Non-ionic waterborne polyurethane resin as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high-molecular polymers, and particularly relates to nonionic waterborne polyurethane resin as well as a preparation method and application thereof. The invention relates to a high-temperature-resistant polyester polyol, which comprises the following components: 70-85 parts by mass of macromolecular polyol; 20 to 30 parts by mass of polyisocyanate; 5-15 parts by mass of a small molecular alcohol chain extender; 1-6 parts by mass of a small molecular alcohol end-capping reagent; 2-10 parts by mass of an amine chain extender; 0.01 to 0.5 part by mass of a catalyst; wherein the small molecular alcohol end-capping reagent is hydroxyethyl piperidine carboxylic acid isobutyl ester. The self-mosquito-repelling and insect-repelling waterborne polyurethane resin prepared by the invention can realize a lasting mosquito-repelling effect without adding a mosquito repellent.

Description

Technical Field

[0001] The invention belongs to the technical field of high molecular polymers, and in particular relates to a non-ionic waterborne polyurethane resin and a preparation method and application thereof. Background Art

[0002] Waterborne polyurethane (WPU) uses water as a dispersion medium. It has the advantages of being non-flammable, low VOC emissions, low production costs and a wide range of uses. It is widely used in many fields, and waterborne polyurethane leather is one of them. Waterborne polyurethane can be divided into three categories according to the charge properties of the hydrophilic group: anionic, cationic and non-ionic. Non-ionic waterborne polyurethane forms a balanced repulsive force through the "association" of hydrophilic groups and water molecules and the steric effect, so that the polymer molecules are stably dispersed in the water phase. Therefore, when ionic compounds such as acids, bases, and salts are added, it still has excellent stability, which makes it easier to prepare the wetting agent.

[0003] In summer, flies and mosquitoes are easy to breed. In addition to causing a series of common allergic symptoms such as itching and pain on human skin, mosquito bites can also spread a variety of viral diseases, such as dysentery, dengue fever and epidemic encephalitis B, etc. According to relevant research, there are more than 80 diseases spread by mosquitoes. The existing non-ionic waterborne polyurethane resin does not have the function of repelling mosquitoes. Therefore, it is necessary to provide a non-ionic waterborne polyurethane resin and its preparation method and application to solve the above problems. Summary of the invention

[0004] In order to overcome the defects in the prior art, the present invention provides a nonionic waterborne polyurethane resin and a preparation method and application thereof. The nonionic waterborne polyurethane resin of the present invention not only has the function of repelling mosquitoes and insects, but also can repel mosquitoes and insects for a long time.

[0005] To achieve one of the above purposes, the present invention adopts the following technical solution:

[0006] A nonionic waterborne polyurethane resin comprises the following components:

[0007] 70-85 parts by weight of macromolecular polyol;

[0008] 20 to 30 parts by weight of polyisocyanate;

[0009] 5 to 15 parts by weight of small molecule alcohol chain extender;

[0010] 1 to 6 parts by weight of small molecule alcohol capping agent;

[0011] 2 to 10 parts by weight of amine chain extender;

[0012] Catalyst 0.01-0.5 parts by mass;

[0013] Wherein, the small molecule alcohol capping agent is hydroxyethylpiperidinecarboxylic acid isobutyl ester.

[0014] Preferably, the macromolecular polyol is composed of 30 to 60 parts by mass of polyethylene glycol polyol and 25 to 40 parts by mass of other polyols, wherein the other polyols include any one or a combination of two or more of polyester polyols, polycarbonate polyols, polytetramethylene ether polyols, polyethylene oxide polyols, polypropylene oxide polyols, polyester ether polyols, polysiloxane polyols and bio-based polyols.

[0015] Preferably, the molecular weights of polyethylene glycol and macromolecular polyol are both 1000-3000.

[0016] Preferably, the polyisocyanate includes any one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, methylcycloethyl diisocyanate, hexamethylene diisocyanate, dicycloethylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, tetramethyl meta-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, methylcycloethyl diisocyanate and dimethyl diphenylmethane diisocyanate.

[0017] Preferably, the small molecule alcohol chain extender includes any one or a combination of two or more of dimethylolpropionic acid, dimethylolbutyric acid, ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, neopentyl glycol, methylpropylene glycol, 1,6-ethylene glycol, 1,3-propylene glycol, butylethylpropylene glycol, diethylpentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol and cyclohexanediol.

[0018] Preferably, the amine chain extender includes any one or a combination of two or more of isophorone diamine, diaminocyclohexylmethane, ethylenediamine, trimethylethylenediamine and hexamethylenediamine.

[0019] Preferably, the catalyst is an organobismuth catalyst.

[0020] To achieve the second objective, the present invention provides a method for preparing a nonionic waterborne polyurethane resin, comprising the following steps:

[0021] Weigh the raw materials in parts by mass, react the macromolecular polyol and the polyisocyanate at 85-95° C. for 1.5-2.5 hours; then add the small molecule alcohol chain extender and the catalyst at 70-85° C. for 4-5 hours; then add hydroxyethyl piperidine carboxylic acid isobutyl ester and react at 65-75° C. for 1-2 hours; add deionized water for emulsification and then drop the amine chain extender, perform vacuum distillation after the reaction, and obtain a waterborne polyurethane resin.

[0022] Preferably, acetone is added at the same time as the catalyst, and the amount of acetone added is 2w% to 3w% of the total amount of raw materials added, which plays a role in reducing viscosity; acetone is added before adding the amine chain extender, and the amount of acetone added is 10w% to 30w% of the total amount of raw materials added.

[0023] To achieve the third objective, the present invention provides an application of a nonionic waterborne polyurethane resin for preparing durable leather capable of repelling mosquitoes and insects.

[0024] The advantages of the present invention are:

[0025] (1) The present invention provides a self-repellent mosquito and insect repellent water-based polyurethane resin, which reacts isobutyl hydroxyethyl piperidine carboxylate onto a polyurethane linker through a chemical reaction, allowing it to be slowly released, and the purpose of long-lasting mosquito and insect repellency can be achieved without the need for an external mosquito repellent, and the durability is greatly improved. The resin is widely applicable and can be used to make mosquito repellent leather or mosquito repellent rubber products, etc.

[0026] (2) The present invention uses isobutyl hydroxyethyl piperidine carboxylate as a capping agent. The prepared water-based polyurethane has an insect repellent effect after drying. The isobutyl hydroxyethyl piperidine carboxylate is reacted to the polyurethane segment through a chemical reaction, which allows it to be slowly released. Compared with the back-end addition, the durability of the mosquito repellent is greatly improved.

[0027] (3) The present invention can achieve different mosquito repellent effects according to different addition amounts of the waterborne polyurethane resin. Hydroxyethyl piperidine carboxylic acid isobutyl ester is easily soluble in organic solvents and has primary hydroxyl groups, which can react with polyisocyanates. The emulsion synthesis process is simple and efficient, and can be widely used in the leather manufacturing field. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is the structural formula of hydroxyethylpiperidinecarboxylic acid isobutyl ester of the present invention.

[0029] Figure 2 This is a structural formula in which isobutyl hydroxyethylpiperidinylcarboxylate is used as a capping agent to access the main chain. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] 40g of polytetrahydrofuran ether polyol (molecular weight of 1000) and 40g of polyethylene glycol polyol (molecular weight of 1000) were dehydrated at 95°C for 30 minutes, then cooled to 50°C, 30g of toluene diisocyanate was added, the temperature was raised to 85°C for 2.5 hours, the NCO content was measured after 2 hours, and the temperature was lowered to 50°C when the theoretical value was reached, and then 2g of 1,4-butanediol, 0.4g of organic bismuth catalyst and 20g of acetone were added to react at 80°C for 4h, and then 2g of hydroxyethyl piperidine carboxylic acid isobutyl ester was added to react at 65°C for 2h. After the reaction, the NCO content was measured, 40g of acetone was added to reduce the viscosity, and then the temperature was lowered to 10°C, and deionized water was added under high-speed shearing. After the prepolymer was opened, 3g of ethylenediamine was slowly added dropwise, and after reacting for 5min, the acetone in the system was removed by reduced pressure distillation to obtain a waterborne polyurethane resin sample 1 with a solid content of 35.2%.

[0033] The waterborne polyurethane resin sample 1 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito Repellent Properties of Textiles". The test results showed that the repellency rate reached 96.33%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 89.33%.

[0034] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength and elongation at break of the obtained waterborne polyurethane film were tested according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results showed that the tensile strength was 12.8 MPa and the elongation at break was 530.2%. The waterborne polyurethane resin was applied to the formulation for preparing leather to obtain leather with excellent mosquito repellent performance.

[0035] Example 2

[0036] 40 g of poly (neopentyl adipate glycol) polyol (molecular weight 2000) and 38 g of polyethylene glycol polyol (molecular weight 1000) were dehydrated at 95 ° C for 30 min, then cooled to 50 ° C, 24 g of isophorone diisocyanate was added, the temperature was raised to 90 ° C and kept for 2 hours, and the NCO content was measured after 2 hours. When the theoretical value was reached, the temperature was lowered to 50 ° C, and then 6 g of DMPA (dihydroxymethyl propionic acid), 0.6 g of methyl propanediol, 0.4 g of organic bismuth catalyst and 20 g of acetone were reacted at 70°C for 4 h, and then 1.5 g of hydroxyethylpiperidinecarboxylic acid isobutyl ester was added and reacted at 65°C for 2 h. After the reaction, the NCO content was measured, 40 g of acetone was added to reduce the viscosity, and the temperature was lowered to 10°C. Deionized water was added under high-speed shearing. After the prepolymer was opened, 3 g of hexamethylenediamine was slowly added dropwise. After the reaction for 5 min, the acetone in the system was removed by vacuum distillation to obtain a waterborne polyurethane resin sample 2 with a solid content of 34.5%.

[0037] The waterborne polyurethane resin sample 2 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito-Repellent Properties of Textiles". The test results showed that the repellency rate reached 94.67%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 86.73%.

[0038] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength and elongation at break of the obtained waterborne polyurethane film were tested according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results showed that the tensile strength was 18.4 MPa and the elongation at break was 822.2%. The waterborne polyurethane resin was applied to the formulation for preparing leather to obtain leather with excellent mosquito repellent performance.

[0039] Example 3

[0040] 35g of polypropylene glycol polyol (molecular weight 2000) and 40g of polyethylene glycol polyol (molecular weight 2000) were dehydrated at 95°C for 1h, then cooled to 50°C, 25g of 1,6-hexamethylene diisocyanate was added, the temperature was raised to 90°C and kept for 2 hours, the NCO content was measured after 2 hours, and when the theoretical value was reached, the temperature was lowered to 50°C, and then 6g of DMPA (dihydroxymethylbutyric acid), 4g of 1,4-butanediol, and 0.4g of organic The bismuth catalyst and 20g of acetone were reacted at 70°C for 5h, and then 3g of isobutyl hydroxyethylpiperidinecarboxylate was added and reacted at 70°C for 2h. After the reaction, the NCO content was measured, 40g of acetone was added to reduce the viscosity, and then the temperature was lowered to 10°C. Deionized water was added under high-speed shearing. After the prepolymer was opened, 3g of trimethylethylenediamine was slowly added dropwise. After reacting for 5min, the acetone in the system was removed by reduced pressure distillation to obtain a waterborne polyurethane resin sample 3 with a solid content of 34%.

[0041] The waterborne polyurethane resin sample 3 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito-Repellent Properties of Textiles". The test results showed that the repellency rate reached 94.33%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 83.66%.

[0042] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength and elongation at break of the obtained waterborne polyurethane film were tested according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results showed that the tensile strength was 16.4 MPa and the elongation at break was 860.2%. The waterborne polyurethane resin was applied to the formulation for preparing leather to obtain leather with excellent mosquito repellent performance.

[0043] Example 4

[0044] 36g of polypropylene oxide polyol (molecular weight 1000) and 40g of polyethylene glycol polyol (molecular weight 1000) were dehydrated at 95°C for 1h, then cooled to 50°C, 26g of dicyclohexylmethane diisocyanate was added, the temperature was raised to 85°C and kept for 2.5 hours, the NCO content was measured after 2 hours, and when the theoretical value was reached, the temperature was lowered to 50°C, and then 7g of DMPA (dihydroxymethylbutyric acid), 3g of 1,4-butanediol, and 0.4g of Bismuth catalyst and 20g of acetone were reacted at 85°C for 4h, and then 3g of isobutyl hydroxyethylpiperidinecarboxylate was added and reacted at 75°C for 1h. After the reaction, the NCO content was measured, 40g of acetone was added to reduce the viscosity, and then the temperature was lowered to 10°C, and deionized water was added under high-speed shear. After the prepolymer was opened, 3g of isophorone diamine was slowly added dropwise. After reacting for 5min, the acetone in the system was removed by reduced pressure distillation to obtain a waterborne polyurethane resin sample 4 with a solid content of 33.2%.

[0045] The waterborne polyurethane resin sample 4 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito-Repellent Properties of Textiles". The test results showed that the repellency rate reached 97.54%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 90.33%.

[0046] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength and elongation at break of the obtained waterborne polyurethane film were tested according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results showed that the tensile strength was 15.8 MPa and the elongation at break was 772.4%. The waterborne polyurethane resin was applied to the formulation for preparing leather to obtain leather with excellent mosquito repellent performance.

[0047] Example 5

[0048] 42g of polytetrahydrofuran ether polyol (molecular weight 1800) and 40g of polyethylene glycol polyol (molecular weight 2000) were dehydrated at 95°C for 1h, then cooled to 50°C, 24g of 1,4-cyclohexane diisocyanate was added, the temperature was raised to 90°C and kept for reaction for 1.5 hours, the NCO content was measured after two hours, and when the theoretical value was reached, the temperature was lowered to 50°C, and then 5.5g of DMPA (dihydroxymethylbutyric acid), 1g of methylpropylene glycol, and 0.4g of The organic bismuth catalyst and 20g of acetone were reacted at 80°C for 4h, and then 2.4g of hydroxyethylpiperidinecarboxylic acid isobutyl ester was added and reacted at 70°C for 2h. After the reaction, the NCO content was measured, 40g of acetone was added to reduce the viscosity, and then the temperature was lowered to 20°C, and deionized water was added under high-speed shearing. After the prepolymer was opened, 3g of ethylenediamine was slowly added dropwise. After the reaction for 5min, the acetone in the system was removed by reduced pressure distillation to obtain a waterborne polyurethane resin sample 5 with a solid content of 36.1%.

[0049] The waterborne polyurethane sample 5 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito-Repellent Properties of Textiles". The test results showed that the repellency rate reached 94.89%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 88.56%.

[0050] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength and elongation at break of the obtained waterborne polyurethane film were tested according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results showed that the tensile strength was 12.6 MPa and the elongation at break was 886.1%. The waterborne polyurethane resin was applied to the formulation for preparing leather to obtain leather with excellent mosquito repellent performance.

[0051] Comparative Example 1

[0052] 42g of polytetrahydrofuran ether polyol (molecular weight of 1800) and 40g of polyethylene glycol polyol (molecular weight of 2000) were dehydrated at 95°C for 1h, then cooled to 50°C, 24g of 1,4-cyclohexane diisocyanate was added, the temperature was raised to 90°C and kept for reaction for 3 hours, the NCO content was measured after two hours, and the temperature was lowered to 50°C when it reached the theoretical value, and then 5.5g of DMPA (dihydroxymethylbutyric acid), 1g of methyl propanediol, 0.4g of organic bismuth catalyst and 20g of acetone were added and reacted at 70°C for 4h. After the reaction, the NCO content was measured, 40g of acetone was added to reduce the viscosity, and then the temperature was lowered to 20°C, deionized water was added under high-speed shear, and after the prepolymer was opened, 3.4g of ethylenediamine was slowly added dropwise, and after the reaction for 5min, the acetone in the system was removed by reduced pressure distillation to obtain waterborne polyurethane resin sample 6 with a solid content of 35.6%.

[0053] The waterborne polyurethane sample 6 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito-Repellent Properties of Textiles". The test results showed that the repellency rate reached 3.33%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 3.33%.

[0054] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength test and elongation at break test were performed on the obtained waterborne polyurethane film according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results were: the tensile strength was 24.5 MPa, and the elongation at break was 688.8%.

[0055] Comparative Example 2

[0056] 2 g of isobutyl hydroxyethylpiperidinylcarboxylate was added to the waterborne polyurethane sample 6, and the mixture was stirred evenly to obtain the waterborne polyurethane sample 7.

[0057] The waterborne polyurethane sample 7 was made into a leather sample, and the leather sample was tested with reference to GB / T 30126-2013 "Testing and Evaluation of Mosquito Repellent Properties of Textiles". The test results showed that the repellency rate reached 96.77%. The leather sample was placed in a 50°C oven for one month and then tested again, and the repellency rate reached 6.77%. It can be seen that the mosquito repellent effect has decreased significantly.

[0058] The emulsion was spread and solidified to obtain a waterborne polyurethane film. The tensile strength test and elongation at break test were performed on the obtained waterborne polyurethane film according to GB / T 1040-92 "Test Method for Tensile Properties of Plastics". The test results were: the tensile strength was 24.2 MPa, and the elongation at break was 665.67%.

[0059] Through the above comparison, it can be seen that after the waterborne polyurethane resin prepared in Examples 1-5 is prepared into leather, the mosquito repellent durability is significantly higher than the mosquito repellent duration after the waterborne polyurethane resin in Comparative Examples 1-2 is prepared into leather.

[0060] The determination of NCO content in the above examples and comparative examples is used to determine the degree of reaction. Figure 1 is the structural formula of hydroxyethylpiperidinecarboxylic acid isobutyl ester of the present invention; Figure 2 This is the structural formula of Example 1-5, in which isobutyl hydroxyethylpiperidinecarboxylate is used as a capping agent to be connected to the main chain.

[0061] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A nonionic waterborne polyurethane resin, characterized in that: Includes the following components: 70-85 parts by weight of macromolecular polyol; 20 to 30 parts by weight of polyisocyanate; 5 to 15 parts by weight of small molecule alcohol chain extender; 1 to 6 parts by weight of small molecule alcohol capping agent; 2 to 10 parts by weight of amine chain extender; Catalyst 0.01-0.5 parts by mass; Wherein, the small molecule alcohol capping agent is hydroxyethylpiperidinecarboxylic acid isobutyl ester.

2. A nonionic waterborne polyurethane resin according to claim 1, characterized in that: The macromolecular polyol is composed of 30 to 60 parts by mass of polyethylene glycol polyol and 25 to 40 parts by mass of other polyols, wherein the other polyols include any one or a combination of two or more of polyester polyols, polycarbonate polyols, polytetramethylene ether polyols, polyethylene oxide polyols, polypropylene oxide polyols, polyester ether polyols, polysiloxane polyols and bio-based polyols.

3. A nonionic waterborne polyurethane resin according to claim 2, characterized in that: The molecular weights of the polyethylene glycol and the macromolecular polyol are both 1000-3000.

4. A nonionic waterborne polyurethane resin according to claim 1, characterized in that: The polyisocyanate includes any one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, methylcycloethyl diisocyanate, hexamethylene diisocyanate, dicycloethylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, tetramethyl meta-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, methylcycloethyl diisocyanate and dimethyl diphenylmethane diisocyanate.

5. A nonionic waterborne polyurethane resin according to claim 1, characterized in that: The small molecule alcohol chain extender includes any one or a combination of two or more of dimethylolpropionic acid, dimethylolbutyric acid, ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propylene glycol, butylethylpropylene glycol, diethylpentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol and cyclohexanediol.

6. A nonionic waterborne polyurethane resin according to claim 1, characterized in that: The amine chain extender includes any one or a combination of two or more of isophorone diamine, diaminocyclohexylmethane, ethylenediamine, trimethylethylenediamine and hexamethylenediamine.

7. A nonionic waterborne polyurethane resin according to claim 1, characterized in that: The catalyst is an organic bismuth catalyst.

8. A method for preparing a nonionic waterborne polyurethane resin according to any one of claims 1 to 7, characterized in that: The following steps are involved: Weigh the raw materials in parts by mass, react the macromolecular polyol and the polyisocyanate at 85-95° C. for 1.5-2.5 hours; then add the small molecule alcohol chain extender and the catalyst at 70-85° C. for 4-5 hours; then add hydroxyethyl piperidine carboxylic acid isobutyl ester and react at 65-75° C. for 1-2 hours; add deionized water for emulsification and then drop the amine chain extender, perform vacuum distillation after the reaction, and obtain a waterborne polyurethane resin.

9. The method for preparing the nonionic waterborne polyurethane resin according to claim 8, characterized in that: Acetone is added while adding the catalyst, and the amount of acetone added is 2w% to 3w% of the total amount of raw materials added; acetone is added before adding the amine chain extender, and the amount of acetone added is 10w% to 30w% of the total amount of raw materials added.

10. An application of the nonionic waterborne polyurethane resin according to any one of claims 1 to 7, characterized in that: The waterborne polyurethane resin is used for preparing durable leather capable of repelling mosquitoes and insects.

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