阅读说明：本技术 氧化锌分散液及其制备方法、用于制备氧化锌分散液的组成物 (Zinc oxide dispersion liquid, preparation method thereof and composition for preparing zinc oxide dispersion liquid ) 是由 丁立慈 吴昱寯 洪维泽 于 2020-07-14 设计创作，主要内容包括：一种氧化锌分散液及其制备方法、用于制备氧化锌分散液的组成物,所述氧化锌分散液包含氧化锌结构体及式(I)所示的芳香族多元醇。该式(I)所示的芳香族多元醇具有多个末端羟基,且所述末端羟基螯合至该氧化锌结构体的锌原子上,其中,p及q分别表示1至40中的整数。通过该式(I)所示的芳香族多元醇中的苯环基产生立体障碍效应,致使氧化锌结构体彼此间被隔开,从而避免因聚集团聚导致沉淀的问题产生,因此,本发明氧化锌分散液具有良好的分散稳定性,且能满足后续各项应用需求。(A zinc oxide dispersion liquid, a preparation method thereof and a composition for preparing the zinc oxide dispersion liquid are provided, wherein the zinc oxide dispersion liquid comprises a zinc oxide structure body and an aromatic polyol shown in a formula (I). The aromatic polyol represented by the formula (I) has a plurality of terminal hydroxyl groups, and the terminal hydroxyl groups are chelated to the zinc atom of the zinc oxide structure, wherein p and q each represent an integer of 1 to 40. The aromatic polyol of the formula (I) has a steric hindrance effect due to the benzene ring group, so that the zinc oxide structures are in contact with each otherThe zinc oxide dispersion liquid is separated, so that the problem of precipitation caused by aggregation and agglomeration is avoided, and the zinc oxide dispersion liquid has good dispersion stability and can meet the requirements of various subsequent applications.)

1. A zinc oxide dispersion liquid characterized by comprising:

a zinc oxide structure; and

an aromatic polyol represented by the formula (I) having a plurality of terminal hydroxyl groups, wherein the terminal hydroxyl groups are chelated to the zinc atom of the zinc oxide structure,

wherein p and q each represent an integer of 1 to 40.

2. The zinc oxide dispersion liquid according to claim 1, characterized in that: p and q each represent an integer of 1 to 30.

3. The zinc oxide dispersion liquid according to claim 1, characterized in that: the zinc oxide structure is contained in an amount ranging from 1 wt% to 30 wt% based on 100 wt% of the total amount of the zinc oxide dispersion.

4. The zinc oxide dispersion liquid according to claim 3, characterized in that: the zinc oxide structure is contained in an amount ranging from 1 wt% to 20 wt% based on 100 wt% of the total amount of the zinc oxide dispersion.

5. The zinc oxide dispersion liquid according to claim 1, characterized in that: the zinc oxide dispersion is obtained by heating a composition comprising an aromatic polyol having a plurality of terminal hydroxyl groups and a zinc salt, wherein the zinc salt undergoes a nucleophilic reaction to form a zinc intermediate comprising one of a zinc hydroxide and a zinc alkoxide, the zinc intermediate undergoes a condensation reaction to be converted into a zinc oxide structure, and the terminal hydroxyl groups of the aromatic polyol having the formula (I) are chelated to zinc atoms of the zinc oxide structure;

Wherein p and q each represent an integer of 1 to 40.

6. The zinc oxide dispersion liquid according to claim 5, characterized in that: the zinc salt is selected from an acid salt, a zinc alkoxide, zinc chloride, zinc acetylacetonate, or a combination of any of the foregoing.

7. The zinc oxide dispersion liquid according to claim 5, characterized in that: p and q each represent an integer of 1 to 30.

8. The zinc oxide dispersion liquid according to claim 5, characterized in that: the nucleophilic reaction is carried out at a first temperature, and the condensation reaction is carried out at a second temperature higher than the first temperature.

9. The zinc oxide dispersion liquid according to claim 8, characterized in that: the first temperature is in the range of greater than 100 ℃ and less than 130 ℃, and the second temperature is in the range of 130 ℃ to 150 ℃.

10. The zinc oxide dispersion liquid according to claim 5, characterized in that: the zinc oxide structure is contained in an amount ranging from 1 wt% to 30 wt% based on 100 wt% of the total amount of the zinc oxide dispersion.

11. The zinc oxide dispersion liquid according to claim 5, characterized in that: the zinc oxide structure is contained in an amount ranging from 1 wt% to 20 wt% based on 100 wt% of the total amount of the zinc oxide dispersion.

12. The zinc oxide dispersion liquid according to claim 5, characterized in that: the composition further comprises water.

13. A method for producing a zinc oxide dispersion, characterized by comprising: heating a composition comprising an aromatic polyol represented by formula (I) and a zinc salt to obtain a zinc oxide dispersion, wherein the zinc salt undergoes a nucleophilic reaction to form a zinc intermediate comprising one of a zinc hydroxide and a zinc alkoxide, the zinc intermediate undergoes a condensation reaction to be converted into a zinc oxide structure, and the terminal hydroxyl group of the aromatic polyol represented by formula (I) is chelated to a zinc atom of the zinc oxide structure;

wherein p and q each represent an integer of 1 to 40.

14. The method for producing a zinc oxide dispersion according to claim 13, characterized in that: the zinc salt is selected from acid salt, zinc alkoxide, zinc chloride, zinc acetylacetonate, alkyl zinc salt, sulfur-containing zinc salt or the combination of any of the above.

15. The method for producing a zinc oxide dispersion according to claim 13, characterized in that: the nucleophilic reaction is carried out at a first temperature, and the condensation reaction is carried out at a second temperature higher than the first temperature.

16. The method for producing a zinc oxide dispersion according to claim 15, characterized in that: the first temperature is in the range of greater than 100 ℃ and less than 130 ℃, and the second temperature is in the range of 130 ℃ to 150 ℃.

17. The method for producing a zinc oxide dispersion according to claim 13, characterized in that: the composition further comprises water.

18. The method for producing a zinc oxide dispersion according to claim 13, characterized in that: the zinc oxide structure is contained in an amount ranging from 1 wt% to 30 wt% based on 100 wt% of the total amount of the zinc oxide dispersion.

19. The method for producing a zinc oxide dispersion according to claim 18, characterized in that: the zinc oxide structure is contained in an amount ranging from 1 wt% to 20 wt% based on 100 wt% of the total amount of the zinc oxide dispersion.

20. A composition for preparing a zinc oxide dispersion, characterized by comprising:

a zinc salt capable of forming a zinc intermediate including one of a hydroxide and a alkoxide of zinc through a nucleophilic reaction and converting the zinc intermediate into a zinc oxide structure through a condensation reaction; and

an aromatic polyol represented by the formula (I) having a plurality of terminal hydroxyl groups,

wherein p and q each represent an integer of 1 to 40.

Technical Field

The present invention relates to a zinc oxide dispersion and a method for preparing the same, and more particularly, to a zinc oxide dispersion having good dispersion stability and a method for preparing the same.

Background

Zinc oxide is a mineral substance having an antibacterial effect, and can release positive charges to be combined with negatively charged proteins or other anionic groups on the surface of bacteria, so as to prevent the generation of bacterial cell walls and damage cell membranes, thereby achieving a physical sterilization effect.

In general, zinc oxide is in powder form, such as that disclosed in taiwan patent publication No. TW201914961, and thus, there are problems that dust is easily blown up to cause inhalation damage or dispersion uniformity is not good in use. Also, taiwan patent publication No. TW201522204 discloses a method for preparing a zinc oxide thin film, which has problems of safety in operation and health hazards due to the use of toxic solvents, and energy consumption and complicated process due to 10 annealing treatments at 550 ℃. At present, zinc oxide and a polyol such as polyethylene glycol 400 (PEG 400), polyethylene glycol 600 (PEG 600) or polypropylene glycol 450 (PPG 450) are used in the form of a solution to improve the safety and convenience of operation. However, in this solution, zinc oxide cannot be stably dispersed in the polyol, so that the problem of precipitation of zinc oxide due to the agglomeration phenomenon occurs, and there is still a problem of poor operational convenience in the subsequent application.

Disclosure of Invention

A first object of the present invention is to provide a zinc oxide dispersion liquid having good dispersion stability.

The zinc oxide dispersion liquid of the present invention comprises a zinc oxide structure and an aromatic polyol represented by the formula (I),

wherein p and q each represent an integer of 1 to 40. The aromatic polyol represented by the formula (I) has a plurality of terminal hydroxyl groups, and the terminal hydroxyl groups are chelated to the zinc atom of the zinc oxide structure.

In the zinc oxide dispersion liquid of the present invention, p and q each represent an integer of 1 to 30.

In the zinc oxide dispersion liquid of the present invention, the content of the zinc oxide structure ranges from 1 wt% to 30 wt% based on the total amount of the zinc oxide dispersion liquid as 100 wt%.

In the zinc oxide dispersion liquid of the present invention, the content of the zinc oxide structure ranges from 1 wt% to 20 wt% based on the total amount of the zinc oxide dispersion liquid as 100 wt%.

In the zinc oxide dispersion liquid of the present invention, the zinc oxide dispersion liquid is obtained by heating a composition comprising an aromatic polyol represented by formula (I) having a plurality of terminal hydroxyl groups and a zinc salt, wherein the zinc salt is subjected to a nucleophilic reaction to form a zinc intermediate comprising one of a zinc hydroxide and a zinc alkoxide, and the zinc intermediate is subjected to a condensation reaction to be converted into a zinc oxide structure, and the terminal hydroxyl groups of the aromatic polyol represented by formula (I) are chelated to zinc atoms of the zinc oxide structure;

Wherein p and q each represent an integer of 1 to 40.

In the zinc oxide dispersion of the present invention, the zinc salt is selected from an acid salt, a zinc alkoxide, zinc chloride, zinc acetylacetonate, or a combination of any of the foregoing.

In the zinc oxide dispersion liquid of the present invention, p and q each represent an integer of 1 to 30.

In the zinc oxide dispersion of the present invention, the nucleophilic reaction is carried out at a first temperature, and the condensation reaction is carried out at a second temperature higher than the first temperature.

In the zinc oxide dispersion of the present invention, the first temperature ranges from more than 100 ℃ to less than 130 ℃, and the second temperature ranges from 130 ℃ to 150 ℃.

In the zinc oxide dispersion liquid of the present invention, the content of the zinc oxide structure ranges from 1 wt% to 30 wt% based on the total amount of the zinc oxide dispersion liquid as 100 wt%.

In the zinc oxide dispersion liquid of the present invention, the content of the zinc oxide structure ranges from 1 wt% to 20 wt% based on the total amount of the zinc oxide dispersion liquid as 100 wt%.

In the zinc oxide dispersion liquid of the present invention, the composition further includes water.

The second object of the present invention is to provide a method for preparing a zinc oxide dispersion, which can prepare a zinc oxide dispersion having good dispersion stability.

The method of preparing a zinc oxide dispersion according to the present invention comprises heating a composition comprising an aromatic polyol represented by formula (I) and a zinc salt to obtain a zinc oxide dispersion, wherein the zinc salt is subjected to a nucleophilic reaction to form a zinc intermediate comprising one of a hydroxide and an alkoxide of zinc and the zinc intermediate is subjected to a condensation reaction to be converted into a zinc oxide structure, and the terminal hydroxyl group of the aromatic polyol represented by formula (I) is chelated to a zinc atom of the zinc oxide structure,

wherein p and q each represent an integer of 1 to 40.

In the method for preparing a zinc oxide dispersion according to the present invention, the zinc salt is selected from an acid salt, a zinc alkoxide salt, zinc chloride, zinc acetylacetonate, an alkyl zinc salt, a sulfur-containing zinc salt, or a combination of any of the foregoing.

In the method for producing a zinc oxide dispersion of the present invention, the nucleophilic reaction is carried out at a first temperature, and the condensation reaction is carried out at a second temperature higher than the first temperature.

In the method of preparing a zinc oxide dispersion according to the present invention, the first temperature ranges from more than 100 ℃ to less than 130 ℃, and the second temperature ranges from 130 ℃ to 150 ℃.

In the method for preparing a zinc oxide dispersion liquid of the present invention, the composition further includes water.

In the method of preparing a zinc oxide dispersion liquid of the present invention, the content of the zinc oxide structure ranges from 1 wt% to 30 wt% based on 100 wt% of the total amount of the zinc oxide dispersion liquid.

In the method of preparing a zinc oxide dispersion liquid of the present invention, the content of the zinc oxide structure ranges from 1 wt% to 20 wt% based on 100 wt% of the total amount of the zinc oxide dispersion liquid.

The third objective of the present invention is to provide a composition for preparing zinc oxide dispersion.

The composition for preparing the zinc oxide dispersion liquid comprises zinc salt and aromatic polyol shown in a formula (I). The zinc salt is capable of forming a zinc intermediate comprising one of a hydroxide and a alkoxide of zinc via a nucleophilic reaction and the zinc intermediate undergoes a condensation reaction to convert to a zinc oxide structure. The aromatic polyol represented by the formula (I) has a plurality of terminal hydroxyl groups,

wherein p and q each represent an integer of 1 to 40.

The invention has the beneficial effects that: the benzene ring group in the aromatic polyol shown in the formula (I) generates a steric hindrance effect, so that zinc oxide structures are separated from each other, and the problem of precipitation caused by agglomeration is avoided.

Drawings

FIG. 1 is an NMR spectrum showing the result of structural analysis of production example 3 of an aromatic polyol represented by the formula (I) in the present invention;

FIG. 2 is an IR spectrum showing the binding relationship between the aromatic polyol represented by the formula (I) and the zinc oxide structure in the zinc oxide dispersion liquid of the present invention;

FIG. 3 is an IR spectrum showing the binding relationship between the aromatic polyol represented by the formula (I) and the zinc oxide structure in the zinc oxide dispersion liquid of the present invention;

FIG. 4 is an X-ray diffraction spectrum illustrating that zinc oxide structures can be obtained by the method for preparing a zinc oxide dispersion according to the present invention;

FIG. 5 is an X-ray diffraction spectrum illustrating the structure of the zinc oxide structure of the present invention after sintering.

Detailed Description

The zinc oxide dispersion liquid of the present invention contains a zinc oxide structure and an aromatic polyol represented by formula (I).

[ Zinc oxide Dispersion liquid ]

In the zinc oxide dispersion liquid of the present invention, the terminal hydroxyl group of the aromatic polyol represented by the formula (I) is bonded to a zinc atom of a zinc oxide structure, and a steric hindrance effect is produced by the benzene ring group of the aromatic polyol represented by the formula (I) so that the zinc oxide structures can be effectively isolated from each other, thereby avoiding the problem of precipitation caused by agglomeration, therefore, the zinc oxide structure can be stably dispersed in the aromatic polyol shown in the formula (I), so that the zinc oxide dispersion liquid has the characteristic of good dispersion stability, thereby having excellent performance in terms of operational convenience, and further, the zinc oxide dispersion liquid of the present invention has good dispersion stability at high temperatures, therefore, the dispersibility of the zinc oxide dispersion of the present invention is not affected even when the ambient temperature is high during transportation or storage. In addition, the aromatic polyol shown in the formula (I) has a reactive group-hydroxyl group, and can play the role of a reaction reagent in subsequent application, so that the zinc oxide dispersion liquid can reduce the use of the reaction reagent in the subsequent application, thereby reducing the production cost.

The zinc oxide dispersion of the present invention can be applied to biomedical materials (e.g., antibacterial textiles), coating products (e.g., antibacterial coatings), or leather products (e.g., antibacterial artificial leathers), and the like.

< Zinc oxide Structure >

The zinc oxide structure is not particularly limited in morphology. Structurally, the arrangement of zinc atoms and oxygen atoms in the zinc oxide structure is not particularly limited. In some embodiments of the invention, the zinc oxide structure is amorphous zinc oxide.

In order to make the zinc oxide dispersion liquid have better fluidity and be clear and transparent, the zinc oxide structure is preferably contained in an amount ranging from 1 wt% to 30 wt% based on 100 wt% of the total amount of the zinc oxide dispersion liquid. In some embodiments of the invention, the zinc oxide structure is present in an amount ranging from 1 wt% to 20 wt%.

< aromatic polyol represented by the formula (I) >

The aromatic polyol represented by the formula (I) has a plurality of terminal hydroxyl groups, and the terminal hydroxyl groups are chelated to the zinc atom of the zinc oxide structure,

wherein p and q each represent an integer of 1 to 40.

In some embodiments of the invention, p and q each represent an integer of 1 to 30. Also, in some embodiments of the present invention, p and q each represent an integer of 1 to 20.

In order to provide better handling convenience and dispersibility for the zinc oxide dispersion, it is preferable that the aromatic polyol represented by the formula (I) has a viscosity ranging from 800 to 1500cp at 30 ℃. In some embodiments of the invention, the aromatic polyol of formula (I) has a viscosity in the range of 900 to 1200cp at 30 ℃.

The content of the terephthalic acid segment [ -O-C (O) -ph-C (O) -O- ] is in the range of 5 to 50 wt% based on 100 wt% of the total amount of the aromatic polyol represented by the formula (I), and further, the content of the terephthalic acid segment is in the range of 15 to 35 wt%.

The aromatic polyol of formula (I) can be prepared by any known chemical method, for example, bis (2-hydroxyethyl) terephthalate (BHET)]And ethylene oxide. The chemical structure of the bis (2-hydroxyethyl) terephthalate isAnd from the reaction of components comprising terephthalic acid and ethylene oxide. In order to make the aromatic polyol represented by the formula (I) have better water solubility, it is preferable that the ratio of the number of moles of the ethylene oxide to the number of moles of the bis (2-hydroxyethyl) terephthalate is not less than 4.

The aromatic polyol shown in the formula (I) has three characteristics of reactivity, dispersibility and low viscosity, wherein the reactivity refers to that the aromatic polyol shown in the formula (I) can be directly used as a reaction reagent for subsequent application and can react with other reagents for subsequent application [ such as a curing agent (such as a compound containing an isocyanate group) ] without adding a reaction reagent additionally because the aromatic polyol has a hydroxyl group as a reaction group; the dispersibility means that the aromatic polyol represented by the formula (I) has hydroxyl groups and benzene ring groups, can be combined with zinc oxide structures to generate a steric hindrance effect, and helps to separate the zinc oxide structures from each other and stably disperse in the aromatic polyol represented by the formula (I) in a zinc oxide dispersion liquid; the low viscosity means that no organic solvent is required to be added in the process of preparing the zinc oxide dispersion liquid to reduce the viscosity so as to reduce the inconvenience in operation, and the zinc oxide dispersion liquid and the preparation process thereof can meet the environmental protection standard.

[ method for preparing Zinc oxide Dispersion ]

The method for preparing a zinc oxide dispersion according to the present invention comprises heating a composition comprising an aromatic polyol represented by formula (I) and a zinc salt to obtain a zinc oxide dispersion. In the heating, the terminal hydroxyl group of the aromatic polyol represented by the formula (I) is chelated to the zinc atom of the zinc salt, and at the same time, the zinc salt undergoes a nucleophilic reaction to form a zinc intermediate including one of a zinc hydroxide and a zinc alkoxide, and the zinc intermediate undergoes a condensation reaction to be converted into a zinc oxide structure, so that the zinc oxide dispersion comprises the zinc oxide structure and the aromatic polyol represented by the formula (I) chelated to the zinc atom of the zinc oxide structure with the terminal hydroxyl group.

In the method for preparing a zinc oxide dispersion according to the present invention, the aromatic polyol represented by formula (I) which can be used as a dispersant is directly mixed with a zinc salt without preparing a solution form by first obtaining zinc oxide powder and then adding an organic solvent serving as a dispersant, and therefore, the method for preparing a zinc oxide dispersion according to the present invention can simplify the process and reduce the use of an organic solvent, in addition to obtaining a zinc oxide dispersion having good dispersion stability, thereby reducing the production cost.

< composition >

The aromatic polyol represented by the formula (I) is as described above, and therefore, the description thereof is omitted.

The zinc salt may be any salt that can form a zinc intermediate including one of a hydroxide and a alkoxide of zinc through a nucleophilic reaction and can be converted into a zinc oxide structure by a condensation reaction of the zinc intermediate. The zinc salt may be used singly or in combination, and the zinc salt is exemplified by, but not limited to, acid zinc salt, alcohol zinc salt, zinc chloride, alkane zinc salt, sulfur-containing zinc salt, or zinc acetylacetonate [ zinc (ii) acetylacetate]And the like. The acid salt may be used singly or in combination of plural kinds, and the acid zinc salt is, for example, but not limited to, zinc carboxylate, zinc nitrate, zinc chlorate, zinc perchlorate or the like. Such as, but not limited to, zinc acetate dihydrate, Zn (OAc) ₂·2H₂O]Or zinc glycolate, and the like. The zinc alkoxide salt may be used singly or in combination of plural kinds, and the zinc alkoxide salt is, for example, but not limited to, zinc methoxide (C)₂H₆O₂Zn) or zinc diethoxide (C)₄H₁₂O₂Zn), and the like. The alkyl zinc salt may be used singly or in combination, and is exemplified by, but not limited to, dimethyl zinc (Zn, CH)₃)₂]Or diethyl zinc [ diethyl zinc, Zn (C)₂H₅)₂]And the like. The sulfur-containing zinc salt may be used singly or in combination of plural kinds, and the sulfur-containing zinc salt is exemplified by, but not limited to, zinc sulfide (ZnS) or zinc sulfate (ZnSO)₄) And the like. In some embodiments of the invention, the zinc salt is selected from the group consisting of zinc acetate, zinc glycolate, zinc nitrate, zinc chloride, zinc alkoxidesSalt, zinc chlorate, zinc perchlorate, zinc acetylacetonate or a combination of any of the foregoing. In an embodiment of the invention, the zinc salt is zinc acetate. The zinc salt is used in an amount ranging from 15 wt% to 98 wt% based on 100 wt% of the total amount of the composition. In some embodiments of the present invention, the zinc salt is used in an amount ranging from 15 wt% to 40 wt%, based on 100 wt% of the total amount of the composition.

Since zinc salt is easily soluble in water, the composition further includes water in the method for preparing zinc oxide dispersion according to the present invention in order to provide environmental protection and to shorten the time for dispersing zinc salt into aromatic polyol represented by formula (I).

When the composition comprises water, in order to avoid the nucleophilic reaction being too violent and generating a large amount of zinc intermediate in a short time, so as to generate a zinc oxide structure with large particles and easy sedimentation in the condensation reaction process, the method for preparing the zinc oxide dispersion liquid further comprises the step of removing water from the composition. The water removal treatment is performed by heating at a temperature of 100 ℃ or lower. In some embodiments of the invention, the water removal treatment is to remove water from the composition to a water content of less than 1 wt%.

< nucleophilic reaction and condensation reaction >

The nucleophilic reaction (nucleophilic reaction) converts the zinc salt to a zinc intermediate comprising one of a zinc hydroxide and a zinc alkoxide. Such as zinc hydroxide. The zinc alkoxide is, for example, zinc alkoxide or zinc enolate. Specifically, for example, when the zinc salt is a zinc carboxylate salt, a carboxylic acid group in the zinc carboxylate salt is converted into a hydroxyl group or a hydrocarbyloxy group, or, when the zinc salt is zinc chloride, chlorine in the zinc chloride is converted into a hydroxyl group or a hydrocarbyloxy group, or, when the zinc salt is zinc acetylacetonate, acetylacetone in the zinc acetylacetonate is converted into a hydroxyl group or a hydrocarbyloxy group. Examples of the nucleophilic reaction include a substitution reaction, an alcoholysis reaction (alcoholysis reaction), and a hydrolysis reaction (hydrolysis reaction). The nucleophilic reaction can be carried out in the presence of a reactant such as a protic reagent such as water to carry out the hydrolysis reaction, or an alcohol reagent such as a hydrocarbon alcohol to carry out the alcoholysis reaction, or sodium hydroxide to carry out the substitution reaction. Such as alkanol or enol, etc. For example, the reactant is water when the zinc salt is a zinc carboxylate salt or a zinc alkoxide salt, or the reactant is an alkanol when the zinc salt is zinc chloride or zinc acetylacetonate, or the reactant is sodium hydroxide when the zinc salt is zinc chloride. In some embodiments of the invention, the nucleophilic reaction is a hydrolysis reaction. The condensation reaction converts the zinc intermediate into a zinc oxide structure. The nucleophilic reaction and the condensation reaction can be carried out simultaneously or the nucleophilic reaction is carried out first and then the condensation reaction is carried out. In some embodiments of the invention, the nucleophilic reaction is performed at a first temperature, and the condensation reaction is performed at a second temperature, and the second temperature is higher than the first temperature. In some embodiments of the invention, the first temperature ranges from greater than 100 ℃ to less than 130 ℃ and the second temperature ranges from 130 ℃ to 150 ℃.

The invention will be further described in the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the practice of the invention.

Preparation of BHET

264.3 g (1.59mol) of terephthalic acid, 2.9 g of sodium carbonate and 158.5 g of water were placed in a 1 liter stainless steel reactor, the above materials were stirred and heated to a temperature of 120 ℃, ethylene oxide was slowly injected into the reactor at a flow rate of 1mL/min, the temperature of the reactor was controlled to 120 ℃ and the pressure was controlled to 7.0kgf/cm²Thereafter, 245.2 g (5.57mol) of ethylene oxide was injected, the reaction was continued for 15 minutes, and then the temperature was lowered to 110 ℃ to remove water and toluene by distillation under reduced pressure, and the mixture was cooled to room temperature to obtain BHET.

Production example 1 aromatic polyol represented by formula (I)

300 g (1.18mol, 100 parts by weight) of BHET and 0.04298 g (100ppm) of potassium hydroxide (KOH) were charged into the reaction tank at 9.0kgf/cm²The temperature was raised to 130 ℃ under pressure. After the reaction temperature reaches 130 ℃ and BHET is melted, slowly injecting the mixture into a ring in a reaction tank at a flow rate of 1mL/minEthylene oxide until 129.8 g (2.95mol, 43.3 parts by weight) of ethylene oxide are added; subsequently, the materials in the reaction vessel were mixed at 500rpm to carry out the reaction. After the reaction is continued for about 0.5 hour, the aromatic polyol, hereinafter referred to as PHB2.5, is obtained.

Production examples 2 to 6 aromatic polyol represented by formula (I)

The aromatic polyols represented by the formula (I) of production examples 2 to 6 were produced in a similar manner to the procedure of production example 1 except that: the amount of ethylene oxide added was varied, and the obtained aromatic polyol represented by formula (I) was abbreviated as PHB6, PHB10, PHB20, PHB30 and PHB40 in the order, see table 1.

Evaluation item

Appearance type: the appearance patterns of the aromatic polyols of the formula (I) of preparation examples 1 to 6 at room temperature were observed, and the results are shown in Table 1.

Viscosity (unit: cp): the aromatic polyol represented by the formula (I) of preparation examples 1 to 6 was measured at 30 ℃ using a Brookfield DV-E digital viscometer, and the results are shown in Table 1.

Molecular weight: the aromatic polyol represented by the formula (I) of preparation examples 1 to 6 was analyzed by a mass spectrometer (made by Waters, model number Xevo TQ-GC), and the results are shown in Table 1.

The content (unit: wt%) of terephthalic acid segment in the aromatic polyol represented by the formula (I): a fixed amount of the aromatic polyol represented by the formula (I) of preparation examples 1 to 6 was taken and placed in a bottle as a sample, and then a fixed amount of potassium hydroxide (KOH) aqueous solution of a fixed concentration was added to the sample and the empty bottle, respectively, to obtain an experimental group [ aromatic polyol + KOH represented by the formula (I) ] and a control group (KOH); the experimental and control groups were then heated to 95 ℃ and stirred for 3 hours, finally titrated with 1N aqueous hydrochloric acid and the volumes of dilute hydrochloric acid used were recorded. The volume of diluted hydrochloric acid used in the experimental group and the control group is respectively deduced back to the number of grams of KOH used, and the number of grams of KOH in the experimental group is subtracted from the number of grams of KOH in the control group, so that the saponification value can be calculated. Next, the number of moles of the terephthalic acid segment and the content (wt%) of the terephthalic acid segment were calculated, and the results are shown in Table 1. The molar number of terephthalic acid segments was [ saponification value X (1g/1000mg) ]/(56.1X 2). The content (wt%) of the terephthalic acid segment was [ mole number of terephthalic acid segments × molecular weight of terephthalic acid (166.13) ]/weight of the aromatic polyol represented by the formula (I).

And (3) chemical structure analysis: by using¹H-NMR (using DMSO-d)₆Frequency 400MHz as solvent) PHB10 of preparation example 3 was subjected to structural identification analysis, and the obtained spectrum was shown in fig. 1.

Analysis of p and q: a gel permeation chromatograph (manufactured by Waters corporation, model No. Waters 1525, RI detector, water column G2500PWXL) was used, and the test method was exemplified by PHB20 of preparation example 4. PHB20 of preparation example 4 was first saponified by taking a quantitative and fixed concentration of aqueous sodium hydroxide solution and adding it to a sample bottle containing the product, and then the sample bottle was heated and stirred at 95 ℃ for 3 hours to obtain a reaction product. The reaction mixture was filtered through a filter paper and a filter plate [ at this time, the polyethylene glycol produced was dissolved in the water layer, i.e., the first ether segment of the aromatic polyol represented by the formula (I) [ H- (O-CH) ]₂-CH₂)_p-O-CH₂-CH₂-O-]And a second ether segment [ H- (O-CH)₂-CH₂)_q-O-CH₂-CH₂-O-]After saponification, polyethylene glycol is formed and dissolved in water layer]The aqueous layer was then subjected to Gel Permeation Chromatography (GPC) analysis. The results obtained are collated in Table 1.

TABLE 1

From the results in table 1, it is understood that the aromatic polyol represented by the formula (I) in preparation examples 1 to 5 is liquid at room temperature and is very suitable as a reagent for dispersing a zinc oxide structure in terms of handling convenience.

With reference to FIG. 1, the pH of preparation example 3 was adjustedFrom the NMR spectrum of B10, it was found that: (1) no 4.7ppm of BHET was observed, and the absorption peak [ -C (O) -O-CH₂-CH₂-C(O)-O-](ii) a (2) An absorption peak A (ph-4H) at 8ppm, an absorption peak B (terminal hydroxyl group) at 4.5 to 4.6ppm, and an absorption peak C [ -C (O) -O-CH ] at 4.4ppm₂-]The integral area ratio of the absorption peak A to the absorption peak B to the absorption peak C is 4:2:4, and the structure of the aromatic polyol shown in the formula (I) of the invention is satisfied; and (3) the absorption peak of terminal hydroxyl group (-OH) of BHET was not 5ppm, but absorption of terminal hydroxyl group was observed at 4.6ppm, indicating that a first ether segment and a second ether segment were present between the terminal hydroxyl group and the benzene ring group. As is clear from the above, BHET and EO do react with each other to form the aromatic polyol represented by the formula (I).

Furthermore, from the GPC analysis data of preparation 3, it can be seen that both Mw and Mn of the polyethylene glycol are very close to 282, which means that p and q in PHB10 of preparation 3 should be 5, because in preparation 3, the ratio of the number of moles of ethylene oxide to the number of moles of BHET is 10 and the ethylene oxide is uniformly distributed to react with the two terminal hydroxyl groups of BHET, based on which the theoretical molecular weight of the first ether segment or the second ether segment should be 265 (1 +5 × 44+44), and the first ether segment or the second ether segment is grafted with-OH after saponification, respectively, so that the theoretical molecular weight of the obtained polyethylene glycol should be 282, and thus it is concluded that p and q should be 5. In addition, the PDI data for preparation 3 is 1.1216, indicating that p and q are very close.

Example 1 Zinc oxide Dispersion

Step (a): 20.23 g of zinc acetate dihydrate [ Zn (OAc) ]₂·2H₂O, molecular weight: 219.51](available from syn, inc.) was mixed with 60 ml of deionized water and placed in an oil bath at 80 c for heating and stirring for 15 minutes at 500rpm to form an aqueous solution of zinc acetate.

Step (b): 142.5 g of PHB6 of production example 2 was slowly added to the aqueous solution of zinc acetate in step (a) to form a composition, and then, the composition was placed in an oil bath, and the temperature of the oil bath was raised to 120 ℃ so that the temperature of the composition could be maintained at 100 ℃ and the stirring was continued at 500rpm for 1 hour to remove water in the composition to form a clear and transparent mixed solution having a water content of 0.05 to 1% by weight.

Step (c): the temperature of the mixture was raised to 105 ℃ by means of oil bath heating, and stirring was continued at 500rpm for 1 hour to conduct hydrolysis. During the hydrolysis reaction, the acetate group of the zinc acetate is converted into a hydroxyl group, and a zinc intermediate is obtained. Subsequently, the temperature of the mixed solution was raised to 135 ℃ and the mixture was continuously stirred at 500rpm for 1 hour to perform a condensation reaction, in which case the zinc intermediate was converted into amorphous zinc oxide during the condensation reaction, and a clear and transparent zinc oxide dispersion was obtained. After the condensation reaction is finished, the temperature is reduced to room temperature, and the obtained zinc oxide dispersion liquid contains amorphous zinc oxide with the concentration of 5 wt% and aromatic polyol shown in the formula (I).

Examples 2 to 18 Zinc oxide dispersions

The zinc oxide dispersions of examples 2 to 18 were prepared in a similar manner to the zinc oxide dispersion of example 1, except that: the kind of the aromatic polyol represented by the formula (I) or the amount of each component used is shown in Table 2.

Comparative examples 1 and 3 Zinc oxide Dispersion

The zinc oxide dispersions of comparative examples 1 and 3 were prepared in a similar manner to the zinc oxide dispersion of example 1, except that: PHB6 was replaced with PEG400 and PPG450 in sequence, see Table 2.

Comparative example 2 solid Zinc oxide Dispersion

The solid zinc oxide dispersion of this comparative example 2 was prepared in a similar manner to the zinc oxide dispersion of this example 1, except that: PHB6 was replaced with PEG600, see table 2.

TABLE 2

Evaluation item

And (3) structural identification and analysis: PHB6 of preparation example 2, the zinc oxide dispersions of example 1 and example 3 were analyzed by means of an infrared spectrometer (brand: Perkin Elmer, model: Spectrum 100), and the results are shown in FIG. 2 and FIG. 3.

And (3) structural identification and analysis: ethanol was added to the zinc oxide dispersion liquid of example 3 to generate precipitates and subjected to a filtration treatment to obtain a cake, which was then placed in an oven set at 70 ℃ to be subjected to a drying treatment, the cake was analyzed by an X-ray diffractometer (brand: Bruker, model: D2PHASER), and the result was shown in FIG. 4, and then, high-temperature sintering was performed at 450 ℃ for 1 hour to obtain a sintered product. The sinter was analyzed by an X-ray diffractometer (brand: Bruker, model: D2PHASER), and the results are shown in FIG. 5.

Fluidity at room temperature: the zinc oxide dispersions of examples 1 to 18 and the zinc oxide dispersions of comparative examples 1 and 3 were placed in a container, filled to eighths of the full and sealed, and then the container was inverted and observed whether the zinc oxide dispersion was immediately fluid or not, and the zinc oxide dispersion was fluid when it was immediately fluid.

Dispersion stability at Normal temperature: the zinc oxide dispersions of examples 1 to 18 and the zinc oxide dispersions of comparative examples 1 and 3 were allowed to stand at room temperature, and the appearance was visually observed for 180 days, to confirm whether or not the precipitation phenomenon occurred, and the number of days when the precipitation phenomenon occurred was recorded. When the precipitation phenomenon occurs, it indicates that the zinc oxide dispersion liquid does not have the characteristic of dispersion stability.

Dispersion stability at high temperature: the zinc oxide dispersions of examples 1 to 13, 16 and 19, the zinc oxide dispersions of comparative examples 1 and 3 and the solid zinc oxide dispersion of comparative example 2 were left to stand in a hot air circulating oven and the temperature was increased from 30 ℃ to 120 ℃ and once every 30 minutes and 10 ℃ for each time. The appearance was visually observed to 120 ℃ to confirm whether or not the precipitation occurred, and the temperature at which the precipitation occurred was recorded. When the precipitation phenomenon occurs, it indicates that the zinc oxide dispersion liquid does not have the characteristic of dispersion stability.

Dispersion stability: using a stability analyzer (brand: LUM GmbH; model: LUMisizer 651; detection limit: 1 × 10)^-3μ m/s) and at a rotational speed of 1000rpm (corresponding to a centrifugal force with a gravitational acceleration (g) of 135)]The zinc oxide dispersions of examples 1, 6, 10, 13, 16 and 19 and the zinc oxide dispersions of comparative examples 1 and 3 were measured for the sedimentation rate (unit: μm/s) under conditions of a spinning time of 10000 seconds, a light wavelength of 870nm and a temperature of 25 ℃.

Referring to FIG. 2 and FIG. 3, the distance between 3400 and 3640cm^-1The characteristic peak is hydroxyl and is 520-560 cm^-1The characteristic peak of (b) is O-Zn, and as the content of zinc oxide increases, the signal of hydroxyl group decreases and the signal of O-Zn increases, so that it can be inferred that the terminal hydroxyl group of PHB6 chelates with Zn to form O-Zn, which means that the terminal hydroxyl group of the aromatic polyol represented by the formula (I) is indeed chelated to the zinc oxide structure and can generate a steric effect by the benzene ring group of the aromatic polyol represented by the formula (I), thereby helping to separate the zinc oxide structures from each other and stably dispersing in the aromatic polyol represented by the formula (I) in the zinc oxide dispersion.

Referring to FIG. 4, the characteristic peaks (upper broken line) in the X-ray diffraction spectrum of the cake exhibited the structural morphology of zinc oxide having a hexagonal wurtzite structure conforming to JCPDS card NO.36-1451 (lower broken line) since amorphous zinc oxide would begin to tend to align with the lowest energy without the aromatic polyol represented by the formula (I), and based on the above, it was concluded that the method for producing a zinc oxide dispersion of the present invention indeed obtained amorphous zinc oxide. Referring to FIG. 5, the characteristic peaks in the X-ray diffraction spectrum of the sintered body show the structural morphology of zinc oxide having a hexagonal wurtzite structure, which is more consistent with JCPDS card NO.36-1451, and thus it can be seen that the arrangement of oxygen and zinc is more periodic in the structural morphology after the sintering treatment, and thus the width of each characteristic peak in FIG. 5 is narrower than that of each characteristic peak in FIG. 4.

TABLE 3

As can be seen from the experimental results in table 3, the zinc oxide dispersion obtained from PEG400 and PPG450 shows a sedimentation phenomenon at the present time, while the product obtained from PEG600 is solid at room temperature and does not naturally have a sedimentation phenomenon, but after being heated to be liquid, the product undergoes a sedimentation phenomenon at 40 ℃. In contrast, the aromatic polyol of formula (I) is used to prevent the precipitation caused by the agglomeration of zinc oxide, so that the zinc oxide dispersion of the present invention has good dispersion stability, is liquid at room temperature without further heating, and is convenient to operate. Furthermore, the zinc oxide dispersion has good dispersion stability even when the zinc oxide content is more than 5 wt%. As can be seen from the experimental results in table 3, in the test of stability at high temperature, as the ratio of benzene ring groups increases, the steric hindrance provided by the benzene ring groups is more significant, and the zinc oxide structures can be more effectively separated from each other, thereby reducing the phenomenon of aggregation and precipitation caused by collision, and improving the dispersion stability of the zinc oxide dispersion.

As shown by the results of the settling rate data in table 3,the zinc oxide dispersions of examples 1, 6, 10, 13, 16 and 19 have a sedimentation velocity below the detection limit (1X 10)^-3μ m/s) so that it is impossible to measure, and the settling rates of comparative examples 1 and 3 are 3.065 μm/s and 9.056 μm/s, respectively, it is known that the zinc oxide dispersion of the examples is less prone to settling phenomenon and thus has a better dispersing effect than the zinc oxide dispersions of comparative examples 1 and 3, and thus has operational convenience in use and can maintain good dispersibility over a long period of time.

Further, since the aromatic polyol represented by the formula (I) in the zinc oxide dispersion liquid of the present invention can be used as a polyol raw material for producing polyethylene terephthalate, the compatibility between the zinc oxide dispersion liquid of the present invention, ethylene glycol and water was further investigated to confirm that the zinc oxide dispersion liquid of the present invention can allow the condensation polymerization reaction to proceed in a uniform state without precipitation of a zinc oxide structure when it participates in the production of polyethylene terephthalate. Based on the above, the zinc oxide dispersion liquid of example 1 was stirred and mixed with water and Ethylene Glycol (EG), respectively, and subjected to a compatibility test. In the two aspects of mixing water with the zinc oxide dispersion of example 1, the weight ratios of the water to the zinc oxide dispersion of example 1 were 0.5 and 1, and in the two aspects of mixing ethylene glycol with the zinc oxide dispersion of example 1, the weight ratios of the ethylene glycol to the zinc oxide dispersion of example 1 were 2 and 1. In this case, the zinc oxide dispersion of example 1 was changed from a clear and transparent state to a white mist suspension state, which indicates that the compatibility with water or ethylene glycol was not good, but did not cause significant zinc oxide precipitation for 48 hours, and therefore, even when the dispersion was used in combination with a reagent containing water or ethylene glycol in the subsequent use, the dispersion did not cause a precipitation problem, and thus, the dispersion still had the characteristic of being easy to handle in the subsequent use, for example, application example 1 and application example 3 described later.

Application example 1

60 g of an oil solution (available from Dingxing industries, type: ESTESOL 7796) was mixed with 40 g of the zinc oxide dispersion of example 11, and 900 g of water was added to prepare 1000 g of a mixed solution. The content of the amorphous zinc oxide in the mixed solution was 0.4 wt% [ (40 × 10 wt%) × 100%/1000 ]. 100 g of non-woven fabric (purchased from the New century, Toyoto, No. H20190527462) is soaked in the mixed solution for 1 minute, then taken out and placed in a dehydrator (brand: whorlpol, model: WM141D) for dehydration treatment for 1 minute, finally taken out and placed in an oven and baked at 110 ℃ for 10 minutes to form a treated non-woven fabric, and the treated non-woven fabric comprises non-woven fabric, zinc oxide with a structure of hexagonal wurtzite and an oil agent which are dispersed in the non-woven fabric.

Application example 2

100 g of one-liquid polyurethane resin (from Nissh chemical, type: SS-1054F, with a solids content of 30 wt% and a solvent of dimethylformamide) was mixed uniformly with 0.44 g of the zinc oxide dispersion of example 7, and 1 g of a curing agent (from Nissh chemical, type: SC-7190NY) was added and stirred uniformly to form a coating, and then the coating was coated on a release paper to form a wet film having a thickness of about 30 μm, and was baked in an oven set at 150 ℃ for 10 minutes to remove dimethylformamide, thereby forming an artificial skin of zinc oxide having a thickness of 10 μm and a structure of hexagonal wurtzite on the release paper. In the artificial skin, the content of zinc oxide having the structure form of a hexagonal wurtzite structure was 0.14 wt% [ (0.44 × 10 wt%) × 100/(100 × 30 wt% +1+0.44) ].

Application example 3

36 g of the aromatic polyol represented by the formula (I) of preparation example 1 (as a nonionic surfactant), 8 g of dodecylbenzenesulfonic acid (as an anionic surfactant; available from Diyu chemical Co., Ltd.; concentration: 96%; CAS: 68584-22-5) and 31 g of water were mixed uniformly, and 25 g of the zinc oxide dispersion of example 6 was added to form 100 g of a detergent. In the lotion, the content of the amorphous zinc oxide was 1.25 wt% { [ (25 × 5 wt%)/100 ] × 100% }.

Comparative application example 1

The comparative application example 1 was prepared in a similar manner to the application example 3, except that: the zinc oxide dispersion of example 6 was replaced with the zinc oxide dispersion of comparative example 1.

Comparative application example 2

The comparative application example 2 was prepared in a similar manner to the application example 3, except that: the zinc oxide dispersion of example 6 was replaced with the zinc oxide dispersion of comparative example 3.

Evaluation item

And (3) antibacterial test: the treated nonwoven fabric of example 1 and the artificial leather of application example 2 were subjected to an antibacterial test according to the standard technique of FTTS-FA-001.

The results of the data of the antibacterial test showed that the treated nonwoven fabric and the artificial leather had a sterilization rate of 88.8% and an antibacterial effect against staphylococcus aureus and a sterilization rate of 85.9% and 9.4% against klebsiella pneumoniae, and thus it was found that the treated nonwoven fabric and the artificial leather had excellent antibacterial effects.

Analysis of dispersion stability: using a stability Analyzer (trade name: LUM GmbH; model: LUMisizer 651; measurement Limit: 1X 10)^-3μ m/s) and at a rotational speed of 1000rpm [ corresponding to a centrifugal force with a gravitational acceleration (g) of 130 [ ]]The sedimentation rate (unit: μm/s) of the detergents of application example 3, comparative application example 1 and comparative application example 2 was measured under the conditions of a spinning time of 10000 seconds, a light wavelength of 870nm and a temperature of 25 ℃.

In the analysis of the dispersion stability, the sedimentation rate of the application example 3 was 2.715 μm/s, and the sedimentation rates of the comparative application example 1 and the comparative application example 2 were 29.79 μm/s and 156.1 μm/s, respectively, whereby it was found that the lotion of the application example 3 was less likely to cause sedimentation phenomenon and had a better dispersion effect than the lotions of the comparative application examples 1 and 2, and further had operational convenience and maintained good dispersibility over a long period of time.

In summary, the benzene ring group in the aromatic polyol shown in the formula (I) generates a steric hindrance effect, so that the zinc oxide structures are separated from each other, thereby avoiding the problem of precipitation caused by agglomeration.