TPU antistatic masterbatch formula and method

Abstract

The present invention relates to the technical field of polyurethanes, and discloses a TPU antistatic masterbatch formula and method, including 100 parts by weight of polyol, 10.7-16.2 parts by weight of diisocyanate, 8.6-15.2 parts by weight of tertiary amine sulfone chain extender, 1.4-3.7 parts by weight of alkyl bromide, 0.3-0.4 parts by weight of dibutyltin dilaurate, and 0.1-0.13 parts by weight of antioxidant; the present invention introduces an antistatic quaternary ammonium salt group into the main chain of the polyurethane, and the obtained TPU antistatic masterbatch has low surface resistivity, good electrical conductivity, and excellent antistatic performance. In addition, the introduction of a heat-resistant diphenyl sulfone structure is conducive to improving the heat resistance of the polyurethane TUP.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane, in particular to a TPU antistatic masterbatch formulation and method. Background Art

[0002] Polyurethane (TPU) is a polymer resin made from polyols, polyisocyanates, and chain extenders. It can be made into plastics, fibers, rubber elastomers, and other materials, and is widely used in footwear, synthetic leather, foam, adhesives, and other fields. However, traditional polyurethanes have high resistivity and poor conductivity and antistatic properties, which limit their practical applications.

[0003] Adding antistatic agents such as quaternary ammonium salts to polyurethane can improve its antistatic properties. Patent CN101581039B discloses a durable antistatic finish for fabrics and its preparation method. Using a reactive cationic polyurethane aqueous emulsion containing epoxy groups and quaternary ammonium salt cationic groups as a durable antistatic finish, the finish imparts excellent antistatic properties to fabrics. Compared to that invention, the present invention not only enhances the antistatic properties of polyurethane (TPU) but also improves its heat resistance. Summary of the Invention

[0004] Technical Problems Solved: In response to the deficiencies of the prior art, the present invention provides a heat-resistant TPU antistatic masterbatch formula and method.

[0005] Technical solution: TPU antistatic masterbatch formula, including 100 parts by weight of polyol, 10.7-16.2 parts by weight of diisocyanate, 8.6-15.2 parts by weight of tertiary amine sulfone chain extender, 1.4-3.7 parts by weight of alkyl bromide, 0.3-0.4 parts by weight of dibutyltin dilaurate, and 0.1-0.13 parts by weight of antioxidant.

[0006] The preparation method of tertiary amine sulfone chain extender is:

[0007] (1) Add dichloromethane, N-methyliminodiacetic acid, glycidol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide to a reaction flask and react for 6-12 hours. After filtering, add saturated sodium chloride solution to the filtrate, let it stand to separate, extract and remove the aqueous phase, dry the organic phase with anhydrous sodium sulfate, filter and concentrate the filtrate under reduced pressure to obtain a glycidyl ester intermediate.

[0008] (2) Add toluene, glycidyl ester intermediate, 4-phenylsulfonylbenzoic acid, and tetrabutylammonium bromide to the reaction flask, heat to 110-115°C, reflux under condensation for 18-24 hours, distill under reduced pressure, wash with water and acetone, and recrystallize the product with ethanol to obtain a tertiary amine sulfone chain extender. The reaction formula is:

[0009]

[0010] Preferably, the molar ratio of N-methyliminodiacetic acid, glycidol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide in (1) is 1:(2-2.2):(0.08-0.11):(2-2.2).

[0011] Preferably, the molar ratio of the glycidyl ester intermediate, 4-phenylsulfonylbenzoic acid, and tetrabutylammonium bromide in (2) is 1:(2-2.4):(0.07-0.08).

[0012] Preferably, the polyol is polyester polyol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

[0013] Preferably, the diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.

[0014] Preferably, the alkyl bromide is 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane or 1-bromooctane.

[0015] Preferably, the method for preparing TPU antistatic masterbatch is: adding polyol to the reaction bottle, heating and vacuum dehydration, adding diisocyanate at 70-80°C, reacting for 2.5-3h, then adding N,N-dimethylformamide, adding tertiary amine sulfone chain extender, dibutyltin dilaurate, reacting for 1-1.5h, adding alkyl bromide, heating to 100-120°C, reacting for 24-36h, distilling under reduced pressure, adding the product to a twin-screw extruder after drying, adding an antioxidant, melt blending, extruding, and granulating to obtain TPU antistatic masterbatch.

[0016] Beneficial effects: The present invention conducts an esterification reaction between N-methyliminodiacetic acid and glycidol, and then uses tetrabutylammonium bromide as a catalyst to react with 4-phenylsulfonylbenzoic acid to obtain a novel tertiary amine sulfone chain extender, which is then subjected to a polymerization chain extension reaction with polyols and diisocyanates, thereby introducing tertiary amine and heat-resistant diphenylsulfone structures into the main chain of polyurethane, and further undergoes a quaternization reaction with alkyl bromide, thereby introducing antistatic quaternary ammonium salt groups into the main chain of polyurethane. The surface resistivity of the obtained TPU antistatic masterbatch is only 5.17×10 8 to 7.72×10 10 Ω, good electrical conductivity, and excellent antistatic properties. The 5% thermal weight loss temperature and the temperature at which the maximum thermal decomposition rate occurs are high, demonstrating excellent heat resistance. Furthermore, the tertiary amine sulfone chain extender contains a high number of rigid benzene ring groups, which helps increase the Shore A hardness of the polyurethane TUP. DETAILED DESCRIPTION

[0017] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0018] Example 1: (1) 30 mL of dichloromethane, 30 mmol N-methyliminodiacetic acid, 60 mmol glycidol, 2.4 mmol 4-dimethylaminopyridine and 66 mmol dicyclohexylcarbodiimide were added to a reaction flask, and the reaction was allowed to proceed for 12 h. After filtering, a saturated sodium chloride solution was added to the filtrate, and the stratification was allowed to stand. The aqueous phase was extracted and removed, and the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a glycidyl ester intermediate.

[0019] (2) Add 100 mL of toluene, 20 mmol of glycidyl ester intermediate, 44 mmol of 4-phenylsulfonylbenzoic acid, and 1.4 mmol of tetrabutylammonium bromide to the reaction flask, heat to 115°C, reflux under condensation for 18 hours, distill under reduced pressure, wash with water and acetone, and recrystallize the product with ethanol to obtain a tertiary amine sulfone chain extender.

[0020] (3) Add 100 g of polytetramethylene glycol 2000 to the reaction bottle, heat and vacuum dehydrate, add 12.1 g of isophorone diisocyanate at 75 ° C, react for 3 h, then add N, N-dimethylformamide, add 8.6 g (11 mmol) of tertiary amine sulfone chain extender, 0.33 g of dibutyltin dilaurate, react for 1 h, add 1.8 g of 1-bromopropane, heat to 120 ° C, react for 24 h, distill under reduced pressure, and add the product to a twin-screw extruder after drying. Add 0.1 g of antioxidant 1010, melt blend at 170 ° C, extrude, and granulate to obtain TPU antistatic masterbatch.

[0021] Example 2: (1) 40 mL of dichloromethane, 30 mmol N-methyliminodiacetic acid, 66 mmol glycidol, 3.3 mmol 4-dimethylaminopyridine and 66 mmol dicyclohexylcarbodiimide were added to a reaction flask and reacted for 6 h. After filtering, a saturated sodium chloride solution was added to the filtrate, the mixture was allowed to stand for stratification, the aqueous phase was extracted and removed, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a glycidyl ester intermediate.

[0022] (2) Add 120 mL of toluene, 20 mmol of glycidyl ester intermediate, 40 mmol of 4-phenylsulfonylbenzoic acid, and 1.6 mmol of tetrabutylammonium bromide to the reaction flask, heat to 110°C, reflux under condensation for 24 hours, distill under reduced pressure, wash with water and acetone, and recrystallize the product with ethanol to obtain a tertiary amine sulfone chain extender.

[0023] (3) Add 100 g of polyester polyol 2000 to the reaction bottle, heat and vacuum dehydrate, add 10.7 g of toluene diisocyanate at 70 ° C, react for 3 h, then add N, N-dimethylformamide, add 11.4 g of tertiary amine sulfone chain extender, 0.4 g of dibutyltin dilaurate, react for 1.5 h, add 1.4 g of 1-bromoethane, heat to 100 ° C, react for 36 h, distill under reduced pressure, and add the product to a twin-screw extruder after drying. Add 0.13 g of antioxidant 1010, melt blend at 170 ° C, extrude, and granulate to obtain TPU antistatic masterbatch.

[0024] Example 3: (1) 30 mL of dichloromethane, 30 mmol N-methyliminodiacetic acid, 60 mmol glycidol, 2.8 mmol 4-dimethylaminopyridine and 60 mmol dicyclohexylcarbodiimide were added to a reaction flask, and the reaction was allowed to proceed for 12 h. After filtering, a saturated sodium chloride solution was added to the filtrate, and the stratification was allowed to stand. The aqueous phase was extracted and removed, and the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a glycidyl ester intermediate.

[0025] (2) Add 100 mL of toluene, 20 mmol of glycidyl ester intermediate, 48 mmol of 4-phenylsulfonylbenzoic acid, and 1.5 mmol of tetrabutylammonium bromide to the reaction flask, heat to 110°C, reflux under condensation for 24 hours, distill under reduced pressure, wash with water and acetone, and recrystallize the product with ethanol to obtain a tertiary amine sulfone chain extender.

[0026] (3) Add 100 g of polyethylene glycol 2000 to the reaction bottle, heat and vacuum dehydrate, add 16.2 g of diphenylmethane diisocyanate at 70 ° C, react for 3 h, then add N, N-dimethylformamide, add 13.5 g of tertiary amine sulfone chain extender, 0.4 g of dibutyltin dilaurate, react for 1.5 h, add 3.7 g of 1-bromooctane, heat to 110 ° C, react for 36 h, distill under reduced pressure, and add the product to a twin-screw extruder after drying. Add 0.1 g of antioxidant 1010, melt blend at 170 ° C, extrude, and granulate to obtain TPU antistatic masterbatch.

[0027] Example 4: (1) Add 100g of polypropylene glycol 2000 to a reaction flask, heat and vacuum dehydrate, add 10.7g of toluene diisocyanate at 80°C, react for 2.5h, then add N,N-dimethylformamide, add 15.2g of tertiary amine sulfone chain extender (prepared by Example 1), 0.4g of dibutyltin dilaurate, react for 1.5h, add 2.9g of 1-bromohexane, heat to 120°C, react for 24h, distill under reduced pressure, and add the product to a twin-screw extruder after drying. Add 0.1g of antioxidant 1010, melt blend at 170°C, extrude, and granulate to obtain TPU antistatic masterbatch.

[0028] Comparative Example 1: The difference between this comparative example and Example 1 is that an equal molar amount of 4,4'-dihydroxydiphenyl sulfone is used instead of the tertiary amine sulfone chain extender.

[0029] (1) Add 100 g of polytetramethylene glycol 2000 to a reaction flask, heat and vacuum dehydrate, add 12.1 g of isophorone diisocyanate at 75 ° C, react for 3 h, then add N, N-dimethylformamide, add 2.75 g (11 mmol) of 4,4'-dihydroxydiphenyl sulfone, 0.33 g of dibutyltin dilaurate, react for 1 h, add 1.8 g of 1-bromopropane, heat to 120 ° C, mix for 24 h, distill under reduced pressure, and after drying, add the product to a twin-screw extruder, add 0.1 g of antioxidant 1010, melt blend at 170 ° C, extrude, and granulate to obtain TPU masterbatch.

[0030] Comparative Example 2: The difference between this comparative example and Example 1 is that an equimolar amount of N-methyldiethanolamine is used instead of the tertiary amine sulfone chain extender.

[0031] (1) Add 100 g of polytetramethylene glycol 2000 to a reaction bottle, heat and vacuum dehydrate, add 12.1 g of isophorone diisocyanate at 75 ° C, react for 3 h, then add N, N-dimethylformamide, add 1.31 g (11 mmol) of N-methyldiethanolamine, 0.33 g of dibutyltin dilaurate, react for 1 h, add 1.8 g of 1-bromopropane, heat to 120 ° C, react for 24 h, distill under reduced pressure, and after drying, add the product to a twin-screw extruder, add 0.1 g of antioxidant 1010, melt blend at 170 ° C, extrude, and granulate to obtain TPU antistatic masterbatch.

[0032] The TPU antistatic masterbatch is injection molded by an injection molding machine to form a TPU spline.

[0033] The surface resistivity of the TPU strips was tested using a resistivity tester. The smaller the surface resistivity, the better the conductivity and antistatic properties.

[0034] The hardness of the TUP specimen was tested using a hardness tester according to the method of GB / T531.1-2008.

[0035] 4 mg of TPU specimens were weighed and placed in a thermogravimetric analyzer. The thermal properties were tested in a nitrogen atmosphere at a heating rate of 10°C / min and a test temperature of 25-700°C.

[0036] Table 1: Performance Test

[0037]

[0038] In Example 1-4, a tertiary amine sulfone chain extender is used to react with polyol and diisocyanate to carry out a polymerization chain extension reaction, thereby introducing a tertiary amine and a heat-resistant diphenyl sulfone structure into the main chain of the polyurethane. Then, an alkyl bromide such as 1-bromopropane is used to react with the tertiary amine group to undergo a quaternization reaction, further introducing an antistatic quaternary ammonium salt group into the main chain of the polyurethane. The surface resistivity of the obtained TPU antistatic masterbatch is only 5.17×10 8 to 7.72×10 10 Ω, good electrical conductivity, and excellent antistatic properties. The 5% thermal weight loss temperature and the temperature at which the maximum thermal decomposition rate occurs are high, demonstrating excellent heat resistance. Furthermore, the tertiary amine sulfone chain extender contains a high number of rigid benzene ring groups, which helps increase the Shore A hardness of the polyurethane TUP.

[0039] Comparative Example 1 uses 4,4'-dihydroxydiphenyl sulfone instead of a tertiary amine sulfone chain extender, introducing a heat-resistant diphenyl sulfone structure into the polyurethane backbone. The resulting polyurethane (TPU) exhibits high thermal weight loss (5%) and maximum thermal decomposition rate temperatures, demonstrating excellent heat resistance. However, 4,4'-dihydroxydiphenyl sulfone lacks tertiary amine groups and cannot undergo a quaternization reaction with 1-bromopropane. The resulting polyurethane (TPU) lacks quaternary ammonium salt antistatic groups, resulting in high surface resistivity and poor antistatic properties.

[0040] In Comparative Example 2, N-methyldiethanolamine was used instead of the tertiary amine sulfone chain extender. The resulting polyurethane TPU did not contain the heat-resistant diphenyl sulfone structure, resulting in lower temperatures at 5% thermal weight loss and maximum thermal decomposition rate, poor heat resistance, and significantly lower Shore A hardness than that of the other examples.

[0041] The above embodiments are intended only to illustrate the technical solutions of the present invention and are not intended to limit the same. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions described in the above embodiments may be modified or some of the technical features thereof may be replaced with equivalents. Such modifications or replacements do not deviate from the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention. Any matters not described in detail in the present invention are well known to those skilled in the art.

Claims

1. TPU antistatic masterbatch, characterized in that, The raw materials of the TPU antistatic masterbatch include 100 parts by weight of polyol, 10.7-16.2 parts by weight of diisocyanate, 8.6-15.2 parts by weight of tertiary amine sulfone chain extender, 1.4-3.7 parts by weight of alkyl bromide, 0.3-0.4 parts by weight of dibutyltin dilaurate, and 0.1-0.13 parts by weight of antioxidant; The structural formula of the tertiary amine sulfone chain extender is as follows: 。 2. The TPU antistatic masterbatch according to claim 1, characterized in that: The polyol is polyester polyol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

3. The TPU antistatic masterbatch according to claim 1, characterized in that: The diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.

4. The TPU antistatic masterbatch according to claim 1, characterized in that: The alkyl bromide is 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane or 1-bromooctane.

5. The TPU antistatic masterbatch according to claim 1, characterized in that: The preparation method of the tertiary amine sulfone chain extender is: (1) Add dichloromethane, N-methyliminodiacetic acid, glycidol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide to a reaction flask, react for 6-12 hours, filter, extract the filtrate, dry it, and concentrate it under reduced pressure to obtain a glycidyl ester intermediate; (2) Add toluene, glycidyl ester intermediate, 4-phenylsulfonylbenzoic acid, and tetrabutylammonium bromide to the reaction flask, heat to 110-115° C., reflux under condensation for 18-24 hours, distill under reduced pressure, wash, and recrystallize to obtain a tertiary amine sulfone chain extender.

6. The TPU antistatic masterbatch according to claim 5, characterized in that: The molar ratio of N-methyliminodiacetic acid, glycidol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide in (1) is 1:(2-2.2):(0.08-0.11):(2-2.2).

7. The TPU antistatic masterbatch according to claim 5, characterized in that: The molar ratio of the glycidyl ester intermediate, 4-phenylsulfonylbenzoic acid, and tetrabutylammonium bromide in (2) is 1:(2-2.4):(0.07-0.08).

8. A method for preparing the TPU antistatic masterbatch according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: adding polyol to a reaction bottle, heating and vacuum dehydration, adding diisocyanate at 70-80° C., reacting for 2.5-3 hours, then adding N,N-dimethylformamide, adding a tertiary amine sulfone chain extender, and dibutyltin dilaurate, reacting for 1-1.5 hours, adding alkyl bromide, heating to 100-120° C., reacting for 24-36 hours, performing reduced pressure distillation, drying, adding the product to a twin-screw extruder, adding an antioxidant, melt blending, extruding, and granulating to obtain TPU antistatic masterbatch.

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