CN109705648B - Application of novel fluoronaphthalene ester film-forming assistant in color-changing coating - Google Patents

Abstract

The invention relates to a 4-perfluoroalkyl substituted 1, 8-naphthalene diester compound and application thereof. The 1, 8-naphthalene diesterThe compound is shown as formula I. The compound shown in the formula I can be used as a film-forming aid for water-based paint or ink (particularly water-based paint or ink capable of changing color).

In the formula I, R₁And R₂Each independently selected from: c₁～C₁₅Rf is C₁～C₁₀Linear or branched perfluoroalkyl groups of (a).

Description

Application of novel fluoronaphthalene ester film-forming assistant in color-changing coating

Technical Field

The invention relates to a fluorine-containing naphthalene diester compound and application thereof; in particular to a 4-perfluoroalkyl substituted 1, 8-naphthalene diester compound and application thereof.

Background

Film-forming aids are high boiling materials added to coatings or inks to aid in film formation. It can make the polymer with higher glass transition temperature (Tg) film-forming at lower temperature. The film-forming aid is adsorbed on the polymer particles, the particles are more easily deformed due to dissolution, and the Tg of the film-forming aid is low, so that more free volume can be provided, and a better film-forming effect can be achieved. With the increasing awareness of environmental protection, the film-forming additive will develop towards high boiling point, multifunction, safety (low toxicity) and acceptable biodegradability.

Currently, the film forming aids used in aqueous coatings or inks are Texanol, "alcohol ester 12", Lusolvan FBH, Coasol, DBE-IB, DPnB, DOWANOL-PPh, and the like. These film-forming aids have been used in many different applications, but some properties (especially scrub resistance, chalking or/and color uniformity, etc.) have been improved.

Thus, it has been a technical problem to be solved by the present invention to provide a novel film-forming aid which has superior properties over existing film-forming aids.

Disclosure of Invention

The inventor designs and synthesizes fluorine-containing naphthyl ester compounds with novel structures. The fluorine-containing naphthyl ester compound is used as a film forming additive to be applied to water-based ink or paint, and tests show that: the performances of scrub resistance, chalking or/and color uniformity and the like of the water-based ink or coating are better than those of the water-based ink or coating adopting the existing film-forming auxiliary agent (such as the most commonly used 'alcohol ester 12').

The invention aims to provide a fluorine-containing naphthyl ester compound with a novel structure.

The fluorine-containing naphthyl ester compound is a compound shown as a formula I:

in the formula I, R₁And R₂Each independently selected from: c₁～C₁₅Rf is C₁～C₁₀Linear or branched perfluoroalkyl groups of (a).

The invention also discloses an application of the fluorine-containing naphthyl ester compound (the compound shown in the formula I).

Namely: the use of a compound of formula I as a film-forming aid for aqueous coatings or inks, especially water-based coatings or inks which are colour-changeable.

In addition, the invention also aims to provide a method for preparing the compound shown in the formula I.

The method mainly comprises the following steps: 1, 8-naphthalic anhydride (compound shown as formula II) substituted by 4-perfluoroalkyl and corresponding alcohol (R) in the presence of catalyst and inert gas₁OH or/and R₂OH) to obtain the target product through esterification reaction.

Wherein the catalyst is an acidic catalyst (such as p-toluenesulfonic acid, trifluoromethanesulfonic acid or acidic cation exchange resin); the inert gas is a gas which does not participate in the reaction and has stable chemical properties (such as nitrogen, argon or neon); the definition of Rf in formula II is the same as that described above, and the compounds of formula II are known compounds and are commercially available or can be prepared according to published literature.

Detailed Description

In a preferred embodiment of the present invention, R₁And R₂Each independently selected from: c₁～C₁₅Linear or branched alkyl of (a), and R₁And R₂The same;

in a further preferred embodiment, R is₁And R₂Each independently selected from: c₂～C₁₃Linear or branched alkyl of (a), and R₁And R₂The same is true.

In another preferred embodiment of the present invention, Rf is C₄～C₈Linear or branched perfluoroalkyl groups of (a).

The invention provides a method for preparing a compound shown as a formula I, which mainly comprises the following steps: reacting the compound of formula II with the corresponding alcohol (R) in the presence of a catalyst (such as p-toluenesulfonic acid, trifluoromethanesulfonic acid or acidic cation exchange resin) and an inert gas (such as nitrogen gas)₁OH or/and R₂OH) is maintained at reflux or at 100 ℃ to 150 ℃ for at least five hours, and unreacted alcohol (R) is distilled off₁OH or/and R₂OH), cooling the reaction liquid to room temperature, filtering, extracting the filtrate with water, separating an organic phase, and evaporating low-boiling-point substances in the organic phase to obtain a residue, namely the target substance.

The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the invention and do not limit the scope of the invention.

Example 1

Formula I_AThe compound shown (abbreviated as' Compound I_A") preparation:

1mol of 4-perfluorobutyl-1, 8-naphthalic anhydride (formula II)_APlacing 10mol of compound, industrial product, a product of Lily group Co., Ltd.), ethanol (10mol, industrial product, Shanghai Aladdin Biotechnology Co., Ltd.) and 5 g of anhydrous sodium sulfate in a four-neck flask provided with a stirring and condensing tube and a thermometer, slowly heating a reaction system to reflux in the presence of a catalyst (1 mol% of trifluoromethanesulfonic acid) and nitrogen, keeping mechanical stirring for at least 5 hours in the state, evaporating unreacted ethanol, cooling a reaction solution to room temperature (15-30 ℃, the same applies below), carrying out suction filtration, transferring a filtrate to room temperature, and carrying out vacuum filtrationSeparating with a separating funnel, adding appropriate amount of water, repeatedly extracting, separating organic phase, evaporating organic phase to remove low boiling point substance to obtain residue as title compound (compound I)_A)。

¹H NMR(400MHz,CDCl₃):8.74-8.75(m,2H),7.70-7.71(m,2H),8.48(m,1H),4.30-4.31(m,4H),1.29-1.30(m,6H).

HRMS (TOF-ESI): Calcd. (theoretical, same below) [ M-H ] -490.0911, found (experimental, same below) 490.0918.

Example 2

Formula I_BThe compound shown (abbreviated as' Compound I_B") preparation:

compound I was obtained in the same manner as in example 1 except that isopropyl alcohol (industrial product, available from Shanghai Aladdin Biotechnology Ltd.) was used in place of ethanol in example 1_B。

¹H NMR(400MHz,CDCl3):8.74-8.75(m,2H),7.70-7.71(m,2H),8.48(m,1H),5.24(s,2H),1.32-1.33(m,12H).

HRMS(TOF-ESI):Calcd.[M-H]-819.2623，found 819.2673。

Example 3

Formula I_CThe compound shown (abbreviated as' Compound I_C") preparation:

compound I was obtained in the same manner as in example 1 except that n-butanol (industrial product, available from Shanghai Aladdin Biotechnology Ltd.) was used in place of ethanol in example 1, and the other steps and reagents used were the same as in example 1_C。

¹H NMR(400MHz,CDCl3):8.74-8.76(m,2H),7.70-7.75(m,2H),8.48(m,1H),4.32-4.33(m,4H)，1.82-1.83(m,4H)，1.45-1.46(m,4H)，1.01-0.95(m,6H).

HRMS(TOF-ESI):Calcd.[M-H]-547.0612，found 547.0618。

Example 4

Formula I_DThe compound shown (abbreviated as' Compound I_D") preparation:

compound I was obtained by following the same procedures as in example 1 except that n-dodecanol (industrial product, available from Shanghai Allantin Biotechnology Co., Ltd.) was used instead of ethanol in example 1 and the esterification reaction temperature was 100 ℃ in the same manner as in example 1_D。

¹H NMR(400MHz,CDCl3):8.74-8.76(m,2H),7.70-7.76(m,2H),8.48(m,1H),4.32-4.33(m,4H)，1.29-1.83(m,20H)，0.88-0.95(m,6H).

HRMS(TOF-ESI):Calcd.[M-H]-771.3145，found 771.3149。

Example 5

Formula I_EThe compound shown (abbreviated as' Compound I_E") preparation:

compound I was obtained in the same manner as in example 1 except that isotridecanol (industrial product, available from Shanghai Aladdin Biochemical technology Co., Ltd.) was used in place of ethanol in example 1 and the esterification reaction temperature was 110 ℃ C_E。

¹H NMR(400MHz,CDCl3):8.74-8.77(m,2H),7.70-7.78(m,2H),8.49(m,1H),4.33-4.34(m,4H)，1.29-1.83(m,22H)，0.89-0.96(m,6H).

HRMS(TOF-ESI):Calcd.[M-H]-799.3125，found 799.3129。

Example 6

1mol of 4-perfluorooctyl-1, 8-naphthalic anhydride (formula II)_BThe compound shown, industrial product, product of Lily group Co., Ltd.), isopropanol (10mol, industrial product, product of Shanghai Aladdin Biotechnology Ltd.) and 5 g of anhydrous sodium sulfate were placed in a four-neck flask equipped with a stirring and condensing tube and a thermometer, the reaction system was slowly heated to 100 ℃ in the presence of a catalyst (1 mol% of trifluoromethanesulfonic acid) and nitrogen, and mechanical stirring was maintained in this state for at least 5 hours, unreacted isopropanol was distilled off, the reaction liquid was cooled to room temperature, suction filtration was carried out, the filtrate was transferred to a separatory funnel, an appropriate amount of water was added and repeatedly extracted to separate an organic phase, and the residue obtained after low boiling substance was distilled off from the organic phase was the title compound (Compound I)_F)。

¹H NMR(400MHz,CDCl3):8.74-8.76(m,2H),7.71-7.76(m,2H),8.49(m,1H),5.28(s,2H),1.33-1.36(m,12H).

HRMS(TOF-ESI):Calcd.[M-H]-719.1125，found 719.1127。

Film formation and film Performance testing

Example 7

The compound I_A～I_FAnd the existing commercial film-forming assistant, alcohol ester 12 (as a reference) is respectively applied to water-based paints (provided by industrial-grade Nippon paint (China) Co., Ltd.) to respectively obtain water-based paints A to F and reference water-based paints (hereinafter, referred to as "paints A to F" and "reference paints"), and the formulas of the paints A to F and the reference paints are shown in Table 1.

The film-forming properties such as film-forming time and film-forming state, and other properties such as water resistance, alkali resistance, stain resistance, etc. of the coatings A to F and the control coating were tested, and the test results are shown in Table 2.

Table 1.

TABLE 1

^*The color-changing dye is supplied by Shanghai Ganta optical materials Co.

TABLE 2

As can be seen from Table 2, the film-forming properties (such as film-forming level and film-forming time) and scrub resistance, chalking and color uniformity of the aqueous coating or ink using the 4-perfluoroalkyl substituted 1, 8-naphthalene diester compound provided by the present invention as a film-forming aid are superior to those of the aqueous coating or ink using the existing film-forming aid ("alcohol ester 12").

Claims (5)

1. A fluorine-containing naphthyl ester compound is a compound shown as a formula I:

in the formula I, R₁And R₂Each independently selected from: c₁～C₁₅Rf is C₁～C₁₀Linear or branched perfluoroalkyl groups of (a).

2. The fluoronaphthyl compound of claim 1, wherein R is₁And R₂Each independently selected from: c₁～C₁₅Linear or branched alkyl of (a), and R₁And R₂The same is true.

3. The fluoronaphthyl compound of claim 2, wherein R is₁And R₂Each independently selected from: c₂～C₁₃Linear or branched alkyl of (a), and R₁And R₂The same is true.

4. The fluoronaphthyl compound of claim 1, wherein Rf is C₄～C₈Linear or branched perfluoroalkyl groups of (a).

5. The use of a fluoronaphthyl ester-containing compound as defined in any one of claims 1 to 4 as a film-forming aid for aqueous coatings or inks.