Acetic acid dicyclopentenyl oxypropyl ester and preparation method thereof, emulsion paint and preparation method and application thereof

Abstract

The invention provides dicyclopentenyl oxypropyl acetate and a preparation method thereof as well as emulsion paint and a preparation method and application thereof. The dicyclopentenyl oxypropyl acetate has a structure as shown in a formula (I) and / or a formula (II). The dicyclopentenyl oxypropyl acetate provided by the invention is used as a reaction type coalescing agent and is compounded with other common environment-friendly materials, so that the environment-friendly interior wall latex paint which is free of VOC (volatile organic compounds), SVOC (solid volatile organic compounds) or plasticizers and is appropriate in cost is obtained, and the latex paint also has excellent properties such as heat storage stability, water resistance, scrubbing resistance and blocking resistance, and is suitable for being used as an interior wall latex paint. And the paint film is not easy to crack.

Description

Technical Field

[0001] The invention belongs to the technical field of latex paint for interior walls of buildings and relates to dicyclopentenyloxypropyl acetate and a preparation method thereof, latex paint and a preparation method and application thereof. Background Art

[0002] VOC (volatile organic compounds), TVOC (total volatile organic compounds), and SVOC (semi-volatile organic compounds) have become key indicators of concern in many paint-related environmental standards and indoor air quality standards.

[0003] Film-forming aid is a very important additive in water-based synthetic resin latex paint. It is essentially an organic solvent and belongs to VOC, SVOC or plasticizer. It swells the latex resin particles and reduces its aggregation and fusion temperature, thereby reducing the minimum film-forming temperature (MFFT) of the latex resin, allowing the latex paint to form a uniform and continuous coating at a lower temperature.

[0004] CN115433495A discloses an environmentally friendly latex paint and a preparation method thereof, which adopts an antifreeze self-filming acrylic emulsion, a polymer-modified silicate, a hydroxyethyl cellulose ether, a pigment filler and a functional additive. The prepared latex paint does not contain TVOC, SVOC and preservatives. The limitation of the invention is that the requirements for the emulsion are relatively high, and the polymer-modified silicate needs to be modified. There are also disadvantages such as high cost and difficulty in selecting color matching pastes.

[0005] CN1195656A discloses a compound (DCPOMA, dicyclopentenyloxyethane and its derivatives) as a reactive film-forming aid, a method for improving the stability of the reactive film-forming aid, and a method for preparing a low molecular weight liquid polymer using these low molecular weight compounds. Such film-forming aids have the disadvantages of low film-forming efficiency and high cost due to their large molecular weight.

[0006] CN107663392A discloses a reactive film-forming aid, dodecene and its derivatives. The film-forming aid needs to be added with di-tert-butyl nitroxyl when used in latex paint. Di-tert-butyl nitroxyl has strong oxidizing property. When the latex paint prepared with the film-forming aid is stored, the cellulose ether in the component is easily destroyed and degraded, and the thickening effect is lost.

[0007] The document "Active Film-forming Aid - Dicyclopentenyloxyethyl Methacrylate" (Proceedings of the Seventh Seminar on the Development and Application of Acrylic Acid Technology, 2004, 72-75, 4 pages in total) introduces the mechanism and advantages of using dicyclopentenyloxyethyl methacrylate (DPOMA) as a polymerizable active film-forming aid in UV coatings and water-based emulsion coatings, and introduces some specific examples; this type of film-forming substance has two double bonds in its structure and a high cross-linking density. Compared with traditional film-forming aids, it has a greater impact on coating properties and is prone to high shrinkage, resulting in brittle and cracked coatings.

[0008] Therefore, it is desirable in the art to develop a film-forming aid that can be used in latex paints without volatile organic matter and that can provide latex paints with better performance. Summary of the invention

[0009] In view of the deficiencies of the prior art, the object of the present invention is to provide a dicyclopentenyloxypropyl acetate and a preparation method thereof, a latex paint and a preparation method and application thereof. The present invention develops an environmentally friendly interior wall latex paint that does not add VOC, SVOC or plasticizer, has a suitable cost and does not emit organic matter by developing and using a reactive film-forming aid dicyclopentenyloxypropyl acetate and compounding other common environmentally friendly materials.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a dicyclopentenyloxypropyl acetate, wherein the dicyclopentenyloxypropyl acetate has a structure as described in the following formula (I) and / or formula (II):

[0012]

[0013]

[0014] The dicyclopentenyloxypropyl acetate provided by the present invention can be used as a reactive film-forming aid, and can be compounded with other common environmentally friendly materials to obtain a cost-effective environmentally friendly interior wall latex paint without adding VOC, SVOC or plasticizer, and also solves some problems existing in the prior art solutions:

[0015] 1) The present invention can adopt the common odorless acrylic emulsion on the market, and does not need to use the self-filming emulsion. The MFFT of the emulsion can be freely selected according to the development requirements. Most self-filming emulsions do not have the problems of low film hardness and stickiness due to the low film-forming temperature.

[0016] 2) The dicyclopentenyloxypropyl acetate provided by the present invention has a polycycloolefin in its structure, and its crosslinking density is greatly reduced compared with DCPOMA containing two double bonds, thereby solving the problem that DCPOMA containing two double bonds has a high crosslinking density and is prone to brittle cracking of the coating film due to high shrinkage.

[0017] 3) Compared with dicyclopentenyloxyethane and its derivatives, the present invention uses propoxy to replace ethoxy, which enhances the solubility of the resin, significantly improves the film-forming efficiency, and reduces the dosage;

[0018] In a second aspect, the present invention provides a method for preparing dicyclopentenyloxypropyl acetate as described in the first aspect, the preparation method comprising the following steps:

[0019] (1) mixing dicyclopentadiene and propylene glycol, reacting to obtain an intermediate product, propylene glycol dicyclopentenyl ether;

[0020] (2) The propylene glycol-based biscyclopentenyl ether is mixed with acetic acid, a water-carrying agent, a polymerization inhibitor, and a catalyst, and reacted to obtain the biscyclopentenyloxypropyl acetate.

[0021] Reaction mechanism: When propylene glycol reacts with dicyclopentadiene, an acid must be used as a catalyst; propylene glycol and dicyclopentadiene react through an electrophilic addition reaction to generate propylene glycol dicyclopentenyl ether, and acetic acid and propylene glycol dicyclopentenyl ether react through an esterification reaction to generate dicyclopentenyloxypropyl acetate. The reaction equation is as follows:

[0022]

[0023] The products of the structures described by formula (I) and formula (II) in the reaction product are isomers and can be used as film-forming aids for latex paints without separation.

[0024] The reaction in step (2) of the present invention is an esterification reaction, in which the molar ratio of acetic acid to propylene glycol dicyclopentenyl ether, the amount of catalyst, the water-carrying agent and the polymerization inhibitor have a relatively large influence on the esterification rate of the product.

[0025] Preferably, the molar ratio of dicyclopentadiene to propylene glycol is 1:(1.05-1.2), for example, 1:1.05, 1:1.06, 1:1.08, 1:1.1, 1:1.12, 1:1.14, 1:1.16, 1:1.18, 1:1.2, etc.

[0026] Preferably, the catalyst used in the reaction in step (1) comprises p-toluenesulfonic acid.

[0027] Preferably, the reaction in step (1) is carried out under an inert gas atmosphere.

[0028] Preferably, the inert gas comprises nitrogen.

[0029] Preferably, the reaction temperature in step (1) is 130-140°C, such as 130°C, 135°C, 140°C, etc., and the reaction time is 2-4 hours, such as 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc.

[0030] Preferably, the mass ratio of the propylene glycol-based biscyclopentenyl ether to acetic acid is 1:(1.2-1.5), for example, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.

[0031] Preferably, the mass ratio of the propylene glycol-based dicyclopentenyl ether to the water-carrying agent is 1:(1-1.5), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.

[0032] Preferably, the water-carrying agent comprises toluene and / or cyclohexane.

[0033] Preferably, the water-carrying agent comprises toluene and cyclohexane in a mass ratio of 1:(0.8-1.2) (eg, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, etc.).

[0034] Preferably, the mass ratio of the propylene glycol-based biscyclopentenyl ether to the polymerization inhibitor is 1:(0.01-0.03), for example, 1:0.01, 1:0.02, 1:0.03, etc.

[0035] Preferably, the polymerization inhibitor comprises hydroquinone and / or p-hydroxyanisole.

[0036] Preferably, the polymerization inhibitor comprises hydroquinone and p-hydroxyanisole in a mass ratio of (3-8):1 (eg, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, etc.).

[0037] Preferably, the mass ratio of the propylene glycol biscyclopentenyl ether to the catalyst in step (2) is 100:(2-5), for example, 100:2, 100:2.5, 100:3, 100:3.5, 100:4, 100:4.5, 100:5, etc.

[0038] Preferably, the catalyst comprises dibutyltin oxide.

[0039] Preferably, the reaction temperature in step (2) is 135-145°C, such as 135°C, 140°C, 145°C, etc., and the reaction time is 2-5 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, etc.

[0040] Preferably, the reaction in step (2) is carried out under an inert gas atmosphere.

[0041] Preferably, the inert gas comprises nitrogen.

[0042] In a third aspect, the present invention provides a latex paint, wherein the raw materials for preparing the latex paint include the following components in parts by weight:

[0043]

[0044]

[0045] The water-based acrylic copolymer emulsion is a odorless emulsion with a residual monomer content of less than 0.05%.

[0046] The film-forming aid includes the dicyclopentenyloxypropyl acetate as described in the first aspect or the dicyclopentenyloxypropyl acetate prepared according to the preparation method as described in the second aspect.

[0047] In the present invention, the raw materials for preparing the latex paint are measured in parts by weight, and the amount of the aqueous acrylic copolymer emulsion can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, etc.

[0048] In the present invention, the raw materials for preparing the latex paint are measured in parts by weight, and the amount of pigment used can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, etc.

[0049] In the present invention, the raw materials for preparing the latex paint are measured in parts by weight, and the amount of filler used can be 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 65 parts, etc.

[0050] In the present invention, the raw materials for preparing the latex paint are calculated by weight, and the amount of the film-forming aid used can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.

[0051] In the present invention, the raw materials for preparing the latex paint are calculated by weight, and the dosage of other additives can be 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.4 parts, etc.

[0052] In the present invention, the raw materials for preparing the latex paint are measured in parts by weight, and the amount of deionized water used can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, etc.

[0053] Preferably, the pigment comprises rutile titanium dioxide.

[0054] Preferably, the filler includes any one of kaolin, calcium carbonate, talc, wollastonite powder, barite powder, or a combination of at least two of them.

[0055] Preferably, the filler includes 0-20 parts of kaolin (for example, 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, etc.), 0-25 parts of calcium carbonate (for example, 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, etc.), 0-10 parts of talc (for example, 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.), and 0-10 parts of barite powder (for example, 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.).

[0056] Preferably, the other additives include any one or a combination of at least two of a composite drying agent, a dispersant, a wetting agent, a pH adjuster, a defoaming agent, a surfactant antifreeze agent, a bactericidal preservative and a mildew preventive, a cellulose ether thickener, a polyurethane thickener, and an acrylic thickener.

[0057] Preferably, the other additives include 0.1-0.5 parts of a composite drying agent (e.g., 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, etc.), 0.3-1.5 parts of a dispersant (e.g., 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc.), Wetting agent 0.1-0.6 parts (e.g. 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, etc.), pH adjuster 0.1-0.5 parts (e.g. 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, etc.), defoaming agent 0.3-1.0 parts (e.g. 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, etc.), .9 parts, 1 part, etc.), surfactant antifreeze 0.2-0.8 parts (for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, etc.), bactericide, preservative and mildew preventive 0.1-0.7 parts (for example, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, etc.), cellulose ether thickener 0.1-0. 6 parts (for example 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, etc.), polyurethane thickener 0.1-0.6 parts (for example 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, etc.), acrylic thickener 0.1-0.6 parts (for example 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, etc.).

[0058] Preferably, the composite drier includes any one of cobalt, zirconium and zinc salts of cyclohexane acid or a combination of at least two thereof. A small amount of cyclohexane acid salt composite drier cobalt cyclohexane acid salt is added to the latex paint formula provided by the present invention to replace the strongly oxidizing di-tert-butyl nitroxyl, thereby improving the stability of the latex paint; in the early stage of the paint film drying process, dicyclopentenyloxypropyl acetate swells the latex resin particles to help it form a uniform and continuous film, and then through oxidative free radical polymerization, dicyclopentenyloxypropyl acetate and other components of the formula such as hydroxyl groups on the hydroxyethyl cellulose ether structure, carboxyl groups on the latex resin chain and the active film-forming aid itself undergo cross-linking reactions, thereby solving the problems of volatilization of traditional film-forming aids and residual stickiness of the paint film, while improving the water resistance of the latex paint film.

[0059] Preferably, the pH adjuster comprises a potassium methyl silicate pH adjuster.

[0060] Preferably, the bactericidal, antiseptic and mildew-proof agent comprises a bactericide and an antiseptic and mildew-proof agent.

[0061] Preferably, the fungicide is a formaldehyde-free fungicide.

[0062] Preferably, the preservative and mildew preventer comprises a slow-release preservative and mildew preventer.

[0063] Preferably, the acrylic thickener comprises an associative acrylic thickener.

[0064] As a preferred technical solution of the present invention, the raw materials for preparing the latex paint include the following components in parts by weight:

[0065]

[0066]

[0067] In a fourth aspect, the present invention provides a method for preparing the latex paint as described in the third aspect, the preparation method comprising the following steps:

[0068] The latex paint is obtained by mixing and dispersing the water-based acrylic copolymer emulsion, pigment, filler, film-forming aid, other aids and deionized water in a prescribed amount.

[0069] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0070] (1) Add part of deionized water and cellulose ether thickener into a high-speed dispersion kettle, start stirring, and stir at a low speed of 150 to 250 rpm;

[0071] (2) After stirring for 3 to 10 minutes, add dispersant, wetting agent, pH adjuster, part of defoamer, bactericide and other additives in sequence;

[0072] (3) After stirring for 3 to 10 minutes, add pigment, kaolin, talcum powder, calcium carbonate, barite powder and other powders in turn. During the production process, gradually increase the stirring speed according to the slurry viscosity, powder feeding speed and slurry splashing to ensure that there is no powder accumulation and serious powder flying; use a small amount of water to clean the powder on the cylinder wall and the stirring shaft;

[0073] (4) After the powder is added, disperse it at high speed (about 1800 rpm) for 15 to 20 minutes until the slurry fineness is less than 50 microns;

[0074] (5) adding part of the deionized water and all of the aqueous acrylic copolymer emulsion at a moderate stirring speed (about 900 rpm) and stirring for 5 to 15 minutes;

[0075] (6) Add the film-forming aid and stir for 3 to 10 minutes at a medium stirring speed (about 900 rpm);

[0076] (7) then adding the surfactant antifreeze agent, the remaining defoaming agent, and the composite drying agent in sequence at a medium stirring speed (about 900 rpm) and stirring for 3 to 10 minutes;

[0077] (8) Then, add the polyurethane thickener, acrylic thickener, preservative and mildew inhibitor and the remaining deionized water in sequence at a medium stirring speed (about 900 rpm) and stir for 10 to 20 minutes to ensure uniform stirring; take samples for inspection and filter with an 80-mesh filter for packaging if they pass the inspection.

[0078] In a fifth aspect, the present invention provides a use of the latex paint as described in the third aspect in a building interior wall coating.

[0079] Compared with the prior art, the present invention has at least the following beneficial effects:

[0080] The dicyclopentenyloxypropyl acetate provided by the present invention is used as a reactive film-forming aid and is compounded with other common environmentally friendly materials to obtain an environmentally friendly interior wall latex paint without adding VOC, SVOC or plasticizer and with appropriate cost. The latex paint also has excellent comprehensive properties, as shown below:

[0081] (1) Low emission of volatile organic compounds. Excellent test results according to the microchamber method (ISO 16000-3:2011, 16000-6:2011, 16000-9:2006). 3 days: TVOC (C6-C 16 ): less than 0.015mg / m 3 SVOC(C6-C 22 ): less than 0.02mg / m 3 ; 28 days: VOC (C6-C 16 ): less than 0.005mg / m 3 SVOC(C6-C 22 ): less than 0.02mg / m 3 ; Meet the most stringent indoor air quality standards such as German Rhine certification and French A+;

[0082] (2) The emulsion in the formula has a wide range of choices, and there is no need to use a low MFFT self-filming acrylic emulsion like in the background art;

[0083] (3) Paint stability: After being stored in a constant temperature box at 50°C for one month, there was no deterioration, crusting, precipitation or obvious stratification, and no significant change in viscosity;

[0084] (4) Coating properties: scrub resistance and water resistance are better than those using traditional film-forming agents such as alcohol ester twelve and COASOL 290; the coating hardness is slightly higher than that of traditional film-forming agents; a 600 micron thick film has no cracking at room temperature, which is better than other reactive film-forming agents;

[0085] (5) The amount of film-forming aid used is slightly higher than that of traditional film-forming aids, but much lower than that of other reactive film-forming aids. DETAILED DESCRIPTION

[0086] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0087] Preparation Example 1

[0088] In this preparation example, a dicyclopentenyloxypropyl acetate is provided, and the preparation method comprises the following steps:

[0089] 1) Synthesis of propylene glycol dicyclopentenyl ether

[0090] Propylene glycol and refined dicyclopentadiene in a molar ratio of 1.1:1 are added to a normal pressure stainless steel reactor equipped with a stirrer, a thermometer, a condenser and an oil-water separator, and nitrogen is passed through the reactor for protection. p-Toluenesulfonic acid (the amount of which is 2 wt.% of dicyclopentadiene) is slowly added, stirred, and the temperature is raised to reflux (135° C.) for 3 hours. After cooling, sodium carbonate aqueous solution is added for neutralization, and then washed with distilled water for 3 times to obtain a crude product of propylene glycol dicyclopentenyl ether; and then vacuum distillation is performed to obtain propylene glycol dicyclopentenyl ether.

[0091] 2) Synthesis of dicyclopentenyloxypropyl acetate

[0092] Propylene glycol dicyclopentenyl ether (1 part, by mass, the same below), acetic acid (1.3 parts), a water-carrying agent (1.2 parts of a mixture of toluene and cyclohexane, with a mass ratio of 1:1), a polymerization inhibitor (a mixture of hydroquinone and p-hydroxyanisole, wherein 0.01 parts of hydroquinone and 0.002 parts of p-hydroxyanisole) and a catalyst dibutyltin oxide (added in an amount of 3wt.% of propylene glycol dicyclopentenyl ether) are added to a normal pressure stainless steel reaction container equipped with an agitator, a thermometer, a condenser and an oil-water separator. Under nitrogen protection, the reaction temperature is controlled and reflux (140° C.) is maintained. The reaction is stopped after 4 hours of reaction (the reaction end point is when the water output is close to the theoretical value and the acid value of the reaction system remains unchanged for a long time), the temperature is reduced and the reaction is filtered to separate the dibutyltin oxide, the water-carrying agent is separated by atmospheric distillation, and the excess acetic acid is separated by reduced pressure distillation to obtain the dicyclopentenyloxypropyl acetate.

[0093] The present invention selects two MFFT odorless and environmentally friendly emulsions, two emulsion dosages, uses dicyclopentenyloxypropyl acetate as a film-forming aid, and designs three embodiments; selects alcohol ester dodecahydrate, COASOL 290 and dicyclopentadienyloxyethyl acrylate (DPOA) as film-forming aids, and designs six comparative examples, as shown in the following embodiments and comparative examples.

[0094] Examples 1 to 3, Comparative Examples 1 to 6

[0095] A latex paint is provided respectively, and the specific formula (parts by weight) is shown in Table 1.

[0096] The preparation method comprises the following steps:

[0097] (1) Add 1 to the dispersion tank according to the formula in Table 1, adjust the speed of the disperser to 200 rpm, then add 2, 3, 4, 5, 6 in sequence, disperse for 5 minutes, then add 7, 8, disperse for 5 minutes, then add 9, 10, 11, 12, 13 in sequence, and gradually increase the stirring speed according to the powder feeding speed, slurry viscosity, and splashing to ensure that there is no powder accumulation and serious powder flying; after the powder is added, use 14 (deionized water) to clean the powder on the cylinder wall and the stirring shaft; adjust the speed of the disperser to 1800 rpm, high-speed dispersion for 20 minutes, stop the machine, test the slurry fineness, and the fineness is less than 50 microns, which is qualified, put the slurry into the blending tank, and use 15 (deionized water) to clean the dispersion tank, and the cleaning liquid is also put into the blending tank;

[0098] (2) Adjust the speed of the blending cylinder disperser to 900 rpm, add 16, and stir for 5 minutes;

[0099] (3) 17 and 18 (if any) are premixed in a container, added to the blending tank, and stirred for 5 minutes;

[0100] (4) Add 19, 20, 21, 22, and 23 in sequence and stir for 5 minutes;

[0101] (5) 24 was diluted with deionized water at a ratio of 1:1, and the amount of water was deducted from 25, and stirred for 5 minutes;

[0102] (6) Use the remaining 25 (deionized water) to clean the additive container, tools, cylinder wall and stirring shaft, and add all the cleaning water into the blending cylinder;

[0103] (7) Stir at 900 rpm for 15 minutes to ensure uniform mixing, then stop the machine to take samples for inspection;

[0104] (8) After passing the test, filter and package with an 80-mesh filter in time.

[0105] Table 1

[0106]

[0107]

[0108] The above-mentioned Examples 1-3 and Comparative Examples 1-6 were subjected to performance testing, and the testing method was as follows:

[0109] The TVOC content is determined in accordance with JG / T 481-2015 "Low Volatile Organic Compound (VOC) Water-based Interior Wall Coating Materials"; the SVOC content is determined in accordance with ISO16000-25-2011 "Indoor Air Part 25: Determination of Semi-volatile Organic Compound Emissions from Building Products-Microchamber Method";

[0110] The thermal storage stability of the coating is tested in accordance with GB / T 6753.3-1986 "Test method for storage stability of coatings";

[0111] The water resistance of the coating film is tested according to GB / T 1733-1993 "Determination of water resistance of paint film";

[0112] The scrub resistance of the coating film shall be tested in accordance with GB / T 9756-2018 "Synthetic resin emulsion interior wall coating 5.5.11 scrub resistance";

[0113] The anti-blocking property of the coating film refers to GB / T 23982-2009 "Determination of Anti-blocking Property of Wood Coatings". The substrate is asbestos-free cement fiberboard that meets the requirements of GB / T9271-2008, with a size of 150 mm × 70 mm. Each sample is evenly coated with two coats using a 7-inch wolf hair brush, with the first coat weighing 5.5 grams and the second coat weighing 4.5 grams. The recoating interval is 2 hours. Eight samples are prepared for each sample. The samples are dried for 7 days and 28 days under standard conditions. After the samples are dried for a specified time, the painted surfaces of two identical test samples are directly contacted and placed horizontally on a flat and hard test bench, and a 1 kg weight is placed in the center of the back of the upper sample. They are placed under standard conditions for 24 hours and evaluated in accordance with GB / T 23982-2009 9.

[0114] Thick film cracking: Under the test environment specified in GB / T9278, apply one coat of the film using a 600 micron intermittent wet film preparation device on the asbestos-free cement fiberboard that meets the requirements of GB / T9271-2008. Dry the film for the specified time under standard conditions, observe and judge the cracking, and observe with a 50x magnifying glass when necessary.

[0115] The performance data measured according to the above detection method are shown in Table 2.

[0116] The present invention conducted two groups of comparative tests, Example 1, Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were the first group, and the emulsion content was about 30%; Example 3, Comparative Example 4, Comparative Example 5, and Comparative Example 6 were the second group, and the emulsion content was about 11%.

[0117] Table 2

[0118]

[0119] According to Table 2, the TVOC content in the latex paint provided by Comparative Examples 1 and 4 is very high, the SVOC content in the latex paint provided by Comparative Examples 2 and 5 is very high, and there is also relatively serious adhesion; the latex paints provided by Comparative Examples 3 and 6 have relatively serious thick film cracking defects; the TVOC and SVOC contents contained in the latex paints provided by Example 1, Example 2, and Example 3 are much lower than those in ordinary latex paints, and have good paint film properties such as water resistance and scrub resistance, and also solve the problem of easy adhesion of high boiling point film-forming aids (Comparative Example 2), thereby having better practicality and environmental protection.

[0120] In summary, the present invention develops a reactive film-forming agent, dicyclopentenyloxypropyl acetate, as a film-forming agent to replace the volatile film-forming agent required to be added in the traditional latex paint formula. Compared with ordinary latex paint, the content of TVOC and SVOC in the latex paint prepared by the present invention is much lower than the relevant standards, and the water resistance and scrub resistance are better than the latex paint of the same PVC. At the same time, the problem of poor anti-adhesion of high-boiling point film-forming agents is improved; compared with other reactive film-forming agents, it also has the advantages of not easy to crack, small addition amount, good stability, and more practical performance.

[0121] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the dicyclopentenyloxypropyl acetate and its preparation method, latex paint and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A dicyclopentenyloxypropyl acetate, characterized in that The dicyclopentenyloxypropyl acetate has the structure described in the following formula (I) and / or formula (II):

2. A method for preparing dicyclopentenyloxypropyl acetate as claimed in claim 1, characterized in that: The preparation method comprises the following steps: (1) mixing dicyclopentadiene and propylene glycol, reacting to obtain an intermediate product, propylene glycol dicyclopentenyl ether; (2) The propylene glycol-based biscyclopentenyl ether is mixed with acetic acid, a water-carrying agent, a polymerization inhibitor, and a catalyst, and reacted to obtain the biscyclopentenyloxypropyl acetate.

3. The preparation method according to claim 2, characterized in that: The molar ratio of dicyclopentadiene to propylene glycol is 1:(1.05-1.2); Preferably, the catalyst used in the reaction in step (1) comprises p-toluenesulfonic acid; Preferably, the reaction in step (1) is carried out under an inert gas atmosphere; Preferably, the inert gas comprises nitrogen; Preferably, the reaction temperature in step (1) is 130-140° C., and the reaction time is 2-4 hours.

4. The preparation method according to claim 2 or 3, characterized in that: The mass ratio of the propylene glycol dicyclopentenyl ether to acetic acid is 1:(1.2-1.5); Preferably, the mass ratio of the propylene glycol-based dicyclopentenyl ether to the water-carrying agent is 1:(1-1.5); Preferably, the water-carrying agent comprises toluene and / or cyclohexane; Preferably, the water-carrying agent comprises toluene and cyclohexane in a mass ratio of 1:(0.8-1.2); Preferably, the mass ratio of the propylene glycol-based biscyclopentenyl ether to the polymerization inhibitor is 1:(0.01-0.03); Preferably, the polymerization inhibitor comprises hydroquinone and / or p-hydroxyanisole; Preferably, the polymerization inhibitor comprises hydroquinone and p-hydroxyanisole in a mass ratio of (3-8):1; Preferably, the mass ratio of the propylene glycol dicyclopentenyl ether to the catalyst in step (2) is 100:(2-5); Preferably, the catalyst comprises dibutyltin oxide; Preferably, the reaction temperature in step (2) is 135-145° C., and the reaction time is 2-5 hours; Preferably, the reaction in step (2) is carried out under an inert gas atmosphere; Preferably, the inert gas comprises nitrogen.

5. A latex paint, characterized in that: The raw materials for preparing the latex paint include the following components in parts by weight: The film-forming aid includes the dicyclopentenyloxypropyl acetate as claimed in claim 1 or the dicyclopentenyloxypropyl acetate prepared according to the preparation method as claimed in any one of claims 2 to 4.

6. The latex paint according to claim 5, characterized in that: The pigment includes rutile titanium dioxide; Preferably, the filler comprises any one of kaolin, calcium carbonate, talc, wollastonite powder, barite powder, or a combination of at least two thereof; Preferably, the filler includes 0-20 parts of kaolin, 0-25 parts of calcium carbonate, 0-10 parts of talc, and 0-10 parts of barite powder.

7. The latex paint according to claim 5 or 6, characterized in that: The other additives include any one or a combination of at least two of a composite drying agent, a dispersant, a wetting agent, a pH adjuster, a defoaming agent, a surfactant antifreeze agent, a bactericidal preservative and a mildew preventive, a cellulose ether thickener, a polyurethane thickener, and an acrylic thickener; Preferably, the other additives include 0.1-0.5 parts of composite drying agent, 0.3-1.5 parts of dispersant, 0.1-0.6 parts of wetting agent, 0.1-0.5 parts of pH adjusting agent, 0.3-1.0 parts of defoaming agent, 0.2-0.8 parts of surfactant antifreeze agent, 0.1-0.7 parts of bactericide, preservative and mildewproof agent, 0.1-0.6 parts of cellulose ether thickener, 0.1-0.6 parts of polyurethane thickener, and 0.1-0.6 parts of acrylic thickener; Preferably, the composite drying agent comprises any one or a combination of at least two of naphthenic acid salts of cobalt, zirconium and zinc; Preferably, the pH adjuster includes a potassium methyl silicate pH adjuster; Preferably, the bactericidal, antiseptic and mildew-proof agent comprises a bactericide and an antiseptic and mildew-proof agent; Preferably, the bactericide is a formaldehyde-free bactericide; Preferably, the preservative and mildew preventer comprises a slow-release preservative and mildew preventer.

8. The latex paint according to any one of claims 5 to 7, characterized in that: The raw materials for preparing the latex paint include the following components in parts by weight:

9. A method for preparing a latex paint as claimed in any one of claims 5 to 8, characterized in that: The preparation method comprises the following steps: The latex paint is obtained by mixing and dispersing the water-based acrylic copolymer emulsion, pigment, filler, film-forming aid, other aids and deionized water in a prescribed amount.

10. Use of the latex paint as claimed in any one of claims 5 to 8 in a building interior wall coating.

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