Thermoplastic polyurethane elastomer and application thereof

Abstract

The invention provides a thermoplastic polyurethane elastomer, and belongs to the technical field of macromolecules. The high-temperature-resistant polyurethane resin is prepared from the following components in parts by mass: 80 to 110 parts of polyester polyol, 5 to 10 parts of a chain extender, 0.03 to 1 part of a catalyst, 20 to 40 parts of isocyanate, 0 to 2 parts of a nucleating aid, 0.05 to 0.5 part of an antioxidant and 0.05 to 0.2 part of an ultraviolet light absorber. The comprehensive performance and flatness of the fabric can be effectively improved.

Description

Technical Field

[0001] The invention relates to the field of polymer technology, in particular to a thermoplastic polyurethane elastomer and application thereof in fabrics, in particular in underwear fabrics. Background Art

[0002] The trendy underwear on the market is seamless underwear, which is usually better than ordinary underwear in terms of comfort, appearance and functionality. The production of seamless underwear usually uses highly elastic materials, among which high-rebound TPE materials are the most widely used. However, TPE materials have poor bonding effects on fabrics, and most TPU materials with good bonding effects have poor rebound effects as TPE. Only a few companies on the market have TPU materials with good rebound, and most of them can only reach level 3-4 yellowing grades. They are easy to yellow in the air or ultraviolet environment, causing the fabric to turn yellow. In addition, the flatness of the fabrics of trendy underwear on the market is not high, and the arching phenomenon is serious.

[0003] In summary, the comprehensive performance of fabrics currently on the market is poor. Summary of the invention

[0004] In view of this, in order to solve the technical problems of poor comprehensive performance and serious arching phenomenon of fabrics on the market, on the one hand, the present invention provides a thermoplastic polyurethane elastomer that can effectively improve the comprehensive performance and smoothness of the fabric.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A thermoplastic polyurethane elastomer, comprising the following components in parts by mass:

[0007] 80-110 parts of polyester polyol, 5-10 parts of chain extender, 0.03-1 parts of catalyst, 20-40 parts of isocyanate, 0-2 parts of nucleating aid, 0.05-0.5 parts of antioxidant, 0.05-0.2 parts of ultraviolet absorber.

[0008] Preferably, the antioxidant is 1010 or 1076;

[0009] The ultraviolet absorber is preferably one of UV326, UV328 and UV329.

[0010] Preferably, the following components are included, calculated by mass: 95-100 parts of polyester polyol, 5-9 parts of chain extender, 0.05-0.1 parts of catalyst, 25-35 parts of isocyanate, and 1.2-1.8 parts of nucleating agent.

[0011] Preferably, the polyester polyol is one or more of PEA, PPA, PBA, PHA, PNA, PCL, PTMEG, PEBA, PBHA, PBA+PHA (8:2), PCL+PTMEG (5:5) with a molecular weight of 1800-2000; the polyester polyol is more preferably PBHA with a molecular weight of 2000.

[0012] Preferably, the chain extender is one or more of EG, BDO, PDO, HDO, MPO, MPD, 1,4-cyclohexanediol, HQEE, monoethanolamine, diethanolamine, diglycolamine, cyanuric acid, 1,3-bishydroxymethylurea, N,N-bishydroxymethylurea, N,N-di-tert-butylethylenediamine and N,N-diisopropylethylenediamine;

[0013] The chain extender is BDO or a combination of BDO and N,N-di-tert-butylethylenediamine.

[0014] Preferably, the catalyst is a metal catalyst, preferably an organotin or organobismuth catalyst.

[0015] Preferably, the isocyanate is IPDI, HDI, H 12 One or more of MDI, CHDI, TMDI and HTDI;

[0016] The isocyanate is preferably H 12 MDI.

[0017] Preferably, the nucleating aid is an inorganic nucleating agent or a polymer nucleating agent;

[0018] The polymer nucleating agent is preferably one or more of an α-crystal nucleating agent, a β-crystal nucleating agent and a nylon nucleating agent.

[0019] The present invention provides a method for preparing the above-mentioned thermoplastic polyurethane elastomer, comprising the following steps:

[0020] In the first step, the polyester polyol and the chain extender are vacuumed to remove moisture, the vacuum degree is -0.08--0.1MPA, the heating temperature is 105-120°C, the stirring time is 2 hours, and the stirring rate is 100-150r / min;

[0021] The second step is to dilute the catalyst to a 20% concentration with DOTP for later use;

[0022] The third step is to add the polyester polyol, chain extender and diluted catalyst after water removal in proportion and stir evenly for 2-3 minutes. When the temperature of the mixed liquid drops to about 60-80°C, add isocyanate and react for 2-3 minutes.

[0023] In the fourth step, the reactants were poured into a polytetrafluoroethylene tray, and then placed in a 120°C oven for vacuum ripening for 2 hours.

[0024] It should be noted that the antioxidant, nucleating aid and ultraviolet absorber are added in the second step according to the above ratio.

[0025] On the other hand, the present invention also provides the use of the above-mentioned thermoplastic polyurethane elastomer in fabrics.

[0026] The thermoplastic polyurethane elastomer provided by the present invention can effectively improve the comprehensive performance of fabrics. The details are as follows:

[0027] (1) The bonding strength to fabric is high, often more than twice that of TPE materials;

[0028] (2) The anti-aging yellowing effect is good, UV yellowing and phenol yellowing are both level 5, while the existing technology is usually level 3-4;

[0029] (3) Low hardness and good hand feel;

[0030] (4) More environmentally friendly. TPE materials need to be oil-filled to achieve high resilience. The oil-filled raw materials are generally cycloalkane oil, plasticizer oil, etc. These substances are harmful to a certain extent. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is clearly described in detail below in conjunction with specific embodiments.

[0032] The raw materials adopted in the present invention are as follows:

[0033] PBA2000: Manufacturer: Foshan Huaborun, Model: 8020;

[0034] PHA2000: Manufacturer: Foshan Huaborun, Model: 6020;

[0035] PCL2000: Manufacturer: Daicel, Model: 220N;

[0036] PTMEG2000: Manufacturer: Hyosung Chemical, Model: PTMEG2000;

[0037] PBHA2000: Manufacturer: Asahikawa Chemical, Model: YCP-2000HB;

[0038] EG: Manufacturer: Leyan;

[0039] BDO: Manufacturer: Leyan;

[0040] N,N-di-tert-butylethylenediamine: Manufacturer: Leyan;

[0041] IPDI: Manufacturer: Bayer

[0042] H 12 MDI: Manufacturer: Wanhua

[0043] Antioxidant: Manufacturer: BASF, Model: 1010;

[0044] UV absorber: Manufacturer: United States, Model: UV326;

[0045] Catalyst: Manufacturer: Baiyuan;

[0046] Nucleating agent: Manufacturer: Clariant, Model: 4030;

[0047] Example 1

[0048] The specific preparation method of the thermoplastic polyurethane elastomer described in the embodiment of the present invention is as follows:

[0049] Weigh 97.62g of PBHA 2000 molecular weight polyol (excluding water), 5.8g of chain extender (excluding water) BDO and 1.22g of N,N-di-tert-butylethylenediamine, 0.4g of 20% diluted catalyst, 1.6g of nucleating aid, 0.15g of antioxidant, and 0.15g of UV absorber in a Teflon beaker, put it in a vacuum oven at 80℃ for 10 minutes, then take it out and stir it at a stirring rate of 1000RPM for 2-3 minutes. Stir evenly, test the temperature in the cup with an infrared temperature gun, and when the temperature drops to about 70℃, add the weighed H 12 MDI30.18g, react for 2-3 minutes, pour the glue into a polytetrafluoroethylene tray, and then quickly put the tray into a 120℃ oven for aging for 2 hours. Keep the vacuum state during the aging process.

[0050] Example 2

[0051] The only difference between this embodiment and embodiment 1 is that the composition of this embodiment is 97.62g of PBHA2000, 6.7g of BDO, 0.4g of 20% (concentration) diluted catalyst, 1.6g of nucleating aid, 0.15g of antioxidant, 0.15g of UV absorber, and 0.2g of H 12 MDI 32.08g.

[0052] Example 3

[0053] The only difference between this comparative example and Example 1 is that no nucleating agent is added.

[0054] Example 4

[0055] The only difference between this embodiment and embodiment 1 is that the composition of this embodiment is 97.62 g PBHA2000, 7 g BDO, 1.48 g N, N-di-tert-butylethylenediamine, 0.4 g 20% ​​diluted catalyst, 1.6 g nucleating agent, 0.15 g antioxidant, 0.15 g UV absorber, H 12 MDI 33.63g.

[0056] The thermoplastic polyurethane elastomer described in the present invention has the following specific performance requirements: hardness 50-70A; 100% resilience>95%, 200% resilience>90%, 300% resilience>85%; elongation at break>700%.

[0057] Comparative Example 1

[0058] The only difference between this comparative example and Example 1 is that H 12 MDI is replaced by IPDI.

[0059] Comparative Example 2

[0060] The only difference between this comparative example and Example 1 is that PBHA2000 in Example 1 is replaced with PBA2000+PHA2000 (8:2).

[0061] Comparative Example 3

[0062] The only difference between this comparative example and the example is that PBHA2000 in Example 1 is replaced with PCL2000+PTMEG2000 (5:5)

[0063] Comparative Example 4

[0064] The only difference between this comparative example and Example 1 is that the chain extender BDO in the example is replaced by EG.

[0065] The formulas of Examples 1-4 and Comparative Examples 1-4 are shown in Table 1 below:

[0066] Table 1 Formulations of Examples 1-4 and Comparative Examples 1-4

[0067]

[0068] The physical properties of the synthesized TPU are shown in Table 2:

[0069] Table 2 TPU physical properties

[0070]

[0071] Effect example

[0072] 1. The TPU materials prepared in Examples 1-4 and Comparative Examples 1-4 were dissolved in DMAC and coated into a 0.08 mm thick film. The film was cut into strips of 50 cm long and 1 cm wide by a laser machine. A section of 10 cm long and uniformly thick film was taken, and the film properties were tested as shown in Table 3:

[0073] Table 3 Film properties

[0074]

[0075]

[0076] 2. Prepare four pieces of elastic fabric for underwear, cut them into 20*2cm size for later use, take 15*1cm thick 0.08mm film, first use an iron to position the film on the fabric, then cover the film with the same fabric, put it on a pneumatic flat hot press, press at 170℃ for 20S, leave it for 24 hours to test the peeling force. The test results are shown in Table 4 below:

[0077] Table 4 Peel force test results

[0078]

[0079] 3. Prepare four elastic fabrics for underwear, cut them into 25*4cm specifications for use, take 25*1cm thick 0.08mm film, first use an iron to position the film on the fabric, position it along the edge, then fold it along the edge of the film, and then use an iron to position it, put it on a pneumatic flat hot press, press it at 170℃ for 20S, and then leave it for 24 hours, manually stretch the pressed fabric to the maximum length of the fabric and then restore it, stretch it back and forth 10 times, and observe the arching phenomenon of the fabric. The test results are as shown in Table 5:

[0080] Table 5 Fabric arching test results

[0081]

[0082]

[0083] It can be seen from the above Tables 1-5 that the non-yellowing TPU materials prepared in Examples 1-4 of the present invention and Comparative Examples 1-4 have a hardness of 50-75A, have a certain resilience, and have a strong peeling force for the elastic fabric of underwear, which is basically above 10N / cm (the peeling force of TPE high elastic materials on the market only needs to meet 6N / cm or above). The pressed fabrics of Examples 1-4 have high flatness and few waves.

[0084] From the comparison data of Example 1 and Example 2, it can be seen that after replacing N,N-di-tert-butylethylenediamine with BDO, the difference is that the flatness of the pressed surface becomes worse, indicating that the elastic rebound speed decreases; from the data of Example 1 and Example 3, it can be seen that the introduction of nucleating additives helps to improve the recovery speed of TPU materials after stretching. The faster the recovery speed, the smoother the fabric; from the comparison of Example 1 and Example 4, it can be seen that with the increase of chain extender dosage, H 12 The amount of MDI also increases accordingly, and the hard segment content increases. Although the resilience and flatness of the pressed surface are good, the hardness increases from 58A to 68A, the feel becomes worse, and the elongation at break also becomes lower. The lower the elongation, the tighter it is. After the garment is made, the experience is poor. It can be seen from the data of Example 1 and Comparative Example 1 that when H 12 After MDI was replaced by IPDI, the hard segment content decreased and the hardness changed from 58A to 50A, but the resilience became worse, mainly because H 12 The structure of MDI is more regular than that of IPDI. It can be seen from Example 1, Comparative Examples 2 and 3 that the strength of the crystallinity of the polyol has a great influence on the rebound. The crystallinity of Comparative Example 2 is too strong, the soft segment crystallizes, and thus loses the high rebound effect. The crystallinity of Comparative Example 3 is too weak, resulting in easy deformation after stretching, and the rebound effect will also deteriorate. It can be seen from the comparison data of Example 1 and Comparative Example 4 that after replacing BDO with EG, the temperature of the synthesized TPU material increases, the bonding strength decreases, and the rebound elasticity deteriorates a lot. In summary, the formula of Example 1 is most in line with expectations and has the best comprehensive effect.

[0085] The above are only preferred specific implementations of the present invention; however, the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and improved concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A thermoplastic polyurethane elastomer, characterized in that: Calculated by mass, it includes the following components: 80-110 parts of polyester polyol, 5-10 parts of chain extender, 0.03-1 parts of catalyst, 20-40 parts of isocyanate, 0-2 parts of nucleating aid, 0.05-0.5 parts of antioxidant, 0.05-0.2 parts of ultraviolet absorber.

2. A thermoplastic polyurethane elastomer according to claim 1, characterized in that: In parts by mass, the antioxidant is preferably 1010 or 1076; The ultraviolet absorber is preferably one of UV326, UV328 and UV329.

3. A thermoplastic polyurethane elastomer according to claim 1, characterized in that: The composition comprises the following components by weight: 95-100 parts of polyester polyol, 5-9 parts of chain extender, 0.05-0.1 parts of catalyst, 25-35 parts of isocyanate and 1.2-1.8 parts of nucleating agent.

4. A thermoplastic polyurethane elastomer according to claim 1, characterized in that: The polyester polyol is PBHA with a molecular weight of 2000.

5. A thermoplastic polyurethane elastomer according to claim 1, characterized in that: The chain extender is BDO or a combination of BDO and N,N-di-tert-butylethylenediamine.

6. A thermoplastic polyurethane elastomer according to claim 1, characterized in that: The catalyst is a metal catalyst, preferably an organic tin or organic bismuth.

7. A thermoplastic polyurethane elastomer according to claim 1, characterized in that: The isocyanate is H 12 MDI.

8. A thermoplastic polyurethane elastomer according to any one of claims 1 to 7, characterized in that: The nucleating agent is an inorganic nucleating agent or a polymer nucleating agent; The polymer nucleating agent is preferably one or more of an α-crystal nucleating agent, a β-crystal nucleating agent and a nylon nucleating agent.

9. Use of a thermoplastic polyurethane elastomer according to any one of claims 1 to 8 in fabrics.

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