Bicyclopentenyloxypropyl acetate, a preparation method thereof, latex paint and a preparation method and application thereof

Abstract

The application provides a bicyclopentenyl oxypropyl acetate, a preparation method thereof, a latex paint and a preparation method and application thereof, and the bicyclopentenyl oxypropyl acetate has a structure as shown in formula (I) and / or formula (II). The bicyclopentenyl oxypropyl acetate provided by the application is used as a reactive film-forming auxiliary agent, and other common environmentally-friendly materials are compounded to obtain an environmentally-friendly interior wall latex paint which does not add VOC, SVOC or plasticizer and has a suitable cost. The latex paint also has excellent heat storage stability, water resistance, washability, anti-blocking property and the like, and the paint film is not prone to cracking.

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 protection standards and indoor air quality standards.

[0003] Film-forming aids are very important additives in water-based synthetic resin latex paints. They are essentially organic solvents and belong to VOC, SVOC or plasticizers. They swell the latex resin particles, lowering their coalescence and fusion temperature, thereby lowering 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. The paint adopts an antifreeze self-filming acrylic emulsion, a polymer-modified silicate, a hydroxyethyl cellulose ether, a pigment and a filler, and a functional additive. The latex paint produced does not contain TVOC, SVOC, and preservatives. The limitation of this 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 suffer from low film-forming efficiency and high cost due to their high molecular weight.

[0006] CN107663392A discloses a reactive film-forming agent, dodecene and its derivatives. The film-forming agent needs to be added to latex paint when used. Di-tert-butyl nitroxyl has strong oxidizing properties. During storage, the cellulose ether in the latex paint prepared with the film-forming agent is easily destroyed and degraded, thus losing its thickening effect.

[0007] The document "Active Film-Forming Aid - Dicyclopentenyloxyethyl Methacrylate" (Proceedings of the 7th 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-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 agents, it has a greater impact on coating properties and is prone to high shrinkage, resulting in brittle and cracked coatings.

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

[0009] To address the shortcomings of the prior art, the present invention provides biscyclopentenyloxypropyl acetate, a preparation method thereof, a latex paint, and its preparation method and application. By developing and using biscyclopentenyloxypropyl acetate, a reactive film-forming aid, and compounding it with other common environmentally friendly materials, the present invention develops an environmentally friendly interior wall latex paint that is free of VOCs, SVOCs, or plasticizers, is cost-effective, and emits no organic volatilization.

[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 the structure 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, when compounded with other common environmentally friendly materials, can produce a cost-effective environmentally friendly interior wall latex paint that does not add VOCs, SVOCs, or plasticizers. This also solves some of the problems existing in existing technical solutions:

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

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

[0017] 3) Compared with dicyclopentenyloxyethane and its derivatives, the present invention uses propoxy instead of 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-based dicyclopentenyl ether;

[0020] (2) mixing the propylene glycol-based biscyclopentenyl ether with acetic acid, a water-carrying agent, a polymerization inhibitor, and a catalyst, and reacting the mixture 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 undergo an electrophilic addition reaction to form propylene glycol dicyclopentenyl ether, which then undergoes an esterification reaction with acetic acid to form 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 biscyclopentenyl ether, the amount of catalyst, the water-carrying agent and the polymerization inhibitor have a relatively large impact 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 of step (1) includes 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 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 biscyclopentenyl 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 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 described in the first aspect or the dicyclopentenyloxypropyl acetate prepared according to the preparation method described in the second aspect.

[0047] In the present invention, the raw materials for preparing the latex paint are calculated by weight, and the amount of the water-based 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 calculated 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 calculated 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 amount of other additives used 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 calculated 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, and 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 regulator, a defoaming agent, a surfactant antifreeze agent, a bactericidal preservative and mildew inhibitor, a cellulose ether thickener, a polyurethane thickener, and an acrylic thickener.

[0057] Preferably, the other additives include 0.1 to 0.5 parts of a composite drying agent (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, etc.), 0.3 to 1.5 parts of a dispersant (e.g., 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 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, antiseptic 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 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, etc.), 0.1 to 0.6 parts of polyurethane thickener (for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, etc.), 0.1 to 0.6 parts of acrylic thickener (for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, etc.).

[0058] Preferably, the composite drier comprises any one or a combination of at least two of cobalt, zirconium, and zinc cyclohexane salts. A small amount of cobalt cyclohexane salt composite drier, cyclopentenyloxypropyl acetate, 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 stages of the paint film drying process, dicyclopentenyloxypropyl acetate swells the latex resin particles, helping them form a uniform and continuous film. Then, through oxidative free radical polymerization, dicyclopentenyloxypropyl acetate undergoes a cross-linking reaction with other components of the formula, such as the hydroxyl groups on the hydroxyethyl cellulose ether structure, the carboxyl groups on the latex resin chain, and the active film-forming aid itself, thereby solving the problems of volatilization of traditional film-forming aids and residual stickiness in the paint film, while also improving the water resistance of the latex paint film.

[0059] Preferably, the pH adjuster includes 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 antiseptic and mildew preventer comprises a slow-release antiseptic 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 according to 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 additives and deionized water in a formulated 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 to a high-speed dispersing 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 regulator, part of defoamer, fungicide and other additives in sequence;

[0072] (3) After stirring for 3 to 10 minutes, add pigment, kaolin, talc, calcium carbonate, barite powder and other powders in sequence. 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 at high speed (about 1800 rpm) for 15 to 20 minutes until the slurry fineness is less than 50 microns;

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

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

[0076] (7) Then, add the surfactant antifreeze, the remaining defoamer, and the composite drying agent in sequence at a moderate stirring speed (about 900 rpm) and stir for 3 to 10 minutes;

[0077] (8) Then, add the polyurethane thickener, acrylic thickener, antiseptic 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 after passing the inspection.

[0078] In a fifth aspect, the present invention provides a use of the latex paint 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] By using the dicyclopentenyloxypropyl acetate provided by the present invention as a reactive film-forming aid and compounding with other common environmentally friendly materials, a cost-effective environmentally friendly interior wall latex paint without adding VOCs, SVOCs or plasticizers is obtained. 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 micro-chamber 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 ; Comply with the most stringent indoor air quality standards in the world, such as German Rhine certification and French A+;

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

[0083] (3) Paint stability: After storage in a constant temperature box at 50°C for one month, there is 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 solutions of the present application are further illustrated below by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0087] Preparation Example 1

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

[0089] 1) Synthesis of propylene glycol-based dicyclopentenyl ether

[0090] Propylene glycol and refined dicyclopentadiene in a molar ratio of 1.1:1 were added to a normal-pressure stainless steel reactor equipped with a stirrer, a thermometer, a condenser, and an oil-water separator, protected by nitrogen, and p-toluenesulfonic acid (2 wt.% of dicyclopentadiene) was slowly added, stirred, and heated to reflux (135°C) for 3 hours, and then cooled, neutralized with an aqueous sodium carbonate solution, and washed with distilled water three times to obtain a crude product of propylene glycol-based dicyclopentenyl ether; and then subjected to vacuum rectification to obtain the propylene glycol-based dicyclopentenyl ether.

[0091] 2) Synthesis of dicyclopentenyloxypropyl acetate

[0092] Propylene glycol-based dicyclopentenyl ether (1 part, mass parts, the same below), acetic acid (1.3 parts), a water-carrying agent (a mixture of toluene and cyclohexane in a mass ratio of 1:1, 1.2 parts), a polymerization inhibitor (a mixture of hydroquinone and p-hydroxyanisole, 0.01 parts of hydroquinone and 0.002 parts of p-hydroxyanisole), and a catalyst dibutyl tin oxide (added in an amount of 3 wt.% of propylene glycol-based dicyclopentenyl ether) were added to a normal-pressure stainless steel reaction vessel equipped with a stirrer, a thermometer, a condenser, and an oil-water separator, and the reaction temperature was controlled under nitrogen protection, and kept at reflux (140°C) for 4 hours, and then the reaction was stopped (with the water output close to the theoretical value and the acid value of the reaction system unchanged for a long time as the reaction endpoint), filtered after cooling, and the dibutyl tin oxide was separated, and the water-carrying agent was separated by normal-pressure distillation, and the excess acetic acid was separated by vacuum distillation to obtain the dicyclopentenyloxypropyl acetate.

[0093] In the present application, two kinds of MFFT odorless environmentally friendly emulsions were selected, and the two kinds of emulsions were used in an amount, and dicyclopentenyloxypropyl acetate was used as a film-forming aid, and three embodiments were designed; alcohol ester twelve, COASOL 290, and dicyclopentadienyl oxyethyl acrylate (DPOA) were selected as film-forming aids, and six comparative examples were designed, and the specific embodiments are shown in the following examples and comparative examples.

[0094] Examples 1-3 and Comparative Examples 1-6

[0095] A latex paint was provided, and the specific formula (mass parts) 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. During the process, gradually increase the stirring speed according to the powder feeding speed and the slurry viscosity and splashing situation to ensure that there is no powder accumulation and serious powder flying; after the powder is added, use 14 (deionized water) to clean the cylinder wall and the powder on the stirring shaft; adjust the speed of the disperser to 1800 rpm, disperse at high speed 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, clean the dispersion tank with 15 (deionized water), and put the cleaning liquid 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, then 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 to the blending tank;

[0103] (7) Stir the machine 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 Examples 1-3 and Comparative Examples 1-6 were subjected to performance testing using the following methods:

[0109] TVOC content determination according to JG / T 481-2015 "Low volatile organic compounds (VOC) water-based interior wall coating materials"; SVOC content determination according to ISO 16000-25-2011 "Indoor air - Part 25: Determination of emissions of semi-volatile organic compounds from building products - Micro-chamber method";

[0110] Coating heat storage stability is detected according to GB / T 6753.3-1986 "Paint storage stability test method";

[0111] Coating film water resistance is detected according to GB / T 1733-1993 "Paint film water resistance determination method";

[0112] Coating film washability is detected according to GB / T 9756-2018 "Synthetic resin emulsion interior wall coating 5.5.11 washability";

[0113] Coating film anti-blocking property refers to GB / T 23982-2009 "Wood coating anti-blocking property determination method", the substrate uses the asbestos-free cement fiber board in accordance with GB / T9271-2008, the size is 150 millimeters x 70 millimeters, each sample plate is evenly coated with a 7-inch wolf hair brush, 5.5 grams for the first pass and 4.5 grams for the second pass, with a 2-hour interval between re-coating; 8 sample plates are prepared for each sample, and the sample plates are dried for 7 days and 28 days under standard conditions respectively; after the sample plates are dried for the specified time, two identical test sample plates are placed in direct contact, and a 1-kilogram weight is placed on the back center of the upper sample plate, and the sample plates are placed horizontally on a flat and hard test table for 24 hours under standard conditions, and the evaluation is carried out according to GB / T 23982-2009 9;

[0114] Thick film cracking: under the test environment specified in GB / T9278, a 600-micron intermittent wet film applicator is used to coat a pass on the asbestos-free cement fiber board in accordance with GB / T9271-2008, and the cracking condition is observed and evaluated after drying for the specified time under standard conditions, and a 50x magnifying lens is used for observation if necessary.

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

[0116] Two groups of comparative tests are made in the present application, example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 are the first group, and the emulsion content is about 30%; example 3, comparative example 4, comparative example 5 and comparative example 6 are the second group, and the emulsion content is about 11%.

[0117] Table 2

[0118]

[0119] According to Table 2, the latex paint provided by Comparative Example 1 and Comparative Example 4 has a high TVOC content, the latex paint provided by Comparative Example 2 and Comparative Example 5 has a high SVOC content, and there is a relatively serious blocking; the latex paint provided by Comparative Example 3 and Comparative Example 6 has a relatively serious thick film cracking defect; the latex paint provided by Example 1, Example 2 and Example 3 has a far lower content of TVOC and SVOC than the content of TVOC and SVOC in ordinary latex paint, has good film properties such as water resistance and washability, and also solves the problem of easy blocking of high-boiling-point film-forming additives (Comparative Example 2), thereby having better practicality and environmental protection.

[0120] In summary, by developing a reactive film-forming additive, bicyclopentenyl oxyl propyl acetate, as a film-forming additive to replace the volatile film-forming additive required in the traditional latex paint formula, the content of TVOC and SVOC in the latex paint prepared by the present application is far lower than the relevant standard, the water resistance and washability are better than those of the same PVC latex paint, and the problem of poor blocking resistance of high-boiling-point film-forming additives is improved; compared with other reactive film-forming additives, the present application has the advantages of not being easy to crack, having a small amount of addition, and good stability, and has better practicality.

[0121] The applicant declares that the bicyclopentenyl oxyl propyl acetate, the preparation method thereof, the latex paint and the preparation method and application thereof of the present application are illustrated by the above examples, but the present application is not limited to the above examples, i.e., it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement on the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.

Claims

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

2. A method for preparing biscyclopentenyloxypropyl 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).

4. The preparation method according to claim 2, characterized in that The catalyst used in the reaction of step (1) includes p-toluenesulfonic acid.

5. The preparation method according to claim 2, characterized in that The reaction in step (1) is carried out under an inert gas atmosphere.

6. The preparation method according to claim 5, characterized in that The inert gas includes nitrogen.

7. The preparation method according to claim 2, characterized in that The reaction temperature in step (1) is 130-140° C., and the reaction time is 2-4 hours.

8. The preparation method according to claim 2, characterized in that The mass ratio of the propylene glycol biscyclopentenyl ether to the acetic acid is 1:(1.2-1.5).

9. The preparation method according to claim 2, characterized in that The mass ratio of the propylene glycol dicyclopentenyl ether to the water-carrying agent is 1:(1-1.5).

10. The preparation method according to claim 2, characterized in that The water-carrying agent includes toluene and / or cyclohexane.

11. The preparation method according to claim 10, characterized in that: The water-carrying agent comprises toluene and cyclohexane in a mass ratio of 1: (0.8-1.2).

12. The preparation method according to claim 2, characterized in that The mass ratio of the propylene glycol biscyclopentenyl ether to the polymerization inhibitor is 1:(0.01-0.03).

13. The preparation method according to claim 2, characterized in that The polymerization inhibitor includes hydroquinone and / or p-hydroxyanisole.

14. The preparation method according to claim 13, characterized in that The polymerization inhibitor comprises hydroquinone and p-hydroxyanisole in a mass ratio of (3-8):

1.

15. The preparation method according to claim 2, characterized in that The mass ratio of propylene glycol biscyclopentenyl ether to the catalyst in step (2) is 100:(2~5).

16. The preparation method according to claim 2, characterized in that The catalyst in step (2) includes dibutyltin oxide.

17. The preparation method according to claim 2, characterized in that The reaction temperature in step (2) is 135-145° C., and the reaction time is 2-5 hours.

18. The preparation method according to claim 2, characterized in that The reaction in step (2) is carried out under an inert gas atmosphere.

19. The preparation method according to claim 18, characterized in that The inert gas includes nitrogen.

20. A latex paint, characterized in that: The raw materials for preparing the latex paint include the following components in parts by weight: 10-40 parts of water-based acrylic copolymer emulsion; 5~25 parts of pigment; Filler 0~65 parts; 1~5 parts of film-forming aid; Other additives 1.5~7.4 parts; 20-50 parts of deionized water; The film-forming aid includes the dicyclopentenyloxypropyl acetate according to claim 1 or the dicyclopentenyloxypropyl acetate prepared according to the preparation method according to any one of claims 2 to 19.

21. The latex paint according to claim 20, characterized in that The pigment includes rutile titanium dioxide.

22. The latex paint according to claim 20, characterized in that The filler includes any one of kaolin, calcium carbonate, talc, wollastonite powder, and barite powder, or a combination of at least two of them.

23. The latex paint according to claim 22, characterized in that The filler includes 0-20 parts of kaolin, 0-25 parts of calcium carbonate, 0-10 parts of talc powder, and 0-10 parts of barite powder.

24. The latex paint according to claim 20, 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 regulator, a defoaming agent, a surfactant antifreeze agent, a bactericidal preservative and mildew preventive, a cellulose ether thickener, a polyurethane thickener, and an acrylic thickener.

25. The latex paint according to claim 24, characterized in that The other additives include 0.1-0.5 parts of a composite drying agent, 0.3-1.5 parts of a dispersant, 0.1-0.6 parts of a wetting agent, 0.1-0.5 parts of a pH regulator, 0.3-1.0 parts of a defoaming agent, 0.2-0.8 parts of a surfactant antifreeze agent, 0.1-0.7 parts of a bactericidal, preservative and mildew-proof agent, 0.1-0.6 parts of a cellulose ether thickener, 0.1-0.6 parts of a polyurethane thickener, and 0.1-0.6 parts of an acrylic thickener.

26. The latex paint according to claim 24, characterized in that The composite drying agent includes any one of naphthenic acid salts of cobalt, zirconium and zinc, or a combination of at least two of them.

27. The latex paint according to claim 24, characterized in that The pH adjuster includes potassium methyl silicate pH adjuster.

28. The latex paint according to claim 24, characterized in that The bactericidal, antiseptic and mildew-proof agent comprises a bactericide and an antiseptic and mildew-proof agent.

29. The latex paint according to claim 28, characterized in that The bactericide is a formaldehyde-free bactericide.

30. The latex paint according to claim 28, characterized in that The antiseptic and mildew preventer comprises a slow-release antiseptic and mildew preventer.

31. The latex paint according to claim 20, characterized in that The raw materials for preparing the latex paint include the following components in parts by weight: 10-40 parts of water-based acrylic copolymer emulsion; 5~25 parts of pigment; Kaolin 0-20 parts; Calcium carbonate 0-25 parts; 0-10 parts of talcum powder; Barite powder 0-10 parts; 1~5 parts of film-forming aid; 0.1~0.5 parts of composite drying agent; Dispersant 0.3~1.5 parts; Wetting agent 0.1~0.6 parts; 0.1~0.5 parts of pH regulator; 0.3~1.0 parts of defoaming agent; 0.2~0.8 parts of surfactant antifreeze; 0.1~0.7 parts of bactericidal, antiseptic and mildew-proof agent; 0.1~0.6 parts of cellulose ether thickener; 0.1~0.6 parts of polyurethane thickener; 0.1~0.6 parts of acrylic thickener; 20~50 parts of deionized water.

32. A method for preparing a latex paint as claimed in claim 20, 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 additives and deionized water in a formulated amount.

33. Use of the latex paint according to claim 20 in interior wall coatings of buildings.

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