WO2022000844A1

WO2022000844A1 - Bio-based self-thickening resin, preparation method therefor and use thereof

Info

Publication number: WO2022000844A1
Application number: PCT/CN2020/119548
Authority: WO
Inventors: 汪金; 赵汝权; 李晓敏; 叶彩平; 何燚鹏
Original assignee: 嘉宝莉化工集团股份有限公司
Priority date: 2020-07-02
Filing date: 2020-09-30
Publication date: 2022-01-06
Also published as: CN111925496B; CN111925496A

Abstract

A bio-based self-thickening resin, a preparation method therefor and use thereof. The bio-based self-thickening resin is mainly prepared from a polyol, oleic acid, castor oil, a diisocyanate, an oligomer polyol and a chain extender. The bio-based self-thickening resin has a relatively high viscosity, and the viscosity is adjustable. The bio-based self-thickening resin is on the basis of a plant seed as a raw material, has a content of bio-based components of 20% or more, has bio-based properties and excellent comprehensive performance, and can pass through international bio-based authentication. An aqueous coating prepared by using the bio-based self-thickening resin has excellent self-thickening performance and strong stability, and the coating film thereof has good blocking resistance and water resistance, and is particularly suitable for woodware.

Description

A kind of bio-based self-thickening resin and its preparation method and application

technical field

The invention belongs to the field of coatings, and particularly relates to a bio-based self-thickening resin and a preparation method and application thereof.

Background technique

Waterborne polyurethane is widely used in the field of coatings because of its excellent adhesion, hot sticking and cold brittleness resistance, high toughness and scratch resistance. However, the currently commercially available general-purpose waterborne polyurethane has low viscosity, which will cause the settlement of the finished coating during storage, unevenness, sagging, and dripping during the construction period. Therefore, an external thickener is required when formulating coatings. The thickener has significant hydrophilicity and flexibility to ensure sufficient swelling in the water phase, but it will affect the blocking resistance, water resistance and anti-fouling properties of the dry film of the coating, thereby reducing the overall performance of the product. Therefore, waterborne polyurethane resins with self-thickening properties have become the focus of research.

However, the current self-thickening water-based resin mainly achieves the purpose of thickening by adjusting the pH or relying on the addition of substances equivalent to thickeners, such as amino acids and bentonite. , and the resin obtained by adding fossil raw materials equivalent to thickeners still fails to meet the requirements in terms of viscosity and stability, which will also affect the performance of coatings, and is not conducive to the green and sustainable development of the coatings industry.

Therefore, there is an urgent need to provide a bio-based self-thickening resin with high viscosity and storage stability, which can prepare coatings with excellent blocking resistance, water resistance and anti-fouling properties.

SUMMARY OF THE INVENTION

The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a bio-based self-thickening resin, the bio-based self-thickening resin has high viscosity and storage stability, and can be used to prepare products with excellent blocking resistance, water resistance and anti-fouling. Sexual paint.

A bio-based self-thickening resin mainly prepared from polyol, oleic acid, castor oil, diisocyanate, oligomer polyol and chain extender.

The preparation method of the bio-based self-thickening resin comprises the following steps:

(1) polyol, oleic acid and catalyst are mixed, heated, and reacted to obtain polymer 1;

(2) polymer 1, castor oil, diisocyanate, chain extender 1 and solvent obtained in step (1) are mixed, and the reaction is made to obtain polymer 2;

(3) Add oligomer polyol, diisocyanate and chain extender 2 to the polymer 2 obtained in step (2), and remove the solvent after the reaction to obtain the bio-based self-thickening resin.

Preferably, the mass ratio of the polyol to the oleic acid in step (1) is 1:(2-5); further preferably, the mass ratio of the polyol to the oleic acid in step (1) is 1:(3-4).

Preferably, the polyol is pentaerythritol and/or glycerol.

Preferably, the catalyst is titanate, such as tetraisopropyl titanate and tetrabutyl titanate.

Preferably, the mass ratio of polymer 1, castor oil, diisocyanate and chain extender 1 in step (2) is (20-50): (10-40): (20-50): (10-25 ); further preferably, the mass ratio of the polymer 1, castor oil, diisocyanate and chain extender 1 in step (2) is (20-40): (10-40): (20-40): (10-18).

Preferably, the chain extender 1 in step (2) is dimethylol propionic acid or/and dimethylol butyric acid.

Preferably, in step (3), the mass ratio of polymer 2, oligomer polyol, diisocyanate and chain extender 2 is (20-50): (20-40): (10-30): ( 1-10); further preferably, the mass ratio of polymer 2, oligomer polyol, diisocyanate and chain extender 2 described in step (3) is (30-50): (20-40): ( 12-30): (2-7).

Preferably, the oligomer polyol in step (3) is polyester diol or/and polycarbonate diol, and further preferably, the oligomer polyol in step (3) is polyethylene glycol At least one of lactone diol, polybutylene adipate diol, or polycarbonate polyol.

Preferably, the diisocyanate in steps (2) and (3) is at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.

Preferably, the chain extender 2 in step (3) is at least one of ethylene glycol, propylene glycol or butylene glycol.

Preferably, in step (3), a neutralizing agent may be added before removing the solvent, and the neutralizing agent is at least one of triethylamine, diethanolamine, nitrogen methyldiethanolamine or dimethylethanolamine.

Preferably, the solvent described in step (2) is at least one of acetone, methyl ethyl ketone, nitrogen methyl pyrrolidone, and nitrogen ethyl pyrrolidone, and the specific addition amount is appropriately regulated according to the viscosity of the reaction system.

Specifically, the preparation method of the bio-based self-thickening resin includes the following steps:

(1) Add polyol and part of oleic acid (about 1/3 of the total mass of oleic acid) to the reaction kettle with the reflux condensing device, and gradually heat up to 160-180 ° C under nitrogen atmosphere to carry out esterification dehydration reaction, while The temperature at the top of the rectifying tower is controlled to be 100-115 ° C; the remaining oleic acid is added dropwise to the reaction kettle, and it is dripped at a constant speed for 1-1.5 hours, and a catalyst with a total mass of 0.03-0.08% of the reactant is added, and the reaction temperature is The temperature is raised to 200-220°C at a rate of 0.5-1.5°C/min, and the pressure of the autoclave is reduced to within 0.1-0.3MPa, and the reaction is kept at low pressure for 2-3 hours. The hydroxyl value of the product was monitored, and after the reaction was completed, the material was discharged for use, which was marked as polymer 1.

(2) add polymer 1, castor oil and diisocyanate to the reactor with reflux condensing device, react 2-3 hours at 70-85 DEG C, and add organic solvent to reduce viscosity according to system viscosity during the period; In the reactor Add the small molecule intra-emulsification chain extender 1 and an organic solvent, keep the reaction for 2-3 hours, and discharge the material after the reaction is completed, which is marked as polymer 2.

(3) add polymer 2, oligomer polyol and diisocyanate to the reactor with reflux condensing device, react at 70-85 ℃ for 1-3 hours, add organic solvent to reduce viscosity according to system viscosity during the period; Chain extender 2 is added dropwise to the reaction kettle, and the reaction is kept for 3-4 hours; after the temperature of the system drops below 40 ° C, a neutralizing agent is added, and water is added to disperse after stirring for 0.5 hours; thickening resin.

Preferably, the heating described in step (1) is preferably in a gradient heating manner, specifically, the temperature is raised from room temperature to 130-150°C, then kept for 0.5-1 hour, and then heated to 150-160°C for 0.5-1 hour. hours, and finally the temperature was raised to 165-180 °C and kept for 0.5-1 hour. Gradient heating helps control the reaction rate within a reasonable range.

A bio-based self-thickening water-based paint, comprising the following components: the bio-based self-thickening resin, a film-forming aid, a leveling agent, a wetting agent, a thickening agent, a dispersant, and water.

Preferably, the bio-based self-thickening water-based paint, in parts by weight, includes:

Further preferably, the bio-based self-thickening water-based paint, in parts by weight, includes:

Preferably, the bio-based self-thickening water-based paint further comprises at least one of inorganic pigments, antifreeze agents, bactericides, matting powders, and cross-linking agents.

The inorganic pigment is at least one of aluminum powder, copper powder, carbon black, zinc white or titanium dioxide.

Preferably, the film-forming aid is propylene glycol butyl ether, dipropylene glycol methyl ether or dipropylene glycol butyl ether.

Preferably, the leveling agent is BYK-350, BYK-356 or BYK-381.

Preferably, the defoamer is BYK-019, BYK-021 or BYK-A550.

Preferably, the wetting agent is BYK-187, BYK-3400 or BYK-3410.

Preferably, the antivirus and bactericide BIOCIDE D10.

Preferably, the thickener is WT-113, WT-115 or WT-120.

Preferably, the dispersant is BYKUMEN, GA40 or EDL-4080.

Preferably, the crosslinking agent is epoxy siloxane or carbodiimide.

A preparation method of a bio-based self-thickening water-based paint, comprising the following steps:

The bio-based self-thickening resin, film-forming aid, leveling agent, wetting agent, thickener, dispersant and water are weighed and mixed to obtain the bio-based self-thickening water-based paint.

The bio-based self-thickening water-based paint can be prepared into varnishes, primers and topcoats, and can be sprayed on wooden articles, such as wooden tables and chairs, furniture and the like. The bio-based self-thickening water-based paint has a special bonding force with wood, is sprayed on wood, has strong viscosity stability, and the coating film has good anti-blocking property and water resistance.

With respect to the prior art, the beneficial effects of the present invention are as follows:

(1) the present invention prepares bio-based self-thickening resin with polyol, oleic acid, castor oil, diisocyanate, oligomer polyol as main raw materials, by adopting oleic acid and castor oil as raw materials, replacing fossil raw materials, castor oil It contains 70% of trifunctionality and 30% of difunctionality, making full use of it for polymerization reaction, the obtained emulsion has strong storage stability, and at the same time, the interaction between emulsion droplets can be increased, and the microscopic performance is enhanced friction effect. , the macroscopic performance is the self-thickening effect.

(2) The bio-based self-thickening resin has high viscosity and can adjust the viscosity. Using it to prepare water-based coatings, the addition of water helps to weaken the interaction between emulsion droplets, and the film-forming aids help To enhance the micro friction effect, the water-based paint has excellent self-thickening performance and strong stability.

(3) The bio-based self-thickening resin is based on plant seeds as raw materials, the content of bio-based components reaches more than 20%, has bio-based characteristics, has excellent comprehensive performance, and can pass the international bio-based certification.

(4) The water-based paint prepared with the bio-based self-thickening resin as the main resin has strong viscosity stability, and the coating film has good anti-blocking property and water resistance, and is especially suitable for woodware.

detailed description

In order to make those skilled in the art understand the technical solutions of the present invention more clearly, the following examples are now given for illustration. It should be noted that the following examples do not limit the protection scope of the present invention.

In the following examples, BYK-350, BYK-356, BYK-381, BYK-019, BYK-021, BYK-A550, BYK-187, BYK-3400, BYK-3410, BYK-UMEN were purchased from BYK, Germany; Antivirus and fungicide BIOCIDE D10 was purchased from Dow Chemical; thickeners WT-113, WT-115, WT-120 were purchased from Deqian Chemical Co., Ltd.; dispersant GA40 was purchased from Ciba Refinery (China) Co., Ltd. Unless otherwise specified, other used raw materials, reagents or devices can be obtained from conventional commercial channels, or can be obtained by existing known methods.

Example 1

(1) add 100g glycerol and 100g oleic acid in the reactor with reflux condensing device, under nitrogen atmosphere from room temperature rise to 140 ℃ rear insulation 0.5 hour, be warming up to 150 ℃ subsequently, be incubated 0.5 hour, finally The temperature was raised to 170° C., the esterification dehydration reaction was carried out, and the temperature was maintained for 1 hour. At the same time, the temperature at the top of the rectifying tower is controlled to be 100-105 °C;

(2) drip the remaining 200g of oleic acid in the reactor, drip it at a constant speed in 1 hour, and add the tetrabutyl titanate of 0.05% of the total mass of the reactant as a catalyst, while the temperature of reaction is heated to 210 ° C at a certain speed, and Reduce the autoclave pressure to less than 0.1MPa, and keep the reaction at low pressure for 2 hours. Monitor the hydroxyl value of the product, and after the reaction is finished, discharge it for standby, and record it as polymer 1-1;

(3) add 200g polymer 1-1, 100g castor oil and 200g hexamethylene diisocyanate to the reactor with reflux condensing device, react at 75 DEG C for 3 hours, add 200g butanone according to the system viscosity to reduce viscosity;

(4) add 120g of dimethylol propionic acid and 100g of nitrogen methyl pyrrolidone in the reactor, heat preservation reaction for 2 hours, after the completion of the reaction, discharging is for subsequent use, and is marked as polymer 2-1;

(5) add 350g of polymer 2-1, 300g of polycaprolactone diol and 120g of dicyclohexylmethane diisocyanate to the reactor with reflux condensing device, and react at 80°C for 2 hours, during which time according to the viscosity of the system Add 200g butanone to reduce viscosity;

(6) dripped 20g butanediol and 50g butanone in the reactor, and kept the reaction for 3 hours;

(7) after the temperature of the system drops to within 40°C, add 20g of triethylamine, stir for 0.5 hour and then add water to disperse;

(8) The organic solvent is removed to obtain the final bio-based self-thickening water-based polyurethane resin, which is denoted as bio-based self-thickening resin-1.

Example 2

(1) add 100g pentaerythritol and 130g oleic acid in the reactor with reflux condensing device, be warmed up to 140 ℃ of back insulation 1 hour from room temperature under nitrogen atmosphere, be warming up to 150 ℃ subsequently, be incubated 0.5 hour, be warming up to at last 170°C, esterification dehydration reaction was carried out, and the temperature was kept for 1 hour. At the same time, the temperature at the top of the rectifying tower is controlled to be 100-105 °C;

(2) drip the remaining 270g of oleic acid in the reactor, drip it at a constant speed in 1 hour, and add the tetraisopropyl titanate of 0.05% of the total mass of the reactant as a catalyst, while the temperature of reaction is heated to 210 ° C at a certain speed. , and reduce the autoclave pressure to less than 0.1MPa, and keep the reaction at low pressure for 3 hours. The hydroxyl value of the product is monitored, and after the reaction is finished, the material is discharged for subsequent use, which is recorded as polymer 1-2;

(3) add 400g polymer 1-2, 100g castor oil and 300g isophorone diisocyanate to the reactor with reflux condensing device, react at 80 DEG C for 3 hours, add 300g butanone according to the viscosity of the system to reduce viscosity;

(4) 100g of dimethylolpropionic acid and 100g of nitrogen ethyl pyrrolidone were added to the reactor, and the reaction was incubated for 3 hours.

(5) add 500g of polymer 2-2, 200g of polybutylene adipate diol and 150g of toluene diisocyanate to the reactor with reflux condensing device, react at 75°C for 2 hours, according to the system Add 200g acetone to reduce viscosity;

(6) dripped 30g ethylene glycol and 50g acetone in the reactor, and kept the reaction for 3 hours;

(7) after the temperature of the system is lowered to within 40°C, add 40g of nitrogen methyldiethanolamine, stir for 0.5 hour and then add water to disperse;

(8) The organic solvent is removed to obtain the final bio-based self-thickening water-based polyurethane resin, which is denoted as bio-based self-thickening resin-2.

Example 3

(1) add 100g pentaerythritol and 100g oleic acid in the reactor with reflux condensing device, be warmed up to 140 ℃ from room temperature under nitrogen atmosphere and be incubated 1 hour later, be warming up to 150 ℃ subsequently, be incubated 0.5 hour, be warming up to at last 170°C, esterification dehydration reaction was carried out, and the temperature was kept for 1 hour. At the same time, the temperature at the top of the rectifying tower is controlled to be 100-105 °C;

(2) drip the remaining 200g of oleic acid in the reactor, drip it at a constant speed in 1 hour, and add the tetraisopropyl titanate of 0.05% of the total mass of the reactant as a catalyst, while the temperature of reaction is heated to 210 ° C at a certain speed , and reduce the autoclave pressure to less than 0.1MPa, and keep the reaction at low pressure for 3 hours. The hydroxyl value of the product is monitored, and after the reaction is finished, the material is discharged for use, and is recorded as polymer 1-3;

(3) add 200g polymer 1-3, 400g castor oil and 400g isophorone diisocyanate to the reactor with reflux condensing device, react at 80 DEG C for 3 hours, add 400g butanone according to the system viscosity to reduce viscosity;

(4) add 150g of dimethylol butyric acid and 100g of nitrogen ethyl pyrrolidone in the reaction kettle, keep the reaction for 2-3 hours, discharge for subsequent use after the reaction is completed, and mark it as polymer 2-3;

(5) add 300g of polymer 2-3, 400g of polycarbonate diol and 300g of dicyclohexylmethane diisocyanate to the reactor with reflux condensing device, react at 75 ° C for 2 hours, and add according to system viscosity during 200g acetone to reduce viscosity;

(6) dripped 70g propylene glycol and 250g butanone in the reactor, insulation reaction 2 hours;

(7) after the temperature of the system is lowered to within 40°C, 35g of diethanolamine is added, and after stirring for 0.5 hours, water is added to disperse;

(8) The organic solvent is removed to obtain the final bio-based self-thickening water-based polyurethane resin, which is denoted as bio-based self-thickening resin-3.

Example 4

(1) add 30g glycerol, 70g pentaerythritol and 120g oleic acid in the reactor with reflux condensing device, be incubated 1 hour after rising to 140 DEG C from room temperature under nitrogen atmosphere, be warming up to 150 DEG C subsequently, be incubated 0.5 After 1 hour, the temperature was finally raised to 170° C., the esterification dehydration reaction was carried out, and the temperature was kept for 1 hour. At the same time, the temperature at the top of the rectifying tower is controlled to be 100-105 °C;

(2) drip the remaining 240g of oleic acid in the reactor, drip it at a constant speed in 1 hour, and add the tetrabutyl titanate of 0.05% of the total mass of the reactant as a catalyst, while the temperature of reaction is heated to 210 ° C at a certain speed, and The autoclave pressure was reduced to within 0.1 MPa, and the reaction was kept at low pressure for 3 hours. The hydroxyl value of the product is monitored, and after the reaction is finished, the material is discharged for use, and is recorded as polymer 1-4;

(3) add 300g polymer 1-4, 200g castor oil and 300g hexamethylene diisocyanate to the reactor with reflux condensing device, react at 75 DEG C for 3 hours, add 200g butanone according to system viscosity to reduce viscosity;

(4) add 180g of dimethylol butyric acid and 100g of nitrogen ethyl pyrrolidone in the reactor, heat preservation reaction for 2-3 hours, after the completion of the reaction, discharging is for subsequent use, and is marked as polymer 2-4;

(5) add 300g of polymer 2-4, 200g of polycaprolactone diol and 300g of dicyclohexylmethane diisocyanate to the reaction kettle with reflux condensing device, react at 75°C for 2 hours, during the period according to the viscosity of the system Add 200g acetone to reduce viscosity;

(6) dripped 60g ethylene glycol and 250g butanone in the reactor, and kept the reaction for 2 hours;

(7) after the temperature of the system drops to within 40°C, add 25g of dimethylethanolamine, stir for 0.5 hour and then add water to disperse;

(8) The organic solvent is removed to obtain the final bio-based self-thickening water-based polyurethane resin, which is denoted as bio-based self-thickening resin-4.

Example 5

(1) add 30g glycerol, 70g pentaerythritol and 100g oleic acid to the reactor with reflux condensing device, be incubated 1 hour from room temperature to 140 DEG C under nitrogen atmosphere, be warming up to 150 DEG C subsequently, be incubated 0.5 After 1 hour, the temperature was finally raised to 170° C., the esterification dehydration reaction was carried out, and the temperature was kept for 1 hour. At the same time, the temperature at the top of the rectifying tower is controlled to be 100-105 °C;

(2) drip the remaining 100g of oleic acid in the reactor, drip it at a constant speed in 1 hour, and add the tetrabutyl titanate of 0.05% of the total mass of the reactant as a catalyst, while the temperature of reaction is heated to 210 ° C at a certain speed, and The autoclave pressure was reduced to within 0.1 MPa, and the reaction was kept at low pressure for 3 hours. The hydroxyl value of the product is monitored, and after the reaction is finished, the material is discharged for use, and is recorded as polymer 1-5;

(3) add 200g polymer 1-5, 100g castor oil and 250g hexamethylene diisocyanate to the reactor with reflux condensing device, react at 75 DEG C for 3 hours, add 150g butanone according to system viscosity during viscosity;

(4) add 80g of dimethylol butyric acid and 100g of nitrogen ethyl pyrrolidone in the reactor, heat preservation reaction for 2-3 hours, after the completion of the reaction, discharging is for subsequent use, and is marked as polymer 2-5;

(5) add 200g of polymer 2-5, 200g of polycaprolactone diol and 300g of dicyclohexylmethane diisocyanate to the reactor with reflux condensing device, react at 75°C for 2 hours, during the period according to the viscosity of the system Add 200g acetone to reduce viscosity;

(6) dripped 60g ethylene glycol and 150g butanone in the reactor, and kept the reaction for 2 hours;

(7) after the temperature of the system is lowered to within 40°C, add 10g of dimethylethanolamine, stir for 0.5 hour and then add water to disperse;

(8) The organic solvent is removed to obtain the final bio-based self-thickening water-based polyurethane resin, which is denoted as bio-based self-thickening resin-5.

Example 6

(1) 90 parts by weight of bio-based self-thickening resin-1, 0.2 parts by weight of BYK-021, 1 part by weight of propylene glycol butyl ether, 2 parts by weight of propylene glycol are stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) Add 0.3 parts by weight of BYK-350, 0.3 parts by weight of BYK-3400, 0.05 parts by weight of BIOCIDE D10 to the mixture and add the stirring device successively, stir at a high speed for 1 hour, then add 3 parts by weight of polycarbide imine, after high-speed stirring for 0.5 hours, a coating was obtained, which was recorded as coating-1.

The coating can be sprayed on the surfaces of metal, plastic, wood, etc., and has strong viscosity stability, and the coating film has good blocking resistance and water resistance.

Example 7

Preparation of high gloss waterborne varnish

(1) 88 parts by weight of bio-based self-thickening resin-3, 0.3 parts by weight of BYK-019, 2 parts by weight of dipropylene glycol methyl ether, 2 parts by weight of propylene glycol are stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) Add 0.3 parts by weight of BYK-356, 0.3 parts by weight of BYK-187, and 0.05 parts by weight of BIOCIDE D10 to the mixture and add the stirring device successively, stir at high speed for 1 hour, then add 3 parts by weight of epoxy silicon Oxane, high-speed stirring for 0.5 hours to obtain a water-based varnish, which is recorded as paint-2.

Example 8

Preparation of matt waterborne varnishes

(1) 85 parts by weight of bio-based self-thickening resin-2, 0.4 parts by weight of BYK-A 550, 3 parts by weight of dipropylene glycol butyl ether, 1 part by weight of propylene glycol are stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) adding 2 weight parts of matting powder, 0.3 weight part of BYK-381, 0.3 weight part of BYK-3410, 0.05 weight part of BIOCIDE D10 to the mixture and adding stirring device successively, stirring at high speed for 1 hour, then adding 2 parts by weight of polycarbodiimide was stirred at high speed for 0.5 hours to obtain a water-based varnish, which was recorded as coating-3.

Example 9

Preparation of Matte Waterborne Wood Varnish

(1) 88 parts by weight of bio-based self-thickening resin-4, 0.2 parts by weight of BYK-019, 2 parts by weight of dipropylene glycol methyl ether, 2 parts by weight of propylene glycol are stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) Add 1 weight part of matting powder, 0.2 weight part of BYK-381, 0.3 weight part of BYK-3400, 0.1 weight part of BIOCIDE D10 to the mixture and add the stirring device successively, stir at high speed for 1 hour, then add 3 parts by weight of epoxy siloxane was stirred at high speed for 0.5 hours to obtain water-based wood varnish, which was recorded as coating-4.

Example 10

Preparation of water-based wood white finish

(1) 3 parts by weight of deionized water, 0.5 part by weight of BYKUMEN, 0.1 part by weight of BYK-021, 0.1 part by weight of BYK-3400, 20 parts by weight of titanium dioxide were added to the stirring device successively, and stirred at a high speed for 0.5 hours Get white pulp, take it out for later use;

(2) 60 parts by weight of bio-based self-thickening resin-3, 0.4 parts by weight of BYK-A 550, 4 parts by weight of propylene glycol butyl ether, and 1 part by weight of propylene glycol were added to the stirring device successively, and stirred at a medium speed for 0.5 hours get a mixture;

(3) adding step (1) gained white slurry, stirring at medium speed for 0.5 hour;

(4) 0.3 parts by weight of BYK-356, 0.3 parts by weight of BYK-3400, 0.1 part by weight of WT-120, 0.05 part by weight of BIOCIDE D10 were added to the mixture in order to a stirring device, stirred at high speed for 1 hour, and then Add 2 parts by weight of polycarbodiimide, and stir at a high speed for 0.5 hours to obtain a water-based wood white primer, which is recorded as paint-5.

Example 11

Preparation of water-based wood white primer

(1) The deionized water of 2 weight parts, the GA40 of 1 weight part, the defoamer of 0.05 weight part, the wetting agent of 0.2 weight part, the titanium dioxide of 30 weight parts are added to the stirring device successively, and the high-speed stirring is carried out for 1 hour. Get white pulp, take it out for later use;

(2) 50 parts by weight of bio-based self-thickening resin-4, 0.2 parts by weight of BYK-019, 3 parts by weight of dipropylene glycol methyl ether, and 1 part by weight of propylene glycol were sequentially added to the stirring device, and stirred at a medium speed for 0.5 hours get a mixture;

(3) adding step (1) gained white slurry, stirring at medium speed for 0.5 hour;

(4) Add 0.1 part by weight of BYK-356, 0.5 part by weight of BYK-187, 0.2 part by weight of WT-115, 0.1 part by weight of BIOCIDE D10 into the mixture and add it to the stirring device in turn, and stir at high speed for 1 hour to obtain Water-based wood white finish, recorded as paint-6.

Example 12

Preparation of water-based wood white finish

(2) 60 parts by weight of bio-based self-thickening resin-5, 0.4 parts by weight of BYK-A 550, 4 parts by weight of propylene glycol butyl ether and 1 part by weight of propylene glycol were added to the stirring device successively, and stirred at a medium speed for 0.5 hours get a mixture;

(3) adding step (1) gained white slurry, stirring at medium speed for 0.5 hour;

(4) 0.3 parts by weight of BYK-356, 0.3 parts by weight of BYK-3400, 0.1 part by weight of WT-120, 0.05 part by weight of BIOCIDE D10 were added to the mixture in order to a stirring device, stirred at high speed for 1 hour, and then Add 2 parts by weight of polycarbodiimide, and stir at high speed for 0.5 hours to obtain a water-based wood white primer, which is recorded as paint-7.

Comparative Example 1

(1) 60g of polycaprolactone, 5g of dimethylolpropionic acid and 30g of toluene diisocyanate were reacted at 70° C. for 3 hours to obtain a prepolymer;

(2) add 6g ethylene glycol to the prepolymer, react for 1.5 hours, then add 30g butanone to reduce viscosity;

(3) add 3.5g triethylamine and neutralize 0.5 hour, then add 200g water dispersion;

(4) Butanone was distilled off to obtain Comparative Example Resin-1.

Comparative Example 2

The difference between Comparative Example 2 and Example 2 is that dimethylolpropionic acid is used to replace the oleic acid in Example 2, and the remaining raw materials and preparation methods are the same as those of Example 2 to obtain Comparative Resin-2.

Comparative Example 3

The difference between Comparative Example 3 and Example 2 is that the castor oil in Example 2 is replaced by hydroxylated stearyl stearate, and the remaining raw materials and preparation methods are the same as those in Example 2 to obtain Comparative Resin-3.

Comparative Example 4

(1) 90 parts by weight of the comparative example resin, 0.2 parts by weight of BYK-021, 1 part by weight of propylene glycol butyl ether, 2 parts by weight of propylene glycol were stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) Add 0.3 parts by weight of BYK-350, 0.3 parts by weight of BYK-3400, 0.05 parts by weight of BIOCIDE D10 to the mixture and add the stirring device successively, stir at a high speed for 1 hour, then add 3 parts by weight of polycarbide imine, high-speed stirring for 0.5 hours to obtain water-based wood varnish, which is recorded as Comparative Example Paint-1.

Comparative Example 5

(1) 90 parts by weight of purchased resin (bio-based self-thickening resin produced by Covestro), 0.2 parts by weight of defoamer, 1 part by weight of film-forming aid, and 2 parts by weight of propylene glycol were mixed at a medium speed Stir for 0.5 hour to obtain a mixture;

(2) adding 0.3 weight part of leveling agent, 0.3 weight part of wetting agent, 0.05 weight part of anti-virus bactericide to the mixture and adding stirring device successively, stirring at high speed for 1 hour, then adding 0.5 weight part thickening agent agent and 3 parts by weight of polycarbodiimide, and stirred at high speed for 0.5 hours to obtain a water-based wood varnish, which is recorded as Comparative Example Paint-2.

Comparative Example 6

(1) 85 parts by weight of comparative resin-2, 0.4 parts by weight of BYK-A 550, 3 parts by weight of dipropylene glycol butyl ether, 1 part by weight of propylene glycol are stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) adding 2 weight parts of matting powder, 0.3 weight parts of BYK-381, 0.3 weight parts of BYK-3410, 0.05 weight parts of BIOCIDE D10 to the mixture and adding the stirring device successively, stirring at high speed for 1 hour, then adding 2 parts by weight of polycarbodiimide was stirred at high speed for 0.5 hour to obtain water-based wood varnish, which was recorded as Comparative Paint-3.

Comparative Example 7

(1) 85 parts by weight of comparative resin-3, 0.4 parts by weight of BYK-A 550, 3 parts by weight of dipropylene glycol butyl ether, 1 part by weight of propylene glycol are stirred at a medium speed for 0.5 hours to obtain a mixture;

(2) adding 2 weight parts of matting powder, 0.3 weight part of BYK-381, 0.3 weight part of BYK-3410, 0.05 weight part of BIOCIDE D10 to the mixture and adding stirring device successively, stirring at high speed for 1 hour, then adding 2 parts by weight of polycarbodiimide was stirred at high speed for 0.5 hours to obtain water-based wood varnish, which was recorded as Comparative Paint-4.

Product effect test

The resins prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to viscosity measurement, and the results are shown in Table 1.

Table 1 Resin viscosity test result table

Note: The viscosity data are all measured with 4 cups under the condition of 25±1℃.

The coatings prepared in Examples 6-12 (corresponding to coatings 1-7 in sequence) and the coatings prepared in Comparative Examples 4-7 (corresponding to coatings 1-4 in sequence) were tested for performance, and the test results are shown in Table 2.

Table 2 Viscosity and coating film performance test results of coatings

Note: The viscosity data are all measured by coating 4 cups under the condition of 25±1℃; for the scoring items involved, 1 is the worst and 10 is the best.

It can be seen from Table 1 of the test results that the bio-based self-thickening resins prepared in Examples 1-5 of the present invention exhibit obvious self-thickening effects. Little change, showing good viscosity stability. It can be seen from the viscosity reduction test by adding water that the viscosity of the resin generally has a significant decrease in viscosity, and by adding a film-forming aid to increase the viscosity, it can be seen that the resin shows a significant increase in viscosity, showing better viscosity adjustment. It is convenient for the deployment of finished products during actual production and construction. However, the viscosity stability of the resin prepared in Comparative Example 1-3 is obviously inferior to that of the resin prepared in Example 1-5 after storage at room temperature and thermal storage. Afterwards, the viscosity change was also inferior to that of the Examples, and the viscosity controllability was poor.

It can be seen from the test results table 2 that, compared with the comparative coatings 1-4, the coatings prepared in the present application showed good viscosity stability, the viscosity did not decrease after 6 months of storage at room temperature, and the viscosity remained basically the same after 14 days at 50°C. level, thanks to its self-thickening properties. The coatings prepared in Examples 6-12 of the present invention also exhibit good water resistance and blocking resistance, and have excellent comprehensive properties. At the same time, considering the high price of the thickener, the self-thickening water-based paint of the present invention has a low cost and a significant cost-effectiveness advantage.

Claims

A bio-based self-thickening resin is characterized in that it is mainly prepared from polyol, oleic acid, castor oil, diisocyanate, oligomer polyol and chain extender.
The preparation method of bio-based self-thickening resin according to claim 1, is characterized in that, comprises the following steps:

(1) polyol, oleic acid and catalyst are mixed, heated, and reacted to obtain polymer 1;

(2) polymer 1, castor oil, diisocyanate, chain extender 1 obtained in step (1) are mixed with solvent, and polymer 2 is obtained by reaction;

(3) Add oligomer polyol, diisocyanate and chain extender 2 to the polymer 2 obtained in step (2), and remove the solvent after the reaction to obtain the bio-based self-thickening resin.
The preparation method according to claim 2, wherein the mass ratio of the polyol to the oleic acid in step (1) is 1:(2-5); preferably, the mass ratio of the polyol in step (1) The mass ratio of polyol to the oleic acid is 1:(3-4).
The preparation method according to claim 2, wherein the mass ratio of polymer 1, castor oil, diisocyanate and chain extender 1 described in step (2) is (20-50): (10-40) : (20-50): (10-25); Preferably, the mass ratio of the polymer 1, castor oil, diisocyanate and chain extender 1 in step (2) is (20-40): (10 -40):(20-40):(10-18).
The preparation method according to claim 2, wherein the mass ratio of polymer 2, oligomer polyol, diisocyanate and chain extender 2 described in step (3) is (20-50): (20 -40): (10-30): (1-10); preferably, the mass ratio of polymer 2, oligomer polyol, diisocyanate and chain extender 2 in step (3) is (30- 50):(20-40):(12-30):(2-7).
The preparation method according to claim 2, wherein the oligomer polyol in step (3) is polyester diol or/and polycarbonate diol.
The preparation method according to claim 2, wherein the chain extender 1 described in step (2) is dimethylol propionic acid or/or dimethylol butyric acid; The chain agent 2 is at least one of ethylene glycol, propylene glycol or butylene glycol.
A bio-based self-thickening water-based paint, characterized in that it comprises the bio-based self-thickening resin according to claim 1, and also includes a film-forming aid, a leveling agent, a wetting agent, a thickening agent, a dispersing agent and water .
bio-based self-thickening water-based paint according to claim 8, is characterized in that, by weight, comprises the following components:
The application of the bio-based self-thickening water-based paint according to claim 8 or 9, characterized in that, the bio-based self-thickening water-based paint is sprayed on woodware.