CN115819716A - A kind of sunflower oil modified aqueous polyurethane dispersion and its preparation method and application - Google Patents

Abstract

The invention provides a sunflower oil modified waterborne polyurethane dispersion and its preparation method and application. In parts by weight, the raw materials for preparing the sunflower oil modified waterborne polyurethane dispersion include 20 to 30 parts of polymer polyols , 6-13 parts of isocyanate and 10-15 parts of sunflower oil-based dihydroxy acid. In the present invention, using sunflower oil-based dihydroxy acid as the raw material for the preparation of polyurethane can be used as both a hydrophilic chain extender and an internal emulsifier. Compared with conventional chain extenders, such as dimethylolpropionic acid, It has excellent thermodynamic properties, and has higher hardness and tensile strength; the resulting polyurethane has higher modulus, tensile strength and softening point; and sunflower oil, as a bio-based raw material, can be widely obtained from nature Obtaining, reducing dependence on fossil energy, low cost and good environmental protection.

Description

A kind of sunflower oil modified aqueous polyurethane dispersion and its preparation method and application

technical field

The invention belongs to the technical field of synthetic leather, and in particular relates to a sunflower oil modified waterborne polyurethane dispersion and a preparation method and application thereof.

Background technique

As one of the most important polymers today, polyurethane has attracted widespread attention from scientists all over the world because of its wide range of uses and unique properties. Synthesized by polyaddition reactions between isocyanates and polyols, polyurethanes are an essential part of modern life with diverse applications in plastics, construction industry, automotive, medical science, synthetic leather, furniture, coatings, etc. The synthesis of polyurethane from bio-based materials is of great significance. Solvent-based polyurethanes are widely used in many industrial fields, such as coatings, inks and adhesives, etc., and they are usually used in formulations with a solid content of 25%. A huge defect of these systems is the use of toxic solvents in their preparation process, such as N,N-dimethylformamide, toluene and methyl ethyl ketone, etc. These organic solvents have certain volatility, and there are A small amount of solvent enters the air and has adverse effects on the environment. The United States and European countries have begun to implement more stringent laws to completely eliminate or reduce the amount of organic volatile solvents released into the atmosphere. Therefore, new water-based polyurethane materials used in industries such as leather, paint and coatings to replace organic solvent polyurethane products have emerged. Water-based polyurethanes containing carboxylic acid, sulfonic acid, and tertiary amine groups use water as a solvent, which reduces air pollution and energy consumption in industrial production, and improves occupational health. In addition, the viscosity of water-based polyurethane is controllable during the synthesis process.

Anionic waterborne polyurethane is prepared by using polyol, diisocyanate and dimethylolpropionic acid as chain extenders, then using triethylamine and residual carboxyl groups to generate ionic groups, emulsification and post-chain extension. Among the numerous dihydroxy acids, dimethylolpropionic acid (DMPA) is the one most commonly used in most reports to stabilize polyurethane dispersions in the aqueous phase. For example, CN115160534A discloses a water-based polyurethane, which is obtained by polymerizing alicyclic polyester polyol, diisocyanate and hydrophilic chain extender. The usage amount of the hydrophilic chain extender is between 0.05 parts by weight and 1.5 parts by weight. The hydrophilic chain extender includes dimethylolpropionic acid. However, DMPA is synthesized from formaldehyde through complicated pathways, and is considered an expensive material in the industry, and the thermodynamic and mechanical properties of the resulting polyurethane need to be further improved.

Therefore, to develop a water-based polyurethane material with good thermodynamic properties, higher hardness and tensile strength, low cost and no pollution is a technical problem to be solved urgently in this field.

Contents of the invention

Aiming at the deficiencies in the prior art, the object of the present invention is to provide a sunflower oil modified aqueous polyurethane dispersion and its preparation method and application. The raw materials for preparing the sunflower oil-modified water-based polyurethane dispersion include sunflower oil-based dihydroxy acid, which is beneficial to improving the mechanical properties and thermal properties of the water-based polyurethane.

For reaching this purpose, the present invention adopts following technical scheme:

In the first aspect, the present invention provides a sunflower oil modified waterborne polyurethane dispersion. In parts by weight, the raw materials for preparing the sunflower oil modified waterborne polyurethane dispersion include 20-30 parts of polymer polyol, 6 isocyanate ~13 parts and 10-15 parts of sunflower oil-based dihydroxy acid.

In the present invention, using sunflower oil-based dihydroxy acid as the raw material for the preparation of polyurethane can be used as both a hydrophilic chain extender and an internal emulsifier. Compared with conventional chain extenders, such as dimethylol propionic acid, It has excellent thermodynamic properties, and has higher hardness and tensile strength; the obtained polyurethane has higher modulus, tensile strength and softening point; and sunflower oil, as a bio-based raw material, can be widely obtained from nature Obtaining, reducing dependence on fossil energy, low cost and good environmental protection.

Preferably, in parts by weight, the raw materials for the preparation of the sunflower oil modified waterborne polyurethane dispersion include 20 to 30 parts of polymer polyols, for example, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26, 27, 28, 29, etc.

Preferably, in parts by weight, the raw materials for preparing the sunflower oil-modified waterborne polyurethane dispersion include 6 to 13 parts of isocyanate, for example, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, etc.

Preferably, in parts by weight, the raw materials for preparing the sunflower oil-modified waterborne polyurethane dispersion include 10-15 parts of sunflower oil-based dihydroxy acid, for example, 10.2 parts, 10.4 parts, 10.6 parts, 10.8 parts, 11 parts, 11.2 parts, 11.4 parts, 11.6 parts, 11.8 parts, 12 parts, 12.2 parts, 12.4 parts, 12.6 parts, 12.8 parts, 13 parts, 13.2 parts, 13.4 parts, 13.6 parts, 13.8 parts, 14 parts, 14.2 parts , 14.4, 14.6, 14.8, etc.

Preferably, the sunflower oil-modified dihydroxy acid accounts for 28-35% of the total mass of the polymer polyol and sunflower oil-based dihydroxy acid, such as 28.5%, 29%, 29.5%, 30%, 30.5% %, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, etc.

Preferably, the sunflower oil-based dihydroxy acid is prepared by the following method, the method comprising:

(i) sunflower oil is mixed with formic acid and hydrogen peroxide, and reacted to obtain epoxidized sunflower oil;

(ii) reacting the epoxidized sunflower oil obtained in step (i) with methanol to obtain methoxylated sunflower oil;

(iii) Saponifying the methoxylated sunflower oil obtained in step (ii) with an alkali to obtain the sunflower oil-based dihydroxy acid.

Preferably, the mass ratio of sunflower oil to formic acid and hydrogen peroxide in step (i) is 1:(0.3～0.8):(0.3～0.7), wherein, the specific value in (0.3～0.8) can be, for example, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.54, 056, 0.58, 0.6, 0.62, 0.64, 0.66, 0.68, 0.7, 0.72, 0.74, 0.76, 0.78, etc.; The specific values in (0.3～0.7) can be, for example, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.54, 056, 0.58, 0.6, 0.62, 0.64, 0.66, 0.68 .

Preferably, the mixing in step (i) includes mixing the sunflower oil and formic acid, and then adding hydrogen peroxide for reaction.

Preferably, the temperature at which the sunflower oil is mixed with formic acid is 40-60°C, for example, 45°C, 50°C, 55°C, etc.

Preferably, the mixing time is 0.5-2 hours, for example, 0.8 hours, 1 hours, 1.5 hours, 1.8 hours and so on.

Preferably, the reaction temperature in step (i) is 45-65°C, for example, 48°C, 50°C, 52°C, 56°C, 60°C, 62°C, 64°C, etc.

Preferably, the reaction time in step (i) is 1-5 h, for example, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, etc.

In the present invention, after the reaction described in step (i), it also includes cooling to room temperature, and washing with distilled water to eliminate excess acid, then dissolving the product in dichloromethane, and performing simple organic phase separation. Manganese sulfate was dried and filtered; finally dichloromethane was evaporated with a rotary evaporator to obtain a clear viscous product.

Preferably, the reaction system in step (ii) further includes a catalyst.

Preferably, the catalyst includes at least one of trifluoromethanesulfonic acid, sulfuric acid or p-toluenesulfonic acid.

Preferably, in the reaction system described in step (ii), the mass ratio of epoxidized sunflower oil to methanol and the catalyst is 1:(5～10):(0.0001～0.0005), wherein, in (5～10) The specific values may be, for example, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.; the specific values in (0.0001-0.0005) may be, for example, 0.0002, 0.0003, 0.0004, etc.

Preferably, the reaction temperature in step (ii) is 65-90°C, for example, 70°C, 75°C, 80°C, 85°C, etc.

Preferably, the reaction time in step (ii) is 1 to 5 hours, for example, 2 hours, 3 hours, 4 hours, etc.

In the present invention, after the reaction described in step (ii) is finished, it also includes cooling to room temperature and washing with distilled water to eliminate excess acid, then dissolving the product in methylene chloride and performing simple organic phase separation. Manganese sulfate was dried and then filtered; finally, the methoxylated sunflower oil was obtained by evaporating dichloromethane with a rotary evaporator.

Preferably, the reaction system in step (iii) further includes a solvent.

Preferably, in the reaction system described in step (iii), the mass ratio of methoxylated sunflower oil to alkali and solvent is 1:(0.4～0.9):(1.2～1.8), wherein, (0.4～0.9) The specific values in (1.2～1.8) can be, for example, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, etc.

In the present invention, the reaction temperature in step (iii) can make the system reflux.

Preferably, the reaction time in step (iii) is 4-8 hours, for example, 5 hours, 6 hours, 7 hours, etc.

In the present invention, after the reaction described in step (iii), it also includes the steps of neutralizing with acid, extracting the organic phase with dichloromethane, and washing with saturated sodium chloride solution; after washing, dry with manganese sulfate, use The organic phase was removed by a rotary evaporator to obtain the sunflower oil-based dihydroxy acid.

In the present invention, the acid is used to neutralize residual alkali, and the acid used includes at least one of sulfuric acid, hydrochloric acid or phosphoric acid.

Preferably, the number average molecular weight of the polymer polyol is 500-2000, such as 600, 800, 1000, 1200, 1400, 1600, 1800, etc.

Preferably, the polymer polyol comprises at least one of polytetramethylene ether diol, polyethylene oxide ether diol, polycaprolactone diol or polybutylene adipate diol kind.

Preferably, the isocyanate includes at least one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate or 1,6-hexamethylene diisocyanate.

Preferably, in parts by weight, the raw materials for preparing the sunflower oil-modified waterborne polyurethane dispersion also include 0.3 to 0.6 parts of a neutralizing agent, such as 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, etc. .

Preferably, the solid content of the sunflower oil-modified aqueous polyurethane dispersion is 30-40%, for example, it may be 32%, 34%, 36%, 38% and so on.

Preferably, the viscosity of the sunflower oil-modified waterborne polyurethane dispersion is 1000-2000 mPa·s, for example, 1200 mPa·s, 1400 mPa·s, 1600 mPa·s, 1800 mPa·s, etc.

Preferably, the particle size of the sunflower oil-modified aqueous polyurethane dispersion is 80-150 nm, for example, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, etc.

In a second aspect, the present invention provides a method for preparing the sunflower oil modified aqueous polyurethane dispersion according to the first aspect, the preparation method comprising:

After the polymer polyol is mixed with the sunflower oil-based dihydroxy acid, it is reacted with isocyanate, and after the reaction, water is added for emulsification to obtain the sunflower oil-modified aqueous polyurethane dispersion.

Preferably, the mixing temperature is 50-70°C, for example, 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, etc.

Preferably, the step of vacuum dehydration is also included after the mixing.

Preferably, the reaction temperature is 70-80°C, such as 72°C, 74°C, 76°C, 78°C, etc.

Preferably, the reaction time is 2-5 hours, for example, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, etc.

Preferably, after the reaction, the step of adding an organic solvent to dilute and continue the reaction is also included.

Preferably, adding an organic solvent to dilute and continuing the reaction takes 2 to 4 hours, for example, 2.5 hours, 3 hours, 3.5 hours, etc.

In the present invention, the organic solvent includes methyl ethyl ketone (MEK) or acetone (AC).

Preferably, an organic solvent is added for dilution, and after continuing the reaction, it also includes adding a neutralizing agent to carry out the neutralization reaction.

In the present invention, the neutralizing agent includes a basic compound, preferably one or more combinations of KOH, ammonia water, NaOH or triethylamine.

In the present invention, an organic solvent is added for dilution, and after the reaction is continued, the NCO content in the detection system is qualified, and a neutralizing agent is added for neutralization.

Preferably, the time for the neutralization reaction is 0.5-1 h, for example, 0.6 h, 0.7 h, 0.8 h, 0.9 h, etc.

Preferably, the step of removing the organic solvent is also included after the emulsification.

In the present invention, in the raw materials for the preparation of the water-based polyurethane, the molar ratio of the isocyanate group to the total hydroxyl group of the polymer polyol and the chain extender is (1.1-1.05):1.

In the third aspect, the present invention provides a synthetic leather, wherein the raw material of the synthetic leather includes the sunflower oil modified aqueous polyurethane dispersion as described in the first aspect.

The numerical ranges described in the present invention not only include the above-listed point values, but also include any point values between the above-mentioned numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the ranges. The specific pip value to include.

Compared with prior art, the beneficial effect of the present invention is:

The sunflower oil modified water-based polyurethane dispersion provided by the present invention uses commercially available sunflower oil as a raw material to prepare a green and renewable sunflower oil-based dihydroxy acid, which can be used as both a chain extender and an internal Emulsifier, as a raw material for the preparation of polyurethane, has more excellent thermodynamic properties, higher hardness and tensile strength than conventional hydrophilic chain extenders. And as a bio-based raw material, sunflower oil can be widely obtained from nature, reducing the dependence on fossil energy; improving the modulus, tensile strength and softening point of polyurethane; low cost and environmentally friendly.

Detailed ways

The technical solutions of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

In the present invention, the viscosity of the water-based polyurethane dispersion is tested by a viscometer; the particle size of the water-based polyurethane dispersion is tested by a particle size meter.

Preparation Example 1

A kind of sunflower oil base dihydroxy acid, the preparation method of described sunflower oil base dihydroxy acid comprises:

(1) Add 10 parts of commercially available sunflower oil and 0.3 parts of formic acid into a reaction kettle equipped with a mechanical stirrer and a thermometer, stir at 40°C for 0.5h, then add 0.3 parts of hydrogen peroxide dropwise, and keep the temperature at 45 Continue to react and stir for 1 h at ℃, so that the sunflower oil is epoxidized. After the reaction, the mixture is cooled to room temperature and washed with distilled water to eliminate excess acid. Then, the obtained product is dissolved in dichloromethane for simple organic The phases were separated, the organic layer was dried with manganese sulfate and filtered, and finally the dichloromethane was evaporated with a rotary evaporator to obtain epoxidized sunflower oil.

(2) Mix 10 parts of epoxidized sunflower oil obtained in step (1) with 50 parts of methanol, and add 0.001 part of catalyst trifluoromethanesulfonic acid, react at 65 ° C, vigorously stir and reflux for 1 h, and use the same method (1) The same method is used to purify it to obtain methoxylated sunflower oil.

(3) Add 100 parts of methoxylated sunflower oil obtained in step (2), 40 parts of sodium hydroxide, and 120 parts of ethanol into a round-bottomed flask equipped with a condenser, carry out 4h reflux reaction, and then use sulfuric acid to carry out Neutralization; the organic phase was extracted with dichloromethane, washed with saturated sodium chloride solution, dried on manganese sulfate, and the organic phase was removed using a rotary evaporator to obtain the sunflower oil-based dihydroxy acid.

Preparation example 2

A kind of sunflower oil base dihydroxy acid, the preparation method of described sunflower oil base dihydroxy acid comprises:

(1) Add 10 parts of commercially available sunflower oil and 0.5 parts of formic acid into a reaction kettle equipped with a mechanical stirrer and a thermometer, stir at 50°C for 1 hour, then add 0.5 parts of hydrogen peroxide dropwise, and keep the temperature at 50°C Continue the reaction and stir for 3h to make the epoxidation of sunflower oil. After the reaction is over, the mixture is cooled to room temperature and washed with distilled water to eliminate excess acid. Then the obtained product is dissolved in dichloromethane for simple organic phase After separation, the organic layer was dried with manganese sulfate and filtered, and finally the dichloromethane was evaporated with a rotary evaporator to obtain epoxidized sunflower oil.

(2) Mix 10 parts of epoxidized sunflower oil obtained in step (1) with 70 parts of methanol, and add 0.003 parts of catalyst sulfuric acid, react at 80 ° C, vigorously stir and reflux for 3 hours, and use the same method as in step (1) Purify it according to the method to obtain methoxylated sunflower oil.

(3) Add 100 parts of methoxylated sunflower oil obtained in step (2), 70 parts of sodium hydroxide, and 150 parts of ethanol into a round-bottomed flask equipped with a condenser, carry out a reflux reaction for 6 hours, and then use sulfuric acid to carry out Neutralization; the organic phase was extracted with dichloromethane, washed with saturated sodium chloride solution, dried on manganese sulfate, and the organic phase was removed using a rotary evaporator to obtain the sunflower oil-based dihydroxy acid.

Preparation example 3

A kind of sunflower oil base dihydroxy acid, the preparation method of described sunflower oil base dihydroxy acid comprises:

(1) Add 10 parts of commercially available sunflower oil and 0.8 parts of formic acid into a reaction kettle equipped with a mechanical stirrer and a thermometer, stir at 60°C for 2h, then add 0.7 parts of hydrogen peroxide dropwise, and keep the temperature at 65°C Continue the reaction and stir for 5 h to epoxidize the sunflower oil. After the reaction is over, the mixture is cooled to room temperature and washed with distilled water to eliminate excess acid. The resulting product is then dissolved in dichloromethane for simple organic phase After separation, the organic layer was dried with manganese sulfate and filtered, and finally the dichloromethane was evaporated with a rotary evaporator to obtain epoxidized sunflower oil.

(2) Mix 10 parts of epoxidized sunflower oil obtained in step (1) with 100 parts of methanol, and add 0.005 parts of catalyst sulfuric acid, react at 90 ° C, vigorously stir and reflux for 5 hours, and use the same method as in step (1) Purify it according to the method to obtain methoxylated sunflower oil.

(3) Add 100 parts of methoxylated sunflower oil obtained in step (2), 90 parts of sodium hydroxide, and 180 parts of ethanol into a round-bottomed flask equipped with a condenser, carry out reflux reaction for 8 hours, and then carry out the reaction with sulfuric acid successively. Neutralization; the organic phase was extracted with dichloromethane, washed with saturated sodium chloride solution, dried on manganese sulfate, and the organic phase was removed using a rotary evaporator to obtain the sunflower oil-based dihydroxy acid.

Preparation Example 4

A sunflower oil-based dihydroxy acid, the difference from Preparation Example 1 is that in the preparation method of the sunflower oil-based dihydroxy acid, the amount of formic acid in step (1) is 0.1 part, and other raw materials and amounts And preparation method is all identical with preparation example 1.

Preparation Example 5

A sunflower oil-based dihydroxy acid, the only difference from Preparation Example 1 is that in the preparation method of the sunflower oil-based dihydroxy acid, the amount of formic acid in step (1) is 1.1 parts, and other raw materials and amounts And preparation method is all identical with preparation example 1.

Preparation example 6

A sunflower oil-based dihydroxy acid, the difference from Preparation Example 1 is that in the preparation method of the sunflower oil-based dihydroxy acid, the amount of methanol in step (2) is 20 parts, and other raw materials and amounts And preparation method is all identical with preparation example 1.

Preparation Example 7

A sunflower oil-based dihydroxy acid, the only difference from Preparation Example 1 is that in the preparation method of the sunflower oil-based dihydroxy acid, the amount of methanol in step (2) is 120 parts, and other raw materials and amounts And preparation method is all identical with preparation example 1.

Comparative Preparation Example 1

A castor oil-based dihydroxy acid, the only difference between it and Preparation Example 1 is that in the preparation method, the sunflower oil in step (1) is replaced by castor oil in equal parts by weight, other raw materials, dosage and preparation The methods are all the same as in Preparation Example 1.

Example 1

This embodiment provides a sunflower oil modified waterborne polyurethane dispersion, in parts by weight, the preparation raw material of the sunflower oil modified waterborne polyurethane dispersion includes 20 parts of polytetramethylene ether glycol (molecular weight 500) , 10 parts of sunflower oil-based dihydroxy acid (preparation example 1) and 6 parts of diphenylmethane diisocyanate; The solid content of described sunflower oil modified aqueous polyurethane dispersion is 35.1%, and viscosity is 1100mpa.s, grain The diameter is 132nm.

The present embodiment provides a kind of preparation method of sunflower oil modified aqueous polyurethane dispersion, specifically comprises the following steps:

Put polytetramethylene ether glycol and sunflower oil-based dihydroxy acid into a reaction kettle according to the formula amount, heat up to 50° C. to melt, and stir and dehydrate under vacuum. Add diphenylmethane diisocyanate into the reaction kettle, raise the temperature to 70°C and continue the reaction for 2 hours, add 15 parts of butanone to dilute, and continue the reaction for 2 hours; check the NCO value, add 0.3 parts of neutralizing agent KOH after passing the test, and continue stirring 0.5h; subsequently, add 50 parts of deionized water to it for emulsification. The ratio of the NCO value of the isocyanate to the total hydroxyl value of the polymer polyol and sunflower oil based dihydroxy acid was 1.05:1. The obtained material is subjected to rotary vacuum evaporation to remove the organic solvent in the material to obtain the sunflower oil modified aqueous polyurethane dispersion.

Example 2

The present embodiment provides a sunflower oil modified water-based polyurethane dispersion. In parts by weight, the raw materials for the preparation of the sunflower oil modified water-based polyurethane dispersion include 25 parts of polyethylene oxide ether glycol (molecular weight 1000) , 13 parts of sunflower oil-based dihydroxy acid (preparation example 2) and 10 parts of toluene diisocyanate; The solid content of described sunflower oil modified aqueous polyurethane dispersion is 34.8%, and viscosity is 1300mpa.s, and particle diameter is 110nm .

The present embodiment provides a kind of preparation method of sunflower oil modified aqueous polyurethane dispersion, specifically comprises the following steps:

Put the polyethylene oxide ether glycol and sunflower oil-based dihydroxy acid into the reaction kettle according to the formula amount, heat up to 60° C. to melt, and stir and dehydrate under vacuum. Add toluene diisocyanate into the reaction kettle, raise the temperature to 75°C and continue the reaction for 3 hours, add 30 parts of acetone to dilute, and continue the reaction for 3 hours; check the NCO value, add 0.5 parts of neutralizing agent ammonia water after passing the test, and continue to stir for 0.8 hours; then , adding 60 parts of deionized water to it for emulsification. The ratio of the NCO value of the isocyanate to the total hydroxyl value of the polymer polyol and sunflower oil based dihydroxy acid was 1.08:1. The obtained material is subjected to rotary vacuum evaporation to remove the organic solvent in the material to obtain the sunflower oil modified aqueous polyurethane dispersion.

Example 3

The present embodiment provides a sunflower oil modified water-based polyurethane dispersion, in parts by weight, the preparation raw material of the sunflower oil modified water-based polyurethane dispersion includes 30 parts of polybutylene adipate diol (molecular weight 2000), 15 parts of sunflower oil-based dihydroxy acids (preparation example 3) and 13 parts of isophorone diisocyanate; the solid content of the sunflower oil modified aqueous polyurethane dispersion is 35.3%, and the viscosity is 1600mpa.s , the particle size is 90nm.

The present embodiment provides a kind of preparation method of sunflower oil modified aqueous polyurethane dispersion, specifically comprises the following steps:

Put polybutylene adipate diol and sunflower oil-based dihydroxy acid into a reaction kettle according to the formula amount, heat up to 70° C. to melt, and stir and dehydrate under vacuum. Add isophorone diisocyanate into the reaction kettle, raise the temperature to 85°C and continue the reaction for 5 hours, add 45 parts of acetone to dilute, and continue the reaction for 4 hours; check the NCO value, add 0.6 parts of neutralizing agent triethylamine after passing the test, and continue Stir for 1 h; then, add 70 parts of deionized water to it for emulsification. The ratio of the NCO value of the isocyanate to the total hydroxyl value of the polymer polyol and sunflower oil based dihydroxy acid is 1.1:1. The obtained material is subjected to rotary vacuum evaporation to remove the organic solvent in the material to obtain the sunflower oil modified aqueous polyurethane dispersion.

Example 4

This embodiment provides a sunflower oil-modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is the sunflower oil-based dihydroxy acid provided in Preparation Example 4, and other The raw materials, dosage and preparation method are all the same as in Example 1 (the solid content of the sunflower oil modified aqueous polyurethane dispersion is 34.7%, the viscosity is 800mpa.s, and the particle size is 190nm).

Example 5

This embodiment provides a sunflower oil-modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is the sunflower oil-based dihydroxy acid provided in Preparation Example 5, and other The raw materials, dosage and preparation method are all the same as in Example 1 (the solid content of the sunflower oil modified aqueous polyurethane dispersion is 34.9%, the viscosity is 3000mpa.s, and the particle size is 50nm).

Example 6

This embodiment provides a sunflower oil modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is the sunflower oil-based dihydroxy acid provided in Preparation Example 6, and other Raw material, consumption and preparation method are all identical with embodiment 1.

Example 7

This embodiment provides a sunflower oil-modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is the sunflower oil-based dihydroxy acid provided in Preparation Example 7, and other Raw material, consumption and preparation method are all identical with embodiment 1.

Comparative example 1

This comparative example provides a sunflower oil modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is replaced by dimethylol propionic acid DMPA with an equivalent hydroxyl molar amount , other raw materials, consumption and preparation method are all identical with embodiment 1.

Comparative example 2

This comparative example provides a sunflower oil modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is replaced by dimethylol butyric acid DMBA with an equivalent hydroxyl molar amount , other raw materials, consumption and preparation method are all identical with embodiment 1.

Comparative example 3

This comparative example provides a sunflower oil modified water-based polyurethane dispersion, which differs from Example 1 only in that the content of the sunflower oil-based dihydroxy acid is 5 parts, and the amount of polymer polyol is adjusted so that the prepared The molar ratio of hydroxyl groups in the raw materials is constant, and other raw materials, consumption and preparation method are all the same as in Example 1.

Comparative example 4

This comparative example provides a sunflower oil modified water-based polyurethane dispersion, which differs from Example 1 only in that the content of the sunflower oil-based dihydroxy acid is 20 parts, and the amount of polymer polyol is adjusted so that the prepared The molar ratio of hydroxyl groups in the raw materials is constant, and other raw materials, consumption and preparation method are all the same as in Example 1.

Comparative example 5

This comparative example provides a sunflower oil-modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is replaced by the methoxy acid obtained in Preparation Example 1 with an equivalent hydroxyl molar amount. Alkylated sunflower oil, other raw materials, consumption and preparation method are all identical with embodiment 1.

Comparative example 6

This comparative example provides a castor oil modified water-based polyurethane dispersion, which differs from Example 1 only in that the sunflower oil-based dihydroxy acid is replaced by the castor oil obtained in Comparative Preparation Example 1 with an equivalent hydroxyl molar amount. Base dihydroxy acid, other raw materials, consumption and preparation method are all identical with embodiment 1.

Application example

A kind of polyurethane synthetic leather, the preparation method of described polyurethane synthetic leather comprises:

Add 1 part of color paste, 0.3 part of thickener (BR100P) and 0.1 part of leveling agent (BYK- 349) Stir well to obtain a water-based polyurethane slurry, then apply the slurry to the surface of the release paper, and dry it in an oven at 90°C for 3 minutes, and then coat the water-based polyurethane primer (Asahikawa Chemical XCWB-5020) , and then paste the water-based polyurethane base, put it in a 110-degree oven and dry it to get the water-based polyurethane synthetic leather.

Performance Testing:

Test the 100%, 300% modulus and tensile strength of the waterborne polyurethane dispersion according to the FZT 01114-2012 standard; test the softening point of the waterborne polyurethane dispersion according to the GB/T 12007.6-1989 standard.

The specific test results are shown in Table 1:

Table 1

As can be seen from the above table, the sunflower oil modified water-based polyurethane dispersion provided by the present invention uses sunflower oil-based dihydroxy acid as raw material, so that the water-based polyurethane material has high modulus, high tensile strength and high softening point ; meet the requirements of polyurethane performance; as can be seen from Examples 1 to 3, the 100% modulus of the polyurethane synthetic leather is 6.39 to 6.74MPa, the 300% modulus is 17.46 to 18.34MPa, and the tensile strength reaches 35.81 to 42.09MPa, softening The temperature is 188～207℃; the heat resistance is good.

From the comparison of Example 1 with Examples 4-7, it can be seen that the raw materials for the preparation of the sunflower oil-based dihydroxy acid are not in a specific ratio, and the mechanical properties and heat resistance of the synthetic leather are deteriorated.

From the comparison of Example 1 and Comparative Examples 1 and 2, it can be seen that the performance of the sunflower oil-based dihydroxy acid is better than that of conventional hydrophilic chain extenders.

From the comparison of Example 1 and Comparative Examples 3 and 4, it can be known that the sunflower oil-based dihydroxy acid content is within a specific content range, and the prepared dispersion has the best physical properties.

From the comparison of Example 1 and Comparative Examples 5 and 6, it can be seen that the physical properties of the finally obtained aqueous polyurethane dispersions are significantly different when using methoxylated sunflower oil or castor oil-based dihydroxy acid.

In summary, the sunflower oil-modified aqueous polyurethane dispersion provided by the present invention uses commercially available sunflower oil as a raw material to prepare a green and renewable sunflower oil-based dihydroxy acid, which can be used as a chain extender The agent can also be used as an internal emulsifier and as a raw material for the preparation of polyurethane. Compared with conventional hydrophilic chain extenders, it has more excellent thermodynamic properties, and has higher hardness and tensile strength; it improves the modulus of polyurethane, Tensile strength and softening point; and the raw materials are easy to obtain, low in cost, environmentally friendly, and suitable for industrial production.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A sunflower oil modified waterborne polyurethane dispersion, characterized in that, in parts by weight, the raw materials for preparing the sunflower oil modified waterborne polyurethane dispersion include 20 to 30 parts of polymer polyols, 6 to 30 parts of isocyanates 13 parts and 10-15 parts of sunflower oil-based dihydroxy acid. 2. the sunflower oil modified aqueous polyurethane dispersion according to claim 1, is characterized in that, described sunflower oil modified dihydroxy acid accounts for 28% of polymer polyol and sunflower oil base dihydroxy acid gross mass ~35%. 3. according to claim 1 and 2 described sunflower oil modified aqueous polyurethane dispersions, it is characterized in that, described sunflower oil base dihydroxy acid adopts following method to prepare, and described method comprises: (i) sunflower oil is mixed with formic acid and hydrogen peroxide, and reacted to obtain epoxidized sunflower oil; (ii) reacting the epoxidized sunflower oil obtained in step (i) with methanol to obtain methoxylated sunflower oil; (iii) Saponifying the methoxylated sunflower oil obtained in step (ii) with an alkali to obtain the sunflower oil-based dihydroxy acid. 4. sunflower oil modified aqueous polyurethane dispersion according to claim 3, is characterized in that, the mass ratio of sunflower oil described in step (i) and formic acid, hydrogen peroxide is 1:(0.3～0.8): (0.3～0.7); Preferably, the mixing in step (i) includes mixing the sunflower oil with formic acid, then adding hydrogen peroxide to react; Preferably, the temperature at which the sunflower oil is mixed with formic acid is 40-60°C; Preferably, the mixing time is 0.5 to 2 hours; Preferably, the temperature of the reaction in step (i) is 45-65°C; Preferably, the reaction time in step (i) is 1 to 5 hours; Preferably, the system of the reaction described in step (ii) also includes a catalyst; Preferably, the catalyst comprises at least one of trifluoromethanesulfonic acid, sulfuric acid or p-toluenesulfonic acid; Preferably, in the reaction system described in step (ii), the mass ratio of epoxidized sunflower oil to methanol and the catalyst is 1:(5～10):(0.0001～0.0005); Preferably, the temperature of the reaction in step (ii) is 65-90°C; Preferably, the reaction time in step (ii) is 1 to 5 hours; Preferably, the system of the reaction described in step (iii) also includes a solvent; Preferably, in the reaction system described in step (iii), the mass ratio of methoxylated sunflower oil to alkali and solvent is 1:(0.4～0.9):(1.2～1.8); Preferably, the reaction time in step (iii) is 4-8 hours. 5. The sunflower oil modified aqueous polyurethane dispersion according to any one of claims 1 to 4, wherein the number average molecular weight of the polymer polyol is 500 to 2000; Preferably, the polymer polyol comprises at least one of polytetramethylene ether diol, polyethylene oxide ether diol, polycaprolactone diol or polybutylene adipate diol kind; Preferably, the isocyanate includes at least one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate or 1,6-hexamethylene diisocyanate. 6. The sunflower oil-modified water-based polyurethane dispersion according to any one of claims 1 to 5, characterized in that, in parts by weight, the raw materials for preparing the sunflower oil-modified water-based polyurethane dispersion also include 0.3 ~0.6 parts of neutralizer; Preferably, the solid content of the sunflower oil-modified aqueous polyurethane dispersion is 30% to 40%; Preferably, the viscosity of the sunflower oil modified aqueous polyurethane dispersion is 1000-2000mpa·s; Preferably, the particle size of the sunflower oil-modified aqueous polyurethane dispersion is 80-150 nm. 7. a preparation method of the sunflower oil modified waterborne polyurethane dispersion according to any one of claims 1 to 6, characterized in that, the preparation method comprises: After the polymer polyol is mixed with the sunflower oil-based dihydroxy acid, it is reacted with isocyanate, and after the reaction, water is added for emulsification to obtain the sunflower oil-modified aqueous polyurethane dispersion. 8. The preparation method according to claim 7, characterized in that, the mixing temperature is 50-70°C; Preferably, the step of vacuum dehydration is also included after the mixing; Preferably, the reaction temperature is 70-80°C; Preferably, the reaction time is 2 to 5 hours; Preferably, after the reaction, the step of adding an organic solvent for dilution and continuing the reaction is also included; Preferably, adding an organic solvent to dilute and continuing the reaction takes 2 to 4 hours. 9. The preparation method according to claim 8, characterized in that adding an organic solvent for dilution and continuing the reaction further includes adding a neutralizing agent to carry out the neutralization reaction; Preferably, the time for the neutralization reaction is 0.5 to 1 h; Preferably, the step of removing the organic solvent is also included after the emulsification. 10. A synthetic leather, characterized in that the raw material of the synthetic leather comprises the sunflower oil modified aqueous polyurethane dispersion according to any one of claims 1-6.