TPU antistatic master batch formula and method

Abstract

The invention relates to the technical field of polyurethane, and discloses a TPU antistatic master batch formula and method, the TPU antistatic master batch formula comprises 100 parts by weight of polyol, 10.7-16.2 parts by weight of diisocyanate, 8.6-15.2 parts by weight of a tertiary amine sulfuryl chain extender, 1.4-3.7 parts by weight of alkyl bromide, 0.3-0.4 part by weight of dibutyltin dilaurate, and 0.1-0.13 part by weight of an antioxidant; the antistatic quaternary ammonium salt group is introduced into the main chain of polyurethane, and the obtained TPU antistatic master batch is low in surface resistivity, good in conductivity and excellent in antistatic performance. And a heat-resistant diphenyl sulfone structure is introduced, so that the heat resistance of the polyurethane TUP is improved.

Description

Technical Field

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

[0002] Polyurethane TPU mainly consists of polyols, polyisocyanates, chain extenders and other raw materials. The polymerized polymer resin can be made into plastics, fibers, rubber elastomers and other materials. It is widely used in the fields of footwear, synthetic leather, foam, adhesives, etc. Traditional polyurethane has a high resistivity, poor conductivity and antistatic properties, which limits the practical application of polyurethane.

[0003] Adding antistatic agents such as quaternary ammonium salts to polyurethane can improve its antistatic performance. Patent CN101581039B discloses a durable antistatic finishing agent for fabrics and a preparation method thereof, wherein a reactive cationic polyurethane aqueous emulsion having structures such as epoxy groups and quaternary ammonium salt cationic groups is used as a durable antistatic finishing agent to impart good antistatic properties to fabrics. Compared with the invention, the present invention not only improves the antistatic properties of polyurethane TPU, but also improves the heat resistance of polyurethane. Summary of the invention

[0004] Technical problem to be solved: In view of the deficiencies in 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 the tertiary amine sulfone chain extender is:

[0007] (1) Add dichloromethane, N-methyliminodiacetic acid, glycidol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide to a reaction flask, react for 6-12 hours, filter, add saturated sodium chloride solution to the filtrate, let 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-benzenesulfonylbenzoic acid, and tetrabutylammonium bromide to the reaction flask, heat to 110-115° C., condense and reflux 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-benzenesulfonylbenzoic 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: add polyol to the reaction bottle, heat and vacuum dehydrate, add diisocyanate at 70-80°C, react for 2.5-3h, then add N,N-dimethylformamide, add tertiary amine sulfone chain extender, dibutyltin dilaurate, react for 1-1.5h, add alkyl bromide, heat to 100-120°C, react for 24-36h, distill under reduced pressure, add the product to a twin-screw extruder after drying, add an antioxidant, melt blend, extrude, and granulate 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, and then conducts a polymerization chain extension reaction with polyol and diisocyanate, thereby introducing tertiary amine and heat-resistant diphenyl sulfone structure 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 conductivity, excellent antistatic performance. And the temperature at which the thermal weight loss is 5% and the temperature at which the maximum thermal decomposition rate is high, the heat resistance is very good. At the same time, the tertiary amine sulfone chain extender contains more rigid benzene ring groups, which is beneficial to improve the Shore A hardness of polyurethane TUP. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Example 1: (1) Add 30 mL of dichloromethane, 30 mmol of N-methyliminodiacetic acid, 60 mmol of glycidol, 2.4 mmol of 4-dimethylaminopyridine and 66 mmol of dicyclohexylcarbodiimide to a reaction flask, react for 12 h, filter, add saturated sodium chloride solution to the filtrate, let stand to separate the layers, extract and remove the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter and concentrate the filtrate 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-benzenesulfonylbenzoic acid, and 1.4 mmol of tetrabutylammonium bromide into a reaction flask, heat to 115° C., condense and reflux for 18 h, 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) Add 40 mL of dichloromethane, 30 mmol of N-methyliminodiacetic acid, 66 mmol of glycidol, 3.3 mmol of 4-dimethylaminopyridine and 66 mmol of dicyclohexylcarbodiimide into a reaction bottle, react for 6 hours, filter, add saturated sodium chloride solution to the filtrate, let stand to separate the layers, extract and remove the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter and concentrate the filtrate 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-benzenesulfonylbenzoic acid, and 1.6 mmol of tetrabutylammonium bromide into a reaction flask, heat to 110° C., condense and reflux 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, 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) Add 30 mL of dichloromethane, 30 mmol of N-methyliminodiacetic acid, 60 mmol of glycidol, 2.8 mmol of 4-dimethylaminopyridine and 60 mmol of dicyclohexylcarbodiimide to a reaction flask, react for 12 h, filter, add saturated sodium chloride solution to the filtrate, let stand to separate the layers, extract and remove the aqueous phase, dry the organic phase over anhydrous sodium sulfate, filter and concentrate the filtrate 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-benzenesulfonylbenzoic acid, and 1.5 mmol of tetrabutylammonium bromide into a reaction flask, heat to 110° C., condense and reflux for 24 h, 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 bottle, 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, 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 to replace the tertiary amine sulfone-based chain extender.

[0029] (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 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 to replace 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 strip is 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 carry out a polymerization chain extension reaction with a polyol and a diisocyanate, 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 carry out a quaternization reaction with the tertiary amine group, and further introduces 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 conductivity, excellent antistatic performance. And the temperature at which the thermal weight loss is 5% and the temperature at which the maximum thermal decomposition rate is high, the heat resistance is very good. At the same time, the tertiary amine sulfone chain extender contains more rigid benzene ring groups, which is beneficial to improve the Shore A hardness of polyurethane TUP.

[0039] Comparative Example 1 uses 4,4'-dihydroxydiphenyl sulfone to replace the tertiary amine sulfone chain extender, and introduces the heat-resistant diphenyl sulfone structure into the main chain of the polyurethane. The temperature at which the thermal weight loss of the polyurethane TPU is 5% and the temperature at the maximum thermal decomposition rate are high, and the heat resistance is very good. However, 4,4'-dihydroxydiphenyl sulfone does not contain a tertiary amine group and cannot react with 1-bromopropane to undergo a quaternary ammonium reaction. The obtained polyurethane TPU does not contain a quaternary ammonium salt antistatic group, has a large surface resistivity, and has poor antistatic performance.

[0040] Comparative Example 2 uses N-methyldiethanolamine instead of the tertiary amine sulfone chain extender, and the obtained polyurethane TPU does not contain the heat-resistant diphenyl sulfone structure, resulting in lower temperatures when the thermal weight loss is 5% and the maximum thermal decomposition rate, poor heat resistance, and the Shore A hardness is significantly lower than that of the embodiments.

[0041] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention is described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solutions described in the above embodiments can still be modified, or some of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention. Anything not described in detail in the present invention is a well-known technology to those skilled in the art.

Claims

1. TPU antistatic masterbatch, characterized in that: The TPU antistatic masterbatch comprises 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-benzenesulfonylbenzoic acid, and tetrabutylammonium bromide to a reaction flask, heat to 110-115° C., condense and reflux 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-benzenesulfonylbenzoic 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 method comprises the following steps: adding polyol to a reaction bottle, heating and vacuum dehydration, adding diisocyanate at 70-80°C, reacting for 2.5-3h, then adding N,N-dimethylformamide, adding tertiary amine sulfone chain extender, and dibutyltin dilaurate, reacting for 1-1.5h, adding alkyl bromide, heating to 100-120°C, reacting for 24-36h, performing reduced pressure distillation, and adding the product to a twin-screw extruder after drying, adding an antioxidant, melt blending, extruding, and granulating to obtain TPU antistatic masterbatch.

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