible to provide a dendritic aqueous polyurethane composition and a film comprising the same, which can improve water solubility and heat stability by including a specific amount of a dendritic aqueous polyurethane having a specific particle diameter within a specific range in the composition. Characteristics such as adhesion, film formation, and the like. Further, when the dendritic aqueous polyurethane composition is used, when the film is formed, the film can be provided with good transparency, thermal stability, adhesion, mechanical properties and the like.

Figure 1 is a flow chart showing the preparation of dendritic aqueous polyurethane.

Fig. 2 is a graph showing the viscosity distribution of the dendritic aqueous polyurethane of the present invention obtained by polymerization in the ratio of different dendritic polyols.

Fig. 3 is a graph showing the average particle size distribution of the dendritic aqueous polyurethane of the present invention obtained by polymerization in the ratio of different dendritic polyols.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. Preferred embodiments of the present invention will be described in detail below, but in addition to these detailed descriptions, The present invention is also widely applicable to other embodiments, and the scope of the present invention is not limited thereto, which is based on the scope of the following patents.

According to an embodiment of the present invention, a dendritic aqueous polyurethane composition comprises: a first monomer containing an isocyanate group, a second monomer having two or more hydroxyl groups, and a third monomer having a carboxyl group and a hydroxyl group. And a dendritic aqueous polyurethane obtained by polymerizing a tertiary amine; wherein the first monomer has a structure represented by the general formula OCN-R ₁ -NCO, the second monomer comprising a dendritic polyol and having the general formula HO- a diol of the structure represented by R ₂ —OH, the third monomer having a structure represented by the general formula HO-R ₃ —OH, wherein R ₃ contains a carboxyl group, and the dendritic aqueous polyurethane comprises a structure represented by the above chemical formula (D1) or (D2).

Wherein H _n1 ~H _n18 represents a hydrogen atom bonded to a terminal oxygen atom, subscripts n1 to n18 represent the number of a hydrogen atom, not the number of hydrogen atoms, and 3 to 8 of H _n1 to H _n18 are R* Substituted for the group shown, R* has the structure shown by the following formula: , where x/y is 0.1~10.

Among them, x/y is preferably 0.25 to 7 and can have better water solubility.

Wherein R ₁ may be a divalent group selected from the group consisting of a linear or branched alkyl group having 2 to 16 carbon atoms and a stretched alkyl group having 3 to 12 carbon atoms, or a combination thereof, for example, a linear alkyl group such as a propyl group, a propyl group, a butyl group or a pentyl group; a branched alkyl group having an isopropyl group, an isobutyl group, an isoamyl group, or the like; A cycloalkyl group such as a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexylene group or the like.

In one embodiment, R ₂ is a divalent group selected from the group consisting of a linear or branched alkyl group having 2 to 16 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a combination thereof. a linear alkyl group having an ethyl group, a propyl group, a butyl group, a pentyl group, or the like; a branched alkyl group having an isopropyl group, an isobutyl group, an isoamyl group, or the like; a cycloalkyl group such as a benzyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexylene group or the like.

In another embodiment, the second monomer comprises ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol or hexanediol.

In one embodiment, R ₃ is a group of or a combination of a linear or branched alkyl group having 2 to 16 carbon atoms and a ring-shaped alkyl group having 3 to 12 carbon atoms; a divalent group such as a linear alkyl group having an ethyl group, a propyl group, a butyl group, a pentyl group or the like; an isopropyl group, an isobutyl group, an isobutyl group a branched alkyl group such as a carboxyl group; a cycloalkyl group having a cyclopentylcarboxy group, a cyclohexylcarboxy group, a methylcyclohexylcarboxy group, a trimethylcyclohexylcarboxy group, or the like.

Furthermore, in one embodiment, the first monomer is isophorone diisocyanate; the second monomer is polytetrahydrofuran and a dendritic polyol; and the third monomer is 2,2-bis(hydroxymethyl) Propionic acid; the tertiary amine is triethylamine; the dendritic polyol has the configuration shown by the following chemical formula:

The second monomer may further comprise a polyester polyol or a polyether polyol. The polyester polyol can be obtained by polymerization of adipic acid with a diol selected from the group consisting of ethylene glycol, diethylene glycol, butanediol, pentanediol, neopentyl glycol and hexanediol or a combination thereof. It has a weight average molecular weight of 500 to 3,000. The polyether polyol may be polytetramethylene ether glycol, polypropylene glycol or polyethylene glycol having a weight average molecular weight of 1000 to 3000.

The dendritic aqueous polyurethane composition of the present invention contains 0.3 to 2.1% by weight of the dendritic polyol in 100% by weight of the dendritic aqueous polyurethane. More preferably, the dendritic aqueous polyurethane composition contains 0.6 to 2.0% by weight of the dendritic polyol in 100% by weight of the dendritic aqueous polyurethane, and the dendritic aqueous polyurethane at this time has a viscosity at 25 ° C. It is 0.2~2100Pa. s, the weight average molecular weight is 180,000 to 260,000. The dendritic aqueous polyurethane composition has a network structure, and an average particle diameter of 50 to 150 nm is preferred.

Further, according to another embodiment of the present invention, a film comprising a film composed of the above-described dendritic aqueous polyurethane composition of the present invention is disclosed.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

Example 1: Preparation of dendritic aqueous polyurethane composition

The preparation process of the dendritic aqueous polyurethane is shown in FIG. Isophorone diisocyanate (IPDI), polytetrahydrofuran (PTMG); molecular weight 2000) and 2,2-Bis (hydroxymethyl)propionic acid (2,2-Bis(hydroxymethyl)propionic acid ( DMPA)) After removing water for 12 hours in a vacuum oven set at 70 ° C, the solvent Acetone used in this example was previously placed in a molecular sieve to reduce its water content. The equivalents of the reactants are shown in Table 1. According to the ratio of Table 1, PTMG and DMPA were placed in a double-necked flask and uniformly mixed. The temperature was set at 120 ° C, and the water was removed by vacuum for 2 hours, followed by cooling to 70 ° C under nitrogen. Under the environment, 15 mL of acetone was added, the temperature was raised to 80 ° C, and some IPDI was added to carry out the reaction. After 4 hours, dendritic polyol (Dendrimer; Bolton H20 or P500, the dendritic polyol shown in Fig. 1 was P500) was added, and after half an hour. The remaining ratio of IPDI is added to continue the reaction until the reaction is completed. Add 5 ml of acetone, cool to 50 ° C, and add TEA for 1 hr. Another ice bath was set up, and the above-mentioned synthesized dendritic aqueous PU prepolymer was added to deionized water and the chain extender EDA and stirred for 1 hour to form a dendritic aqueous PU dispersion (dendritic aqueous polyurethane composition) having a solid concentration of 30% by weight.

PTMG: polytetrahydrofuran

DMPA: 2,2-bis(hydroxymethyl)propionic acid

IPDI: Isophorone diisocyanate

TEA: Triethylamine

EDA: ethylenediamine

Dendrimer: Bolton H20 (available from Huanqi International Trading Co., Ltd.)

The obtained dendritic aqueous polyurethane composition was subjected to various characteristic tests such as viscosity, average particle diameter, glass transition temperature (Tg), GPC, DSC, TGA, and UV/VIS transmittance measurement.

Fig. 2 is a graph showing the viscosity distribution of the dendritic aqueous polyurethane of the present invention obtained by polymerization in the ratio of different dendritic polyols. Fig. 3 is a graph showing the average particle size distribution of the dendritic aqueous polyurethane of the present invention obtained by polymerization in the ratio of different dendritic polyols.

Example 2: Production of a film

The prepared dendritic aqueous polyurethane dispersion (Dendrimer ratios of 0%, 0.3%, 0.6%, 0.9%, 1.2%, 1.5%, 1.8%, 2.1%) was taken to a fixed weight (the solid content concentration was 30% by weight) Place in a Teflon vessel of 10 cm x 10 cm and leave it at room temperature for 48 hours. The sample was placed in a vacuum oven at 80 ° C, and after drying, it was a dendritic aqueous polyurethane film having a thickness of 0.8 mm. The obtained film was subjected to tensile test and transmittance test, and it was found that the higher the proportion of the dendritic water-based polyurethane, the higher the tensile strength, but the elongation was lowered, and the penetration rate was maintained at about 90%, not because of the addition of dendritic There are too many variations in the proportion of waterborne polyurethane.

According to the present invention, it is possible to provide a dendritic aqueous polyurethane composition and a film comprising the same, which can improve water solubility and heat stability by including a specific amount of a dendritic aqueous polyurethane having a specific particle diameter within a specific range in the composition. Characteristics such as adhesion, film formation, and the like. Further, when the dendritic aqueous polyurethane composition is used, when the film is formed, the film can be provided with good transparency, thermal stability, adhesion, mechanical properties and the like.

The present invention has been described in detail with reference to the preferred embodiments of the present invention, and the scope of the invention is not limited thereto, and it is understood that various modifications and changes can be made without departing from the spirit and scope of the invention. In addition, any of the objects or advantages or features of the present invention are not required to be achieved by any embodiment or application of the invention. In addition, the abstract sections and headings are only used to assist in the search of patent documents and are not intended to limit the scope of the invention.

Claims (17)

A dendritic aqueous polyurethane composition comprising: a first monomer containing an isocyanate group, a second monomer having two or more hydroxyl groups, a third monomer having a carboxyl group and a hydroxyl group, and a branch obtained by polymerizing a tertiary amine An aqueous polyurethane; wherein the first monomer has a structure represented by the general formula OCN-R ₁ -NCO, the second monomer comprising a dendritic polyol and a structure having the general formula HO-R ₂ -OH a diol having a structure represented by the general formula HO-R ₃ -OH, wherein R ₃ contains a carboxyl group, and the dendritic aqueous polyurethane comprises a configuration represented by the following chemical formula: Wherein H _n1 ~H _n18 represents a hydrogen atom bonded to a terminal oxygen atom, subscripts n1 to n18 represent the number of a hydrogen atom, not the number of hydrogen atoms, and 3 to 8 of H _n1 to H _n18 are R* Substituted for the group shown, R* has the structure shown by the following formula: , where x/y is 0.1~10. The dendritic aqueous polyurethane composition according to claim 1, wherein R ₁ is a linear or branched alkyl group selected from carbon atoms 2 to 16, and a cycloalkyl group having 3 to 12 carbon atoms. Divalent groups in groups or combinations thereof. The dendritic aqueous polyurethane composition according to claim 1, wherein R ₂ is a linear or branched alkyl group selected from carbon atoms 2 to 16, and a cycloalkyl group having 3 to 12 carbon atoms. Divalent groups in groups or combinations thereof. The dendritic aqueous polyurethane composition of claim 1, wherein the second monomer comprises ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol or hexanediol. The dendritic aqueous polyurethane composition according to claim 1, wherein R ₃ is a linear or branched alkyl group selected from the group consisting of a carboxyl group having 2 to 16 carbon atoms, and a carboxyl group-containing carbon number 3~ A divalent group of 12 groups of cycloalkyl groups or a combination thereof. The dendritic aqueous polyurethane composition according to claim 1, wherein the first monomer is isophorone diisocyanate. The dendritic aqueous polyurethane composition of claim 1, wherein the second monomer comprises polytetrahydrofuran. The dendritic aqueous polyurethane composition according to claim 1, wherein the third monomer is 2,2-bis(hydroxymethyl)propionic acid. The dendritic aqueous polyurethane composition according to claim 1, wherein the tertiary amine is triethylamine. The dendritic aqueous polyurethane composition according to claim 1, wherein the dendritic polyol has a configuration represented by the following chemical formula: The dendritic aqueous polyurethane composition of claim 1, wherein the second monomer further comprises a polyester polyol or a polyether polyol. The dendritic aqueous polyurethane composition according to claim 11, wherein the polyester polyol is adipic acid and is selected from the group consisting of ethylene glycol, diethylene glycol, butanediol, pentanediol, and neopentyl The diol in which alcohol and hexanediol are grouped or a combination thereof is obtained by polymerization, and has a weight average molecular weight of 500 to 3,000. The dendritic aqueous polyurethane composition according to claim 11, wherein the polyether polyol is polytetramethylene ether glycol having a weight average molecular weight of 1000 to 3000, and polypropylene. Glycol or polyethylene glycol. The dendritic aqueous polyurethane composition according to claim 1, wherein the dendritic aqueous polyurethane contains 100% by weight of the dendritic polyol in an amount of 0.3 to 2.1% by weight. The dendritic aqueous polyurethane composition according to claim 1, wherein the dendritic aqueous polyurethane comprises 100 to 2.0% by weight of the dendritic polyol, and the dendritic aqueous polyurethane The viscosity at 25 ° C is 0.2~2100Pa. s, the weight average molecular weight is 180,000 to 260,000. The dendritic aqueous polyurethane composition according to claim 15, wherein the dendritic aqueous polyurethane composition has a network structure and an average particle diameter of 50 to 150 nm. A film comprising the dendritic aqueous polyurethane composition according to any one of claims 1 to 16.