Use of an aqueous polyurethane composition in an environmentally friendly product that can be kept airtight for a long time and synthesis

Abstract

The application provides application and synthesis of a water-based polyurethane composition in an environmentally-friendly product capable of long-term air tightness. The composition is used in products that need long-term inflation pressure maintaining and are environmentally-friendly and non-toxic; the long-term inflation pressure maintaining air tightness of the product is that, after being sealed, the product is filled with helium to the size of a mold in a constant temperature and humidity environment (25 DEG C, 50% humidity), the size is maintained for more than 90% of time for greater than or equal to 7*24h; the N-nitroso content in the product is 0-0.5mg / kg. The synthesis method is as follows: a low-boiling-point organic solvent is added to an isocyanate-terminated prepolymer, a dibasic amine chain extender is added, a neutralizing agent is added after chain extension, water dispersion is added under high-speed shearing, the water-based polyurethane coarse emulsion is obtained after the end, and the low-boiling-point organic solvent is removed. The product has excellent long-term air tightness, is environmentally-friendly and non-toxic, and can meet the application requirements in high-performance products with excellent long-term air tightness, environmental friendliness and non-toxicity.

Description

Technical Field

[0001] This invention belongs to the field of waterborne polymer materials, and specifically relates to the application and synthesis of a waterborne polyurethane composition in environmentally friendly products that can maintain airtightness for a long time. Background Technology

[0002] Traditional balloons are mainly made of natural latex. However, due to the poor anti-aging properties of natural latex, anti-aging agents are added during processing. These added anti-aging agents release nitrosamines, which are strong carcinogens and pose a significant safety hazard to human health. Furthermore, the European Union has very strict restrictions on nitrosamines in toys. In addition, natural latex has the disadvantage of poor airtightness. Under standard mold inflation conditions, the airtightness of helium can be maintained for less than one day, which is difficult to meet the requirements of high-end applications. Therefore, the downstream mid-to-high-end market urgently needs a high-performance product to replace natural latex.

[0003] As a "new benchmark for green high-performance polymer materials," waterborne polyurethane, a type of polymer, possesses excellent wear resistance, elasticity, toughness, and chemical resistance. Extending this to the field of polyurethane balloons, it combines these inherently superior properties. Waterborne polyurethane is both environmentally friendly and non-toxic, while also exhibiting wear resistance, weather resistance, and high elasticity and flexibility. Its application in balloons not only addresses the safety and performance limitations of traditional materials but also adapts to more complex scenarios (such as long-term outdoor displays and high-end celebratory decorations). This represents a technological iteration in the balloon industry, moving from traditional latex materials to green, high-performance materials. On one hand, it aligns with current environmental policies and market demand for low-carbon products; on the other hand, it drives the industry towards high-end and refined development, expanding the application boundaries of balloons in high-end fields such as commercial displays and art installations. Based on industry development trends, the future market demand for this type of material is expected to reach tens of thousands of tons.

[0004] Therefore, how to manufacture a high-performance product with excellent long-term airtightness, environmental friendliness, and non-toxicity has become one of the technical challenges that urgently need to be addressed in this field. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides an application of a waterborne polyurethane composition in high-performance products with excellent long-term airtightness, environmental friendliness, and non-toxicity. The product of this invention has excellent long-term airtightness, is environmentally friendly and non-toxic, and can meet the application requirements of high-performance products with excellent long-term airtightness, environmental friendliness, and non-toxicity.

[0006] To achieve its objective, the present invention employs the following technical solution:

[0007] The application of a waterborne polyurethane composition in products that maintain airtightness under inflation and are environmentally friendly and non-toxic, the composition being used in products requiring long-term inflation and pressure maintenance and being environmentally friendly and non-toxic, preferably in balloon products; the airtightness of the product under long-term inflation and pressure maintenance is defined as follows: after the product is sealed, it is filled with helium to the mold specifications in a constant temperature and humidity environment of 25°C and 50% humidity, and the dimensions are maintained for ≥7*24h, preferably ≥95% for ≥7*24h; the N-nitroso content in the product is 0-0.5mg / kg.

[0008] In one embodiment of the present invention, the airtightness test method is as follows: inflate the balloon with helium to the size specified by the balloon mold, place it in a constant temperature and humidity room at 25°C and 50% humidity, and test the balloon size every 24 hours; and, the N-nitrosamine determination: the N-nitrosamine of the balloon is tested according to the provisions of GT / T24153-2009, with a detection limit of 0.5 mg / kg; if detected, it is confirmed according to at least one method in Appendix D or Appendix E of ISO19577:2009.

[0009] In one embodiment of the present invention, the polyurethane composition comprises an isocyanate-terminated prepolymer, a polyamine chain extender, and a neutralizing agent; preferably, the raw materials of the isocyanate-terminated prepolymer include: polyisocyanate, macromolecular alcohol, small molecule polyol chain extender, and hydrophilic chain extender.

[0010] Another object of the present invention is to provide a product prepared from an aqueous polyurethane composition.

[0011] A product prepared from an aqueous polyurethane composition, wherein the product is an environmentally friendly and non-toxic product requiring long-term inflation and pressure maintenance, preferably a balloon-type product; preferably, the long-term inflation and pressure maintenance airtightness of the product is such that after the product is sealed, it is filled with helium to the mold specification size in a constant temperature and humidity environment of 25°C and 50% humidity, and the size is maintained for more than 90% for ≥7*24h, preferably more than 95% for ≥7*24h; preferably, the N-nitroso content in the product is 0-0.5mg / kg.

[0012] Another object of the present invention is to provide a waterborne polyurethane composition for use in products that require long-term inflation and pressure maintenance and are environmentally friendly and non-toxic.

[0013] A waterborne polyurethane composition for use in products requiring long-term inflation and pressure maintenance, and which are environmentally friendly and non-toxic, wherein the polyurethane composition comprises an isocyanate-terminated prepolymer and a neutralizing agent; preferably, the raw materials of the isocyanate-terminated prepolymer include: polyisocyanate, macromolecular alcohol, small molecule polyol chain extender, hydrophilic chain extender, and polyamine chain extender.

[0014] In one embodiment of the present invention, the raw material amounts of the composition are as follows, based on the total mass of the isocyanate-terminated prepolymer:

[0015] The amount of polyisocyanate used is 8-12 wt% of the isocyanate-terminated prepolymer.

[0016] The amount of the macromolecular alcohol used is 87-91% of the mass of the isocyanate-terminated prepolymer;

[0017] The amount of the small molecule polyol chain extender is 0-1 wt% of the isocyanate-terminated prepolymer.

[0018] The amount of the hydrophilic chain extender is 0.5-1 wt% of the isocyanate-terminated prepolymer.

[0019] The amount of the polyamine chain extender is 0.5-2.5% of the mass of the isocyanate-terminated prepolymer;

[0020] The amount of neutralizing agent used is 100%-150% of the amount of hydrophilic chain extender that can participate in the neutralization reaction.

[0021] In one embodiment of the present invention, the polyisocyanate comprises one or more of aliphatic, alicyclic, and aromatic groups, preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, pentane diisocyanate, hexahydrotoluene diisocyanate, trimethylhexane diisocyanate, phenylene diisocyanate, 1,4-cyclohexane diisocyanate, dodecyl diisocyanate, 1,5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate, more preferably diphenylmethane diisocyanate and / or toluene diisocyanate.

[0022] In one embodiment of the present invention, the macromolecular alcohol comprises macromolecular polyol a and macromolecular alcohol b; preferably, macromolecular polyol a is a diol formed by the condensation polymerization of phthalic acid and adipic acid with a small linear diol; wherein, phthalic acid is preferably isophthalic acid, and the small linear diol is preferably 1,4-butanediol.

[0023] In this invention, during the synthesis of the waterborne polyurethane composition, in order to pursue the ultimate elongation requirement in product application performance, straight-chain macromolecular polyols are selected as the soft segments as much as possible. However, although well-known straight-chain polyols such as butylene adipate diol and hexanediol adipate diol have regular chain segments, which is conducive to the optimal selection of structure and performance, their strong crystalline state is not allowed. In this invention, a polyol obtained by polycondensation of isophthalic anhydride and adipic acid with 1,4-butanediol is selected as the soft segment.

[0024] In one embodiment of the present invention, preferably, the macromolecular polyol a has a number average molecular weight of 800-8000, more preferably 3000-6000; preferably, the molar ratio of phthalic acid to adipic acid in macromolecular polyol a is controlled at 1:0.5-1:6.

[0025] In this invention, the degree of crystallinity is greatly reduced. By adjusting the ratio of isophthalic anhydride and adipic acid, soft segments with different degrees of crystallinity are obtained. This ensures high elongation of the resin while maintaining its tensile strength and tear strength to a great extent, meeting the performance requirements for balloon applications. This is something that other soft segments do not possess.

[0026] In one embodiment of the present invention, preferably, the macromolecular alcohol b is at least one monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in its main chain and / or side chains, having an average number-average molecular weight of 300-3000 g / mol, preferably 500-1500 g / mol; preferably, the monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in its main chain and / or side chains is a polymer unit containing polyethylene oxide segments containing 90-100 wt% ethylene oxide, preferably Tegomer from TegoChemie. ® D-3403, Perstrop's Ymer TM N120 and one or more of Lotte MPEG520, MPEG1200, and MPEG2200 from South Korea, with MPEG1200 from Lotte MPEG from South Korea being more preferred.

[0027] In one embodiment of the present invention, the small molecule polyol chain extender comprises a diol with a main chain containing at least 2-10 carbons, preferably one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methylpentane-1,5-pentanediol, 1,6-hexanediol, neopentanediol, 1,4-cyclohexyldiethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-3-propylpentanediol, 2,2-dimethylpentanediol, diethylene glycol, glycerol, and trimethylolpropane, more preferably 1,4-butanediol.

[0028] In one embodiment of the invention, the hydrophilic chain extender comprises a compound with ionic or potentially ionic groups that can react with isocyanates, preferably one or more of dimethylolpropionic acid, dimethylolbutyric acid, amino acids, sodium 2-(2-aminoethyl)aminoethanesulfonate, sodium 2-(2-aminoethyl)aminopropanesulfonate, sodium 1,4-butanediol-2-sulfonate and sodium 1,2-dihydroxy-3-propanesulfonate, tartaric acid, N,N-dimethylmaleamic acid, diaminobenzoic acid, and sodium dihydroxypropanesulfonate, preferably dimethylolpropionic acid and sodium 2-(2-aminoethyl)aminoethanesulfonate.

[0029] In one embodiment of the present invention, the neutralizing agent comprises a protonating agent having a neutralizing function, preferably one or more of sodium hydroxide, potassium hydroxide, triethylamine, N,N-dimethylethanolamine, dimethylcyclohexylamine, triethanolamine, methyldiethanolamine, diisopropanolamine, ethyldiisopropylamine, diisopropylcyclohexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol, and ammonia water, more preferably one or more of sodium hydroxide, triethylamine, and N,N-dimethylethanolamine.

[0030] In one embodiment of the present invention, the polyamine chain extender comprises an organic or inorganic primary or secondary amine functional compound containing at least two active hydrogen atoms, preferably one or more of ethylenediamine, 2-methyl-1,5-pentanediamine, isophorone diamine, hydrazine, hydroxyethyl ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, cyclohexanediamine, phenylenediamine, toluenediamine, and dicyclohexylmethanediamine, more preferably isophorone diamine.

[0031] Another object of the present invention is to provide a method for preparing an aqueous polyurethane composition for a product that requires long-term inflation and pressure maintenance and is environmentally friendly and non-toxic.

[0032] A method for preparing an aqueous polyurethane composition for products requiring long-term inflation and pressure maintenance, and which is environmentally friendly and non-toxic, wherein the composition is the above-mentioned composition, and the method comprises the following steps:

[0033] A prepolymer with isocyanate end-capping is synthesized. A low-boiling-point organic solvent is added to the isocyanate end-capping prepolymer, followed by the addition of a diamine chain extender. After chain extension is complete, a neutralizing agent is added, and water is added for dispersion under high-speed shearing. After the process is complete, an aqueous polyurethane crude emulsion is obtained, and the low-boiling-point organic solvent is removed.

[0034] In one embodiment of the present invention, the low-boiling-point solvent comprises an organic solvent with a boiling point below 100°C, preferably one or more of acetone, methyl ethyl ketone, cyclohexane, dichloromethane, dichloroethane, trichloroethane, ethyl acetate, pentane, heptane, and hexane, more preferably acetone; preferably, the amount of the low-boiling-point solvent is 1-2 times the mass of the isocyanate-terminated prepolymer.

[0035] In one embodiment of the present invention, the isocyanate-terminated prepolymer is prepared at a reaction temperature of 70-80°C.

[0036] In one embodiment of the present invention, the low-boiling-point solvent is added to the isocyanate-terminated prepolymer at a temperature below 60°C.

[0037] In one embodiment of the present invention, the reaction temperature of the diamine with the isocyanate prepolymer is 35-40°C.

[0038] Unless otherwise specified, all dimensions mentioned in this invention refer to volumetric dimensions.

[0039] Compared with the prior art, the technical solution provided by the present invention has the following advantages:

[0040] The waterborne polyurethane composition of this invention is applicable to balloons and other fields. It has excellent airtightness and is environmentally friendly and non-toxic. It solves the problem of the release of nitrosamines, a strong carcinogen, when anti-aging agents are added to latex balloons and other products. It also solves the shortcomings of latex balloons and other products such as poor airtightness and allergenicity. Detailed Implementation

[0041] To better understand the technical solution of the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0042] Unless otherwise specified, "%" in the examples or comparative examples refers to "wt%".

[0043] The test methods used in the embodiments or comparative examples are described below:

[0044] Solid content test method: Take an appropriate amount of emulsion in a container made of tin foil, weigh the weight change before and after 20 minutes at 150℃, and calculate its solid content.

[0045] Particle size testing method: The particle size and particle size distribution of the polyurethane dispersion were measured using dynamic light scattering (DLS). In the experiment, a Malvern Zetasizer Nano ZS90 particle size analyzer was used to determine the particle size and particle size distribution of the emulsion. The test temperature was 25℃, the laser angle was 90°, and the test laser wavelength was 633nm.

[0046] pH testing method: A Metrohm pH meter from Switzerland was used.

[0047] Viscosity testing method: The BROOKFIELD viscometer was used, with rotor No. 3 at 30 rpm.

[0048] The slurry, flocculant, and release agent used in the preparation of polyurethane balloons for the emulsions obtained in the following examples or comparative examples are shown in Table 1 below:

[0049] Table 1

[0050]

[0051] The method for testing the application performance of the comparative examples is described below:

[0052] Balloon making process: Clean the balloon mold and dry its surface moisture. Immerse the mold in a flocculant solution of 10% calcium chloride and 2% calcium stearate. Remove the mold and place it in an 80℃ oven to bake for 30 minutes. After baking, remove the mold and cool it to 40℃. Immerse the mold in water-based polyurethane emulsion for 15 seconds. Remove the mold and place it back in an 80℃ oven to bake for 30 minutes. After baking, remove the mold and immerse it in a 2% calcium stearate suspension release agent. Remove the mold from the release agent and place it in an 80℃ oven to bake for 3 minutes to dry the surface moisture. Remove the mold and let it cool at room temperature to demold, and you will get a polyurethane balloon.

[0053] Mechanical property testing method: According to GB / T104092 standard, depending on the sample conditions, the tensile test can be carried out at a tensile speed of 50 mm / min under constant temperature and humidity. The test results can obtain the stress-strain curve of the sample. From the curve, the tensile strength, elongation at break and modulus of the material can be obtained.

[0054] Balloon feel test: Inflate the balloon to the size specified by the mold (if it does not reach the specified size, it has already burst and is not of reference value), and evaluate the feel by touching and squeezing it with your hand, scoring it from 1 to 5 points, with 5 points being the best feel.

[0055] Air tightness: Inflate the balloon with helium to the mold size and place it in a constant temperature and humidity room (25℃, 50% humidity). Test the balloon size every 24 hours. If the volume change is less than 10% in less than 7*24 hours, it does not meet the requirements.

[0056] N-nitrosamine determination: The test for N-nitrosamines in balloons shall be performed in accordance with GT / T24153-2009, with a detection limit of 0.5 mg / kg. If detected, confirmation shall be made by at least one method in Annex D or Annex E of ISO 19577:2009. A list of N-nitrosamine restrictions is provided in Annex A of GB / T24153-2009.

[0057] The raw materials used in the examples or comparative examples are described below:

[0058] WANNATE ® HDI (hexamethylene diisocyanate, Wanhua Chemical Group Co., Ltd.);

[0059] WANNATE ® IPDI (Isophorone diisocyanate, Wanhua Chemical Group Co., Ltd.);

[0060] 3681ET (Polybutylene adipate-isophthalate diol, adipic acid and isophthalic anhydride molar ratio of 2:1, number average molecular weight = 3000, functionality of 2, Wanhua Chemical Group Co., Ltd.);

[0061] 3682ET (Polybutylene adipate-isophthalate diol, adipic acid and isophthalic anhydride molar ratio of 1:2, number average molecular weight = 3000, functionality of 2, Wanhua Chemical Group Co., Ltd.);

[0062] 3683ET (Polybutylene adipate-isophthalate diol, adipic acid and isophthalic anhydride molar ratio of 6:1, number average molecular weight = 3000, functionality of 2, Wanhua Chemical Group Co., Ltd.);

[0063] 4681ET (Polybutylene adipate-isophthalate diol, adipic acid and isophthalic anhydride molar ratio 2:1, number average molecular weight 4000, functionality 2, Wanhua Chemical Group Co., Ltd.);

[0064] PNA3000 (Polypentyl adipate diol, number average molecular weight = 3000, functionality = 2, Wanhua Chemical Group Co., Ltd.);

[0065] BDO (1,4-Butanediol, Wanhua Chemical Group Co., Ltd.)

[0066] A95 (Sodium ethylenediaminoethanesulfonate, Wanhua Chemical Group Co., Ltd.);

[0067] DMPA (dimethylolpropionic acid, Posto);

[0068] BiCat8108 (catalyst, leading in the US)

[0069] TEA (triethylamine, BASF, Germany);

[0070] Acetone (refined by Wanhua Chemical Group Co., Ltd.)

[0071] IPDA (Isophorone Diamine, Wanhua Chemical Group Co., Ltd.)

[0072] BYK024 (Defoamer, BYK Chemicals)

[0073] Calcium stearate (Aladdin reagent)

[0074] Calcium chloride (Aladdin reagent)

[0075] Comparative Example 1

[0076] Natural latex products.

[0077] Comparative Example 2

[0078] Compared with Example 1, the only difference is the type of macromolecular polyol a.

[0079] Add 24.2g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 14.6g WANNATE ® IPDI-80 (isophorone diisocyanate), 360g PNA3000 (poly(neopentyl adipate) diol), 1.5g MPEG1200, 3g dimethylolpropionic acid, 0.2g BiCat8108, and 80g acetone were added. The mixture was heated to 80℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was then lowered to below 60℃, and 564g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 540g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with a solid content of 45% and a particle size of 165nm.

[0080] Example 1

[0081] Add 24.2g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 14.6g WANNATE ® IPDI-80 (isophorone diisocyanate), 360g 3681ET, 1.5g MPEG1200, 3g dimethylolpropionic acid, 0.2g BiCat8108, and 80g acetone were added. The mixture was heated to 80℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was then lowered to below 60℃, and 564g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 540g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with a solid content of 45% and a particle size of 160nm.

[0082] Example 2

[0083] Add 24.2g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 14.6g WANNATE ®IPDI-80 (isophorone diisocyanate), 360g 3682ET, 1.5g MPEG1200, 3g dimethylolpropionic acid, 0.2g BiCat8108, and 80g acetone were added. The mixture was heated to 80℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was lowered to below 60℃, and 564g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 540g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with 45% solids content and a particle size of 176nm.

[0084] Example 3

[0085] Add 24.2g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 14.6g WANNATE ® IPDI-80 (isophorone diisocyanate), 360g 3683ET, 1.5g MPEG1200, 3g dimethylolpropionic acid, 0.2g BiCat8108, and 80g acetone were added. The mixture was heated to 80℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was lowered to below 60℃, and 564g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 540g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with 45% solids content and a particle size of 148nm.

[0086] Example 4

[0087] Add 18.6g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 16.2g WANNATE ®IPDI-80 (isophorone diisocyanate), 370g 4681ET, 1.5g MPEG1200, 3g dimethylolpropionic acid, 0.2g BiCat8108, and 80g acetone were added. The mixture was heated to 81℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was then lowered to below 60℃, and 573g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 542g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with a solid content of 45% and a particle size of 165nm.

[0088] Example 5

[0089] Add 24.2g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 14.6g WANNATE ® IPDI-80 (isophorone diisocyanate), 300g 3681ET, 1.5g MPEG1200, 3g dimethylolpropionic acid, 2.7g BDO, 0.2g BiCat8108, and 69g acetone were added. The mixture was heated to 80℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was lowered to below 60℃, and 564g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 455g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with 45% solids content and a particle size of 158nm.

[0090] Example 6

[0091] Add 24g of WANNATE to a four-necked flask equipped with a reflux condenser, thermometer, and mechanical stirrer. ® HDI (hexamethylene diisocyanate), 14g WANNATE ®IPDI-80 (isophorone diisocyanate), 400g 3681ET, 1.5g MPEG1200, 3g dimethylolpropionic acid, 0.2g BiCat8108, and 88g acetone were added. The mixture was heated to 80℃ and reacted until the theoretical NCO value was reached, at which point the reaction was stopped. The temperature was then lowered to below 60℃, and 620g acetone was added. The mixture was stirred until homogeneous, and the temperature was controlled at 40℃. A mixed solution of 3.6g IPDA, 4g A95, and 30g water was added and reacted for 20 minutes. 2.5g TEA was added to neutralize the reaction and reacted for 3 minutes. 588g deionized water was weighed into a dispersion vessel and poured into the prepolymer within 6 minutes under high-speed shear conditions of 1500r / min. After dispersion, a crude emulsion of the waterborne polyurethane composition was obtained. The acetone in the emulsion was removed by vacuum distillation to obtain a milky white waterborne polyurethane emulsion with 45% solids content and a particle size of 163nm.

[0092] The compositions obtained in each embodiment and comparative example were used to prepare polyurethane balloons according to specific embodiments, and their performance was tested. The performance test results of the obtained polyurethane balloons are shown in Table 2 below:

[0093] Table 2

[0094]

[0095] Note: "--" indicates that the emulsion is not suitable for the relevant test; the volume change after 15 days of testing in the examples was less than 5%.

[0096] As can be seen from the test data in the table above, the composition prepared by the synthesis method of the high airtightness environmentally friendly waterborne polyurethane composition provided by the present invention meets the performance requirements of balloon testing and is environmentally friendly and non-toxic, showing good performance in the field of balloons.

[0097] From a production practice perspective, the preparation method of the waterborne polyurethane resin of this invention is simple and controllable, low in cost, and can achieve excellent performance, thus having significant practical value.

[0098] Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. The application of a waterborne polyurethane composition in an environmentally friendly and non-toxic product that maintains airtightness under inflated conditions, characterized in that, The composition is used in products that require long-term inflation and pressure maintenance and are environmentally friendly and non-toxic, preferably in balloon products; The airtightness of the product during long-term inflation and pressure maintenance is such that after the product is sealed, it is filled with helium to the mold specification size in a constant temperature and humidity environment of 25℃ and 50% humidity, and the size is maintained for more than 90% for ≥7*24h, preferably more than 95% for ≥7*24h. The product contains 0-0.5 mg / kg of N-nitroso groups.

2. The application according to claim 1, characterized in that, The airtightness test method is as follows: inflate the balloon with helium to the dimensions specified by the balloon mold, place it in a constant temperature and humidity chamber at 25℃ and 50% humidity, and test the balloon dimensions every 24 hours; and, The determination of N-nitrosamines: The test for N-nitrosamines in the balloon shall be carried out in accordance with the provisions of GT / T24153-2009, with a detection limit of 0.5 mg / kg; if detected, confirmation shall be made by at least one method in Annex D or Annex E of ISO19577:2009.

3. The application according to claim 1 or 2, characterized in that, The polyurethane composition comprises an isocyanate-terminated prepolymer, a polyamine chain extender, and a neutralizing agent; Preferably, the raw materials of the isocyanate-terminated prepolymer include: polyisocyanate, macromolecular polyol, small molecule polyol chain extender, and hydrophilic chain extender.

4. A product prepared from an aqueous polyurethane composition, characterized in that, The product is one that requires long-term inflation and pressure maintenance and is environmentally friendly and non-toxic, preferably a balloon product; Preferably, the airtightness of the product during long-term inflation and pressure holding is such that after the product is sealed, it is filled with helium to the mold specification size in a constant temperature and humidity environment of 25°C and 50% humidity for a time of ≥7*24h, and preferably the time of ≥7*24h when the size is maintained at ≥95%; Preferably, the N-nitroso content in the product is 0-0.5 mg / kg.

5. A waterborne polyurethane composition for use in products requiring long-term inflation and pressure maintenance, and which is environmentally friendly and non-toxic, characterized in that, The polyurethane composition comprises an isocyanate-terminated prepolymer, a polyamine chain extender, and a neutralizing agent; Preferably, the raw materials of the isocyanate-terminated prepolymer include: polyisocyanate, macromolecular alcohol, small molecule polyol chain extender, and hydrophilic chain extender.

6. The composition according to claim 5, characterized in that, Based on the total mass of the isocyanate-terminated prepolymer, the raw material amounts for the composition are as follows: The amount of polyisocyanate used is 8-12 wt% of the isocyanate-terminated prepolymer. The amount of the macromolecular alcohol used is 87-91% of the mass of the isocyanate-terminated prepolymer; The amount of the small molecule polyol chain extender is 0-1 wt% of the isocyanate-terminated prepolymer. The amount of the hydrophilic chain extender is 0.5-1 wt% of the isocyanate-terminated prepolymer. The amount of the polyamine chain extender is 0.5-2.5% of the mass of the isocyanate-terminated prepolymer; The amount of neutralizing agent used is 100%-150% of the amount of hydrophilic chain extender that can participate in the neutralization reaction.

7. The composition according to claim 5 or 6, characterized in that, The polyisocyanate comprises one or more of aliphatic, alicyclic, and aromatic groups, preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, pentane diisocyanate, hexahydrotoluene diisocyanate, trimethylhexane diisocyanate, phenylene diisocyanate, 1,4-cyclohexane diisocyanate, dodecyl diisocyanate, 1,5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate, more preferably diphenylmethane diisocyanate and / or toluene diisocyanate; And / or, the macromolecular alcohol comprises macromolecular polyol a and macromolecular alcohol b; Preferably, the macromolecular polyol a is a diol formed by the condensation polymerization of phthalic acid and adipic acid with a small molecule straight-chain diol; wherein, the phthalic acid is preferably isophthalic acid, and the small molecule straight-chain diol is preferably 1,4-butanediol; Preferably, the macromolecular polyol a has a number average molecular weight of 800-8000, more preferably 3000-6000; Preferably, the molar ratio of phthalic acid to adipic acid in macromolecular polyol a is controlled at 1:0.5-1:6; Preferably, the macromolecular alcohol b is at least one monohydric alcohol and / or dihydric alcohol whose main chain and / or side chain contain polyethylene oxide segments, having an average number-average molecular weight of 300-3000 g / mol, preferably 500-1500 g / mol. Preferably, the monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chains are polymer units containing polyethylene oxide segments that contain 90-100 wt% ethylene oxide, preferably Tegomer from TegoChemie. ® D-3403, Perstrop's Ymer TM N120 and one or more of Lotte MPEG520, MPEG1200 and MPEG2200 from South Korea, with MPEG1200 from Lotte MPEG from South Korea being more preferred; And / or, the small molecule polyol chain extender comprises a diol with a main chain containing at least 2-10 carbons, preferably one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methylpentane-1,5-pentanediol, 1,6-hexanediol, neopentanediol, 1,4-cyclohexyldiethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-3-propylpentanediol, 2,2-dimethylpentanediol, diethylene glycol, glycerol, and trimethylolpropane, more preferably 1,4-butanediol; And / or, the hydrophilic chain extender comprises a compound with ionic or potentially ionic groups that can react with isocyanates, preferably one or more of dimethylolpropionic acid, dimethylolbutyric acid, amino acids, sodium 2-(2-aminoethyl)aminoethanesulfonate, sodium 2-(2-aminoethyl)aminopropanesulfonate, sodium 1,4-butanediol-2-sulfonate and sodium 1,2-dihydroxy-3-propanesulfonate, tartaric acid, N,N-dimethylolmaleamic acid, diaminobenzoic acid, and sodium dihydroxypropanesulfonate, preferably dimethylolpropionic acid and sodium 2-(2-aminoethyl)aminoethanesulfonate; And / or, the neutralizing agent comprises a protonating agent with neutralizing function, preferably one or more of sodium hydroxide, potassium hydroxide, triethylamine, N,N-dimethylethanolamine, dimethylcyclohexylamine, triethanolamine, methyldiethanolamine, diisopropanolamine, ethyldiisopropylamine, diisopropylcyclohexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol, and ammonia, more preferably one or more of sodium hydroxide, triethylamine, and N,N-dimethylethanolamine; And / or, the polyamine chain extender comprises an organic or inorganic primary or secondary amine functional compound containing at least two active hydrogen atoms, preferably one or more of ethylenediamine, 2-methyl-1,5-pentanediamine, isophorone diamine, hydrazine, hydroxyethyl ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, cyclohexanediamine, phenylenediamine, toluenediamine, and dicyclohexylmethanediamine, more preferably isophorone diamine.

8. A method for preparing an aqueous polyurethane composition for products requiring long-term inflation and pressure maintenance, and which is environmentally friendly and non-toxic, wherein the composition is the composition according to any one of claims 5-7, characterized in that, The method includes the following steps: A prepolymer with isocyanate end-capping is synthesized. A low-boiling-point organic solvent is added to the isocyanate end-capping prepolymer, followed by the addition of a diamine chain extender. After chain extension is complete, a neutralizing agent is added, and water is added for dispersion under high-speed shearing. After the process is complete, an aqueous polyurethane crude emulsion is obtained, and the low-boiling-point organic solvent is removed.

9. The method according to claim 8, characterized in that, The low-boiling-point solvent includes organic solvents with a boiling point below 100°C, preferably one or more of acetone, methyl ethyl ketone, cyclohexane, dichloromethane, dichloroethane, trichloroethane, ethyl acetate, pentane, heptane, and hexane, more preferably acetone; Preferably, the amount of the low-boiling-point solvent is 1-2 times the amount of the isocyanate-terminated prepolymer.

10. The method according to claim 8 or 9, characterized in that, The isocyanate-terminated prepolymer is prepared at a reaction temperature of 70-80℃. And / or, the low-boiling-point solvent is added to the isocyanate-terminated prepolymer at a temperature below 60°C; And / or, the reaction temperature of the diamine with the isocyanate prepolymer is 35-40°C.

Images