Modified ipdi curing agent, preparation method and application thereof

Abstract

The application discloses a modified IPDI curing agent, a preparation method and application thereof, and the modification of the modified IPDI curing agent comprises the following steps: reacting IPDI trimer with 12-hydroxymethyl stearate to obtain a modified IPDI trimer curing agent; and the modified IPDI trimer curing agent is used in combination with an HDI curing agent as a two-component polyurethane floor covering varnish curing agent component, and has good compatibility, high hardness, fast drying, high adhesion and a long construction period after film formation, and is very suitable for a floor covering with weather resistance requirements.

Description

Technical Field

[0001] This invention relates to the field of isocyanate curing agents, and more particularly to a method for preparing a modified IPDI curing agent and its application. Background Technology

[0002] Marble, terrazzo, and other types of flooring materials are widely used in hospitals, commercial spaces, government offices, stations, and other places. These materials have the characteristics of high hardness, resistance to heavy objects, and a variety of colors. However, they also have some disadvantages, such as being easily stained and having stains that are not easy to clean. They also have average wear resistance, and their surface loses its gloss severely after wear, requiring regular polishing and maintenance. Furthermore, these flooring materials have poor resistance to media such as acids, alkalis, and chemicals.

[0003] Epoxy flooring, as a common flooring material, is widely used in various places, but it has disadvantages such as poor weather resistance, poor adhesion, and insufficient acid and alkali resistance. Polyurethane flooring has excellent mechanical properties and good adhesion, among which aliphatic isocyanate flooring with curing agents has excellent weather resistance. IPDI trimer is widely used in automotive repair paint, industrial paint and other fields, but rarely used in the flooring field. This type of curing agent has a high Tg and excellent physical drying properties, and the hardness of the cured paint film is high. However, due to its structure, this type of curing agent has high brittleness, insufficient flexibility, and poor impact strength and adhesion of the paint film. Therefore, it is of great significance to develop a modified IPDI trimer for high-hardness substrate flooring and the two-component floor varnish prepared from it. Summary of the Invention

[0004] To address the above technical problems, this invention provides a modified IPDI trimer curing agent and its preparation method.

[0005] This invention also provides a two-component floor coating. The two-component varnish can be applied to the surface of marble and terrazzo floors by roller coating or self-leveling. The paint film dries quickly, has a long construction period, and the cured paint film has high hardness, excellent adhesion, water resistance, acid and alkali resistance and other properties.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] On the one hand, the present invention provides a method for preparing a modified IPDI curing agent, wherein the IPDI trimer curing agent is mixed uniformly with methyl 12-hydroxystearate and a catalyst under an inert gas protection, and the modified IPDI trimer curing agent is obtained after the reaction.

[0008] In the preparation method of the present invention, the ratio of IPDI trimer to methyl 12-hydroxystearate is calculated according to the molar ratio of NCO groups to OH groups, which is 2-6:1, preferably 3-4:1.

[0009] In the preparation method described in this invention, the reaction temperature is 70-80℃ and the reaction time is 3-4h.

[0010] In the preparation method described in this invention, the catalyst is an organotin catalyst, such as dibutyltin dilaurate catalyst, and the amount used is 200-500 ppm, preferably 300-400 ppm.

[0011] In the preparation method described in this invention, the reaction is completed once the theoretical NCO% is reached, preferably with a theoretical NCO value of 6.16%-7.35%.

[0012] In another aspect, the present invention provides a modified IPDI curing agent prepared by the above method.

[0013] On the other hand, the present invention also provides a two-component floor coating prepared by a modified IPDI trimer curing agent, comprising the following components in parts by weight:

[0014] Component A:

[0015]

[0016]

[0017] Component B:

[0018] 70-80 parts of HDI curing agent

[0019] 20-30 parts of modified IPDI trimer curing agent.

[0020] The polyester resin of the present invention is a modified castor oil polyester polyol with a hydroxyl value of 300-330 mgKOH / g, preferably at least one of BASF Sovermol 750 and JOULE A4105.

[0021] The defoamer of the present invention is a silicone-free polymer defoamer, preferably at least one of BYK-054, BYK-055, BYK-1790, and BYK-1795.

[0022] The leveling agent of the present invention is a polyether-modified polydimethylsiloxane, preferably at least one of BYK-306, BYK-310, BYK-333, and BYK-342.

[0023] The solvent used in this invention is a high-boiling-point solvent, preferably at least one of dimethyl nylonate (DBE) and propylene glycol methyl ether acetate (PMA).

[0024] The catalyst described in this invention is selected from organotin, organozinc, and organobismuth catalysts, with organotin catalysts being preferred, such as dibutyltin dilaurate.

[0025] The HDI curing agent described in this invention is preferably an HDI trimer curing agent HT-100, HT-200, HT-300, HT-500, or HT-600.

[0026] The two-component floor varnish of the present invention has a mass ratio of component A to component B of 1:1-1.1.

[0027] Finally, the present invention also provides a method for preparing a two-component floor varnish, the method comprising the following steps: the preparation process of component A is as follows: polyester resin, defoamer, leveling agent, solvent and catalyst are placed in a high-speed dispersion tank, and stirred at a high speed of 2000-3000 r / min for 30-60 min to mix evenly, and then placed in a sealed container for later use; the preparation process of component B is as follows: HDI curing agent and modified IPDI trimer curing agent are placed in a sealed container, stirred at room temperature for 30-60 min, and then placed in a sealed container for later use.

[0028] The two-component floor varnish is applied by mixing component A and component B evenly, then applying it to the substrate surface and drying it at room temperature to cure it into a film.

[0029] This invention has the following excellent effects:

[0030] (1) The modified IPDI curing agent obtained in this invention, combined with HDI trimer as the curing agent component of a two-component floor clear coat, significantly improves the drying speed and maintains good flexibility of the paint film. Compared with traditional polyether polyol modified isocyanate, the IPDI trimer modified with methyl 12-hydroxystearate benefits from the presence of ester groups, which not only significantly improves flexibility, but also has very good adhesion, wear resistance and media resistance, while improving the compatibility between the simple polyether modified curing agent and the resin.

[0031] (2) The modified IPDI curing agent described in this invention is combined with HDI trimer in a specific ratio as a component of a two-component polyurethane floor curing agent. The two components A and B have good compatibility. After the curing agent forms a film, it has the characteristics of high hardness and long construction period, which is very suitable for floor overlays with weather resistance requirements. Detailed Implementation

[0032] The performance testing method for the two-component floor varnish described in the embodiments of the present invention is carried out in accordance with the method in the national standard GB / T22374-2018.

[0033] The detailed information and manufacturers of the raw materials used in the embodiments and comparative examples of this invention are as follows:

[0034] Castor oil modified polyester polyol Sovermol 750, BASF

[0035] Defoamers (BYK-054, BYK-055, BYK-1790, BYK-1795), BYK Chemicals

[0036] Leveling agents (BYK-306, BYK-310, BYK-333, BYK-342), BYK Chemicals

[0037] Solvent DBE, Beijing Innocare

[0038] Dibutyltin dilaurate, Aladdin

[0039] HDI curing agent (HT-100, HT-200, HT-300, HT-500, HT-600), Wanhua Chemical

[0040] 12-Hydroxystearic acid methyl ester, Beijing Inokai

[0041] IPDI trimer curing agent (brand name IT-170B), Wanhua Chemical, NCO content 11.9%

[0042] Polyethylene glycol monomethyl ether (molecular weight 350), Beijing Innocare

[0043] Example 1

[0044] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 30g of methyl 12-hydroxystearate, and 300ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 70℃ for 4h. The modified IPDI trimer curing agent was obtained after the NCO% was measured by potentiometric titrator and reached the theoretical value of 6.16wt%.

[0045] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 80g castor oil modified polyester polyol Sovermol 750, 0.48g defoamer BYK-055, 0.5g leveling agent BYK-310, 19g solvent DBE, and 0.02g dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 30min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 70g HDI curing agent HT-300 and 30g modified IPDI trimer curing agent in a sealed container, stir at room temperature for 60min, and then place in a sealed container for later use.

[0046] Example 2

[0047] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 30g of methyl 12-hydroxystearate, and 300ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 80℃ for 3h. The modified IPDI trimer curing agent was obtained after the NCO% was measured by potentiometric titrator and reached the theoretical value of 6.16wt%.

[0048] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 84g castor oil modified polyester polyol Sovermol 750, 0.5g defoamer BYK-055, 0.44g leveling agent BYK-310, 15g solvent DBE, and 0.06g dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 40min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 70g HDI curing agent HT-100 and 30g modified IPDI trimer curing agent in a sealed container, stir at room temperature for 50min, and then place in a sealed container for later use.

[0049] Example 3

[0050] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 22.5g of methyl 12-hydroxystearate, and 300ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 75℃ for 3h. The modified IPDI trimer curing agent was obtained after the NCO% was determined to be 7.35wt% according to the theoretical value by potentiometric titration.

[0051] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 82g castor oil modified polyester polyol Sovermol 750, 0.5g defoamer BYK-055, 0.1g leveling agent BYK-310, 17.32g solvent DBE, and 0.08g dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 50min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 75g HDI curing agent HT-600 and 25g modified IPDI trimer curing agent in a sealed container, stir at room temperature for 40min, and then place in a sealed container for later use.

[0052] Example 4

[0053] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 22.5g of methyl 12-hydroxystearate, and 400ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 70℃ for 4h. The modified IPDI trimer curing agent was obtained after the NCO% was determined to be 7.35wt% according to the theoretical value by potentiometric titration.

[0054] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 81g of castor oil modified polyester polyol Sovermol 750, 0.1g of defoamer BYK-055, 0.5g of leveling agent BYK-310, 18.37g of solvent DBE, and 0.03g of dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 60min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 80g of HDI curing agent HT-200 and 20g of modified IPDI trimer curing agent in a sealed container, stir at room temperature for 30min, and then place in a sealed container for later use.

[0055] Example 5

[0056] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 22.5g of methyl 12-hydroxystearate, and 300ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 75℃ for 3h. The modified IPDI trimer curing agent was obtained after the NCO% was determined to be 7.35wt% according to the theoretical value by potentiometric titration.

[0057] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 84g of castor oil modified polyester polyol Sovermol 750, 0.5g of defoamer BYK-055, 0.4g of leveling agent BYK-310, 15g of solvent DBE, and 0.1g of dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 30min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 80g of HDI curing agent HT-100 and 20g of modified IPDI trimer curing agent in a sealed container, stir at room temperature for 60min, and then place in a sealed container for later use.

[0058] Comparative Example 1

[0059] Preparation of two-component floor varnish: Component A is prepared by placing 80g of castor oil modified polyester polyol Sovermol 750, 0.48g of defoamer BYK-055, 0.5g of leveling agent BYK-310, 19g of solvent DBE, and 0.02g of dibutyltin dilaurate in a high-speed dispersion tank, stirring at 3000r / min for 30min until uniformly mixed, and then placed in a sealed container for later use; Component B is HDI curing agent HT-300.

[0060] Comparative Example 2

[0061] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 44.9g of methyl 12-hydroxystearate, and 300ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 80℃ for 3h. The modified IPDI trimer curing agent was obtained after the NCO% was measured by potentiometric titrator and reached the theoretical value of 4.14wt%.

[0062] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 84g castor oil modified polyester polyol Sovermol 750, 0.5g defoamer BYK-055, 0.44g leveling agent BYK-310, 15g solvent DBE, and 0.06g dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 40min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 70g HDI curing agent HT-100 and 30g modified IPDI trimer curing agent in a sealed container, stir at room temperature for 50min, and then place in a sealed container for later use.

[0063] Comparative Example 3

[0064] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 18g of methyl 12-hydroxystearate, and 400ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 75℃ for 3h. The modified IPDI trimer curing agent was obtained after the NCO% was determined to be 8.14wt% according to the theoretical value by potentiometric titration.

[0065] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 82g castor oil modified polyester polyol Sovermol 750, 0.5g defoamer BYK-055, 0.1g leveling agent BYK-310, 17.32g solvent DBE, and 0.08g dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 50min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 75g HDI curing agent HT-600 and 25g modified IPDI trimer curing agent in a sealed container, stir at room temperature for 40min, and then place in a sealed container for later use.

[0066] Comparative Example 4

[0067] (1) Preparation of modified IPDI curing agent: Under nitrogen protection, 100g of IPDI trimer curing agent IT-170B, 33g of methyl 12-hydroxystearate, and 300ppm of dibutyltin dilaurate were added to the reaction mixture and mixed evenly. The mixture was stirred at 70℃ for 4h. The modified IPDI trimer curing agent was obtained after the NCO% was measured by potentiometric titrator and reached the theoretical value of 6.0wt%.

[0068] (2) Preparation of two-component floor varnish: The preparation method of component A is to place 80g castor oil modified polyester polyol Sovermol 750, 0.48g defoamer BYK-055, 0.5g leveling agent BYK-310, 19g solvent DBE, and 0.02g dibutyltin dilaurate in a high-speed dispersion tank, stir at 3000r / min for 30min until uniformly mixed, and then place in a sealed container for later use; The preparation method of component B is to place 70g HDI curing agent HT-300 and 30g modified IPDI trimer curing agent in a sealed container, stir at room temperature for 60min, and then place in a sealed container for later use.

[0069] The two-component floor varnishes described in the above embodiments and comparative examples were mixed with component A at a mass ratio of 1:1 and applied to marble substrates using a roller. After curing at room temperature, the relevant performance of the flooring was tested according to the national standard GB / T22374-2008. The test results of different embodiments and comparative examples are shown in the table below:

[0070] Table 1. Actual Application Performance of Two-Component Floor Coating

[0071]

[0072] As can be seen from the above data, the two-component floor varnish prepared by using the modified IPDI curing agent described in this invention in combination with the HDI trimer curing agent has a fast surface drying speed, excellent adhesion, good impact resistance of the paint film, and also has oil resistance, acid resistance, and alkali resistance. The modified IPDI trimer curing agent is significantly better than the unmodified product in all aspects and is very suitable for floor overlays with weather resistance requirements.

[0073] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a modified IPDI curing agent, the method comprising the following steps: under inert gas protection, mixing an IPDI trimer curing agent with methyl 12-hydroxystearate and a catalyst uniformly, and reacting to obtain a modified IPDI trimer curing agent, wherein the ratio of IPDI trimer to methyl 12-hydroxystearate, calculated according to the molar ratio of NCO groups to OH groups, is 2-6:1, and the amount of catalyst is 200-500 ppm.

2. The preparation method according to claim 1, characterized in that, The ratio of IPDI trimer to methyl 12-hydroxystearate, calculated based on the molar ratio of NCO groups to OH groups, is 3-4:1; and / or, the reaction temperature is 70-80℃, and the reaction time is 3-4h; and / or, the catalyst is an organotin catalyst, with a dosage of 300-400ppm.

3. The preparation method according to claim 1, characterized in that, The catalyst is dibutyltin dilaurate catalyst.

4. The modified IPDI curing agent prepared by the preparation method according to any one of claims 1-3.

5. A two-component floor coating comprising the following components in parts by weight: Component A: 80-84 parts of polyester resin, Defoamer 0.1-0.5 parts, Leveling agent 0.1-0.5 parts, Solvent 15-19 parts, Catalyst 0.02-0.1 parts; Component B: 70-80 parts of HDI curing agent 20-30 parts of modified IPDI trimer curing agent; The modified IPDI trimer curing agent is selected from the modified IPDI curing agents prepared by the preparation method according to any one of claims 1-3.

6. The two-component floor coating as described in claim 5, characterized in that, The polyester resin is a modified castor oil polyester polyol with a hydroxyl value of 300-330 mgKOH / g; and / or, the defoamer is a silicone-free polymeric defoamer.

7. The two-component floor coating as described in claim 5, characterized in that, The polyester resin is at least one of BASF Sovermol 750 and JOULE A4105; and / or the defoamer is at least one of BYK-054, BYK-055, BYK-1790, and BYK-1795.

8. The two-component floor coating as described in any one of claims 5-7, characterized in that, The leveling agent is a polyether-modified polydimethylsiloxane; and / or the solvent is a high-boiling-point solvent.

9. The two-component floor coating as described in claim 8, characterized in that, The leveling agent is at least one of BYK-306, BYK-310, BYK-333, and BYK-342; and / or the solvent is at least one of dimethyl nylonate (DBE) and propylene glycol methyl ether acetate (PMA).

10. The two-component floor coating as described in any one of claims 5-7, characterized in that, The catalyst is selected from organotin, organozinc and organobismuth catalysts; and / or the HDI curing agent is HT-100, HT-200, HT-300, HT-500 and HT-600.

11. The two-component floor coating as described in any one of claims 5-7, characterized in that, The catalyst is selected from dibutyltin dilaurate; and / or the HDI curing agent is HT-100, HT-200, HT-300, HT-500, or HT-600.

12. The two-component floor coating as described in any one of claims 5-7, characterized in that, The two-component floor coating has a mass ratio of component A to component B of 1:1-1.

1.

13. The method for preparing a two-component floor coating as described in any one of claims 5-12, the method comprising the following steps: Component A is prepared by placing polyester resin, defoamer, leveling agent, solvent, and catalyst in a high-speed dispersion tank, stirring at a speed of 2000-3000 r / min for 30-60 min until uniformly mixed, and then placing it in a sealed container for later use; Component B is prepared by placing HDI curing agent and modified IPDI trimer curing agent in a sealed container, stirring at room temperature for 30-60 min, and then placing it in a sealed container for later use.

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