High-elasticity waterborne polyurethane resin and preparation method thereof

Abstract

The invention discloses high-elasticity waterborne polyurethane resin and a preparation method thereof, and belongs to the technical field of resin preparation, and the high-elasticity waterborne polyurethane resin comprises the following components in parts by weight: 30-50 parts of polyol, 10-15 parts of a silane copolymer, 0.05-2 parts of a catalyst, 2-5 parts of a chain extender, 5-10 parts of aliphatic isocyanate, 40-60 parts of water and 1-5 parts of a modifier. According to the high-elasticity permeable waterborne polyurethane resin disclosed by the invention, the high-elasticity permeable waterborne polyurethane resin is prepared by adding the polyol, the silane copolymer, the catalyst, the chain extender, the water, the aliphatic isocyanate and the modifier. The prepared waterborne polyurethane has ultrahigh elasticity and excellent permeability, and the defects of poor permeability, poor toughness, poor water resistance and the like of waterborne polyurethane are overcome.

Description

Technical Field

[0001] This invention belongs to the field of resin preparation technology, and particularly relates to a highly elastic waterborne polyurethane resin and its preparation method. Background Technology

[0002] Waterborne polyurethane is a polymer produced using water as a solvent and polyether or polyester as the main raw materials through a polymer reaction. It is solvent-free and boasts advantages such as low pollution, occupational safety, excellent mechanical properties, good compatibility, and ease of modification. It can be widely used in coatings, adhesives, fabric coatings and finishing agents, leather finishing agents, paper surface treatment agents, and fiber surface treatment agents.

[0003] However, although waterborne polyurethane has many excellent properties, it still has many shortcomings, such as poor water resistance, poor solvent resistance, poor permeability, poor toughness, and poor surface gloss. In view of the above shortcomings, the present invention provides a highly elastic and permeable waterborne polyurethane resin, which is mainly made of polyol and polyvinyl alcohol, has excellent environmental protection, and has excellent elasticity and permeability. Summary of the Invention

[0004] The purpose of this invention is to address the problems of poor water resistance, poor solvent resistance, poor permeability, poor toughness, and poor surface gloss in existing waterborne polyurethanes, and to propose a high-elasticity waterborne polyurethane resin and its preparation method.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: A highly elastic waterborne polyurethane resin, by weight, comprises: 30-50 parts of polyol, 10-15 parts of silane copolymer, 0.05-2 parts of catalyst, 2-5 parts of chain extender, 5-10 parts of aliphatic isocyanate, 40-60 parts of water, and 1-5 parts of modifier.

[0006] As a further description of the above technical solution: The polyol comprises polyether polyol and sulfonate polyester polyol, with a mass ratio of polyether polyol to sulfonate polyester polyol of 20-40:5-20.

[0007] As a further description of the above technical solution: The polyether polyol has a molecular weight of 5000 and a hydroxyl value of 32.5-35.5 mgKOH / g, the sulfonate polyester polyol has a molecular weight of 2000 and a hydroxyl value of 50-60 mgKOH / g, and a sulfonate content of 0.35-0.40 mol.

[0008] As a further description of the above technical solution: The silane copolymer comprises at least one of hydroxyl-terminated polydimethylsiloxane or amino-terminated polysiloxane.

[0009] As a further description of the above technical solution: The catalyst is at least one of tetraisopropyl titanate, organotin, and organobismuth, with dibutyltin dilaurate being the catalyst, which can improve hardness, strength, and toughness.

[0010] As a further description of the above technical solution: The aliphatic isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 1,6-diisocyanate-2,2,4-trimethylhexane, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, and trimethylsilyl isocyanate.

[0011] As a further description of the above technical solution: The chain extender includes a hydrophilic chain extender, which is one of dimethylolpropionic acid and dimethylolbutyric acid.

[0012] As a further description of the above technical solution: The modifier is one or more of polyvinyl alcohol, CMC, and hydroxymethyl cellulose.

[0013] A method for preparing a highly elastic waterborne polyurethane resin specifically includes the following steps: S1. Add the polyether polyol and sulfonic acid polyester polyol to the reactor in the mass ratio, turn on the agitator, maintain the temperature and stir at medium speed for a period of time. S2. Cool the material in the reactor to 90°C, add isophorone diisocyanate and dibutyltin dilaurate, maintain the temperature and stir at medium speed for a period of time. S3. Cool the material in the reactor to 80°C, add hydroxyl-terminated polydimethylsiloxane and dimethylolbutyric acid, maintain the temperature and stir at medium speed for a period of time. S4. Add a certain amount of deionized water, maintain the temperature and stir at medium speed for a period of time, then cool the material in the reactor and add the remaining deionized water. Continue to maintain the temperature and stir at high speed to obtain a semi-finished product of highly elastic and permeable waterborne polyurethane. S5. Polyvinyl alcohol and carboxymethyl cellulose are added to the reactor in a certain mass ratio. The temperature is maintained and the mixture is stirred at high speed for modification. After 2.5 hours, the material is discharged to obtain a highly elastic and permeable waterborne polyurethane resin.

[0014] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: In this invention, a highly elastic and permeable waterborne polyurethane resin is prepared by adding polyol, silane copolymer, catalyst, chain extender, water, aliphatic isocyanate, and modifier. The resin obtained by this invention possesses ultra-high elasticity and excellent permeability, overcoming the shortcomings of waterborne polyurethanes such as poor permeability, poor toughness, and poor water resistance. Detailed Implementation

[0015] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0016] A highly elastic waterborne polyurethane resin, by weight, comprises: 30-50 parts of polyol, 10-15 parts of silane copolymer, 0.05-2 parts of catalyst, 2-5 parts of chain extender, 5-10 parts of aliphatic isocyanate, 40-60 parts of water, and 1-5 parts of modifier.

[0017] Example 1 The polyol comprises polyether polyol and sulfonate polyester polyol, with a mass ratio of 20:20, where the polyether polyol comprises 20 parts and the sulfonate polyester polyol comprises 20 parts.

[0018] The polyether polyol has a molecular weight of 5000 and a hydroxyl value of 32.5 mgKOH / g, the sulfonate polyester polyol has a molecular weight of 2000 and a hydroxyl value of 50 mgKOH / g, and a sulfonate content of 0.35 mol.

[0019] The silane copolymer comprises at least one of hydroxyl-terminated polydimethylsiloxane or amino-terminated polysiloxane, wherein the hydroxyl-terminated polydimethylsiloxane is 10 parts.

[0020] The catalyst is at least one of tetraisopropyl titanate, organotin, and organobismuth. The catalyst is dibutyltin dilaurate, which can improve hardness, strength, and toughness. The amount of dibutyltin dilaurate is 0.3 parts.

[0021] The aliphatic isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 1,6-diisocyano-2,2,4-trimethylhexane, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, and trimethylsilyl isocyanate, wherein the isophorone diisocyanate is present in 8 parts.

[0022] The chain extender includes a hydrophilic chain extender, which is one of dimethylolpropionic acid and dimethylolbutyric acid, with dimethylolbutyric acid comprising 5 parts.

[0023] The modifier is one or more of polyvinyl alcohol, CMC, and hydroxymethyl cellulose, with 2 parts of polyvinyl alcohol and 2 parts of carboxymethyl cellulose.

[0024] A method for preparing a highly elastic waterborne polyurethane resin specifically includes the following steps: S1. Add polyether polyol and sulfonic acid polyester polyol to the reactor in the mass ratio, turn on the agitator, maintain the temperature at 120℃ and stir at medium speed for 30 minutes. S2. Cool the material in the reactor to 90°C, add isophorone diisocyanate and dibutyltin dilaurate, maintain the temperature at 90°C and stir at medium speed for 3 hours. S3. Cool the material in the reactor to 80°C, add hydroxyl-terminated polydimethylsiloxane and dimethylolbutyric acid, maintain the temperature at 80°C and stir at medium speed for 2 hours. S4. Add 20 parts of deionized water, maintain the temperature at 80℃ and stir at medium speed for 30 minutes. Then, cool the material in the reactor to 45℃ and add the remaining deionized water. Continue to maintain the temperature at 45℃ and stir at high speed for 30 minutes to obtain a semi-finished product of highly elastic permeable waterborne polyurethane. S5. Polyvinyl alcohol and carboxymethyl cellulose are added to the reactor in a certain mass ratio. The temperature is maintained at 40-45℃ and the mixture is stirred at high speed for modification. After 2.5 hours, the mixture is discharged to obtain a highly elastic and permeable waterborne polyurethane resin.

[0025] Example 2 The polyol comprises polyether polyol and sulfonate polyester polyol, with a mass ratio of 25:10 for polyether polyol and sulfonate polyester polyol, comprising 30 parts of polyether polyol and 20 parts of sulfonate polyester polyol.

[0026] The polyether polyol has a molecular weight of 5000 and a hydroxyl value of 33.5 mgKOH / g, the sulfonate polyester polyol has a molecular weight of 2000 and a hydroxyl value of 53 mgKOH / g, and a sulfonate content of 0.36 mol.

[0027] The silane copolymer comprises at least one of hydroxyl-terminated polydimethylsiloxane or amino-terminated polysiloxane, wherein the hydroxyl-terminated polydimethylsiloxane is 12 parts.

[0028] The catalyst is at least one of tetraisopropyl titanate, organotin, and organobismuth. The catalyst is dibutyltin dilaurate, which can improve hardness, strength, and toughness. The amount of dibutyltin dilaurate is 0.3 parts.

[0029] The aliphatic isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 1,6-diisocyano-2,2,4-trimethylhexane, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, and trimethylsilyl isocyanate, wherein the isophorone diisocyanate is present in 10 parts.

[0030] The chain extender includes a hydrophilic chain extender, which is one of dimethylolpropionic acid and dimethylolbutyric acid, with dimethylolbutyric acid comprising 5 parts.

[0031] The modifier is one or more of polyvinyl alcohol, CMC, and hydroxymethyl cellulose, with 2 parts of polyvinyl alcohol and 2 parts of carboxymethyl cellulose.

[0032] A method for preparing a highly elastic waterborne polyurethane resin specifically includes the following steps: S1. Add polyether polyol and sulfonic acid polyester polyol to the reactor in the mass ratio, turn on the agitator, maintain the temperature at 120℃ and stir at medium speed for 30 minutes. S2. Cool the material in the reactor to 90°C, add isophorone diisocyanate and dibutyltin dilaurate, maintain the temperature at 90°C and stir at medium speed for 3 hours. S3. Cool the material in the reactor to 80°C, add hydroxyl-terminated polydimethylsiloxane and dimethylolbutyric acid, maintain the temperature at 80°C and stir at medium speed for 2 hours. S4. Add 20 parts of deionized water, maintain the temperature at 80℃ and stir at medium speed for 30 minutes. Then, cool the material in the reactor to 45℃ and add the remaining deionized water. Continue to maintain the temperature at 45℃ and stir at high speed for 30 minutes to obtain a semi-finished product of highly elastic permeable waterborne polyurethane. S5. Polyvinyl alcohol and carboxymethyl cellulose are added to the reactor in a certain mass ratio. The temperature is maintained at 40-45℃ and the mixture is stirred at high speed for modification. After 2.5 hours, the mixture is discharged to obtain a highly elastic and permeable waterborne polyurethane resin.

[0033] Example 3 The polyol comprises polyether polyol and sulfonate polyester polyol, with a mass ratio of 30:15, 40 parts of polyether polyol and 20 parts of sulfonate polyester polyol.

[0034] The polyether polyol has a molecular weight of 5000 and a hydroxyl value of 34.5 mgKOH / g, the sulfonate polyester polyol has a molecular weight of 2000 and a hydroxyl value of 57 mgKOH / g, and a sulfonate content of 0.38 mol.

[0035] The silane copolymer comprises at least one of hydroxyl-terminated polydimethylsiloxane or amino-terminated polysiloxane, wherein the hydroxyl-terminated polydimethylsiloxane is 10 parts.

[0036] The catalyst is at least one of tetraisopropyl titanate, organotin, and organobismuth. The catalyst is dibutyltin dilaurate, which can improve hardness, strength, and toughness. The amount of dibutyltin dilaurate is 0.3 parts.

[0037] The aliphatic isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 1,6-diisocyano-2,2,4-trimethylhexane, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, and trimethylsilyl isocyanate, wherein the isophorone diisocyanate is present in 12 parts.

[0038] The chain extender includes a hydrophilic chain extender, which is one of dimethylolpropionic acid and dimethylolbutyric acid, with dimethylolbutyric acid comprising 5 parts.

[0039] The modifier is one or more of polyvinyl alcohol, CMC, and hydroxymethyl cellulose, with 2 parts of polyvinyl alcohol and 2 parts of carboxymethyl cellulose.

[0040] A method for preparing a highly elastic waterborne polyurethane resin specifically includes the following steps: S1. Add polyether polyol and sulfonic acid polyester polyol to the reactor in the mass ratio, turn on the agitator, maintain the temperature at 120℃ and stir at medium speed for 30 minutes. S2. Cool the material in the reactor to 90°C, add isophorone diisocyanate and dibutyltin dilaurate, maintain the temperature at 90°C and stir at medium speed for 3 hours. S3. Cool the material in the reactor to 80°C, add hydroxyl-terminated polydimethylsiloxane and dimethylolbutyric acid, maintain the temperature at 80°C and stir at medium speed for 2 hours. S4. Add 20 parts of deionized water, maintain the temperature at 80℃ and stir at medium speed for 30 minutes. Then, cool the material in the reactor to 45℃ and add the remaining deionized water. Continue to maintain the temperature at 45℃ and stir at high speed for 30 minutes to obtain a semi-finished product of highly elastic permeable waterborne polyurethane. S5. Polyvinyl alcohol and carboxymethyl cellulose are added to the reactor in a certain mass ratio. The temperature is maintained at 40-45℃ and the mixture is stirred at high speed for modification. After 2.5 hours, the mixture is discharged to obtain a highly elastic and permeable waterborne polyurethane resin.

[0041] Example 4 The polyol comprises polyether polyol and sulfonate polyester polyol, with a mass ratio of 35:20, where the polyether polyol comprises 35 parts and the sulfonate polyester polyol comprises 20 parts.

[0042] The polyether polyol has a molecular weight of 5000 and a hydroxyl value of 35.5 mgKOH / g, the sulfonate polyester polyol has a molecular weight of 2000 and a hydroxyl value of 60 mgKOH / g, and a sulfonate content of 0.40 mol.

[0043] The silane copolymer comprises at least one of hydroxyl-terminated polydimethylsiloxane or amino-terminated polysiloxane, wherein the hydroxyl-terminated polydimethylsiloxane is 10 parts.

[0044] The catalyst is at least one of tetraisopropyl titanate, organotin, and organobismuth. The catalyst is dibutyltin dilaurate, which can improve hardness, strength, and toughness. The amount of dibutyltin dilaurate is 0.3 parts.

[0045] The aliphatic isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 1,6-diisocyano-2,2,4-trimethylhexane, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, and trimethylsilyl isocyanate, wherein the isophorone diisocyanate is present in 10 parts.

[0046] The chain extender includes a hydrophilic chain extender, which is one of dimethylolpropionic acid and dimethylolbutyric acid, with dimethylolbutyric acid comprising 5 parts.

[0047] The modifier is one or more of polyvinyl alcohol, CMC, and hydroxymethyl cellulose, with 2 parts of polyvinyl alcohol and 2 parts of carboxymethyl cellulose.

[0048] A method for preparing a highly elastic waterborne polyurethane resin specifically includes the following steps: S1. Add polyether polyol and sulfonic acid polyester polyol to the reactor in the mass ratio, turn on the agitator, maintain the temperature at 120℃ and stir at medium speed for 30 minutes. S2. Cool the material in the reactor to 90°C, add isophorone diisocyanate and dibutyltin dilaurate, maintain the temperature at 90°C and stir at medium speed for 3 hours. S3. Cool the material in the reactor to 80°C, add hydroxyl-terminated polydimethylsiloxane and dimethylolbutyric acid, maintain the temperature at 80°C and stir at medium speed for 2 hours. S4. Add 20 parts of deionized water, maintain the temperature at 80℃ and stir at medium speed for 30 minutes. Then, cool the material in the reactor to 45℃ and add the remaining deionized water. Continue to maintain the temperature at 45℃ and stir at high speed for 30 minutes to obtain a semi-finished product of highly elastic permeable waterborne polyurethane. S5. Polyvinyl alcohol and carboxymethyl cellulose are added to the reactor in a certain mass ratio. The temperature is maintained at 40-45℃ and the mixture is stirred at high speed for modification. After 2.5 hours, the mixture is discharged to obtain a highly elastic and permeable waterborne polyurethane resin.

[0049] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A highly elastic waterborne polyurethane resin, characterized in that, By weight, it comprises: 30-50 parts of polyol, 10-15 parts of silane copolymer, 0.05-2 parts of catalyst, 2-5 parts of chain extender, 5-10 parts of aliphatic isocyanate, 40-60 parts of water, and 1-5 parts of modifier.

2. The highly elastic waterborne polyurethane resin according to claim 1, characterized in that, The polyol comprises polyether polyol and sulfonate polyester polyol, with a mass ratio of polyether polyol to sulfonate polyester polyol of 20-40:5-20.

3. The highly elastic waterborne polyurethane resin according to claim 2, characterized in that, The polyether polyol has a molecular weight of 5000 and a hydroxyl value of 32.5-35.5 mgKOH / g, the sulfonate polyester polyol has a molecular weight of 2000 and a hydroxyl value of 50-60 mgKOH / g, and a sulfonate content of 0.35-0.40 mol.

4. The highly elastic waterborne polyurethane resin according to claim 1, characterized in that, The silane copolymer comprises at least one of hydroxyl-terminated polydimethylsiloxane or amino-terminated polysiloxane.

5. The highly elastic waterborne polyurethane resin according to claim 1, characterized in that, The catalyst is at least one of tetraisopropyl titanate, organotin, and organobismuth, with dibutyltin dilaurate being the catalyst, which can improve hardness, strength, and toughness.

6. The highly elastic waterborne polyurethane resin according to claim 1, characterized in that, The aliphatic isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 1,6-diisocyanate-2,2,4-trimethylhexane, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, and trimethylsilyl isocyanate.

7. The highly elastic waterborne polyurethane resin according to claim 1, characterized in that, The chain extender includes a hydrophilic chain extender, which is one of dimethylolpropionic acid and dimethylolbutyric acid.

8. The highly elastic waterborne polyurethane resin according to claim 1, characterized in that, The modifier is one or more of polyvinyl alcohol, CMC, and hydroxymethyl cellulose.

9. A method for preparing a highly elastic waterborne polyurethane resin according to any one of claims 1-8, characterized in that, Specifically, the following steps are included: S1. Add the polyether polyol and sulfonic acid polyester polyol to the reactor in the mass ratio, turn on the agitator, maintain the temperature and stir at medium speed for a period of time. S2. Cool the material in the reactor to 90°C, add isophorone diisocyanate and dibutyltin dilaurate, maintain the temperature and stir at medium speed for a period of time. S3. Cool the material in the reactor to 80°C, add hydroxyl-terminated polydimethylsiloxane and dimethylolbutyric acid, maintain the temperature and stir at medium speed for a period of time. S4. Add a certain amount of deionized water, maintain the temperature and stir at medium speed for a period of time, then cool the material in the reactor and add the remaining deionized water. Continue to maintain the temperature and stir at high speed to obtain a semi-finished product of highly elastic and permeable waterborne polyurethane. S5. Polyvinyl alcohol and carboxymethyl cellulose are added to the reactor in a certain mass ratio. The temperature is maintained and the mixture is stirred at high speed for modification. After 2.5 hours, the material is discharged to obtain a highly elastic and permeable waterborne polyurethane resin.