TPU compatilizer, TPU master batch, TPU film and preparation method and application thereof

Abstract

The invention discloses a TPU (thermoplastic polyurethane) compatilizer, a TPU master batch, a TPU film as well as a preparation method and application thereof. The TPU compatilizer raw material composition comprises a first TPU base material, a modifier, an initiator and a first antioxidant, wherein the modifier is organic acid anhydride. The TPU compatilizer disclosed by the invention is applied to a TPU film, and the TPU film has good stability and mechanical properties.

Description

Technical Field

[0001] This invention relates to a TPU compatibilizer, a TPU masterbatch, a TPU film, its preparation method, and its application. Background Technology

[0002] Thermoplastic polyurethane elastomer (TPU) is a block copolymer made primarily from polyisocyanates, oligomeric polyols, and chain extenders. It possesses excellent comprehensive properties such as high strength, high toughness, abrasion resistance, and oil resistance. Furthermore, due to its good processability, it is widely used in numerous industries. TPU film is made from TPU masterbatch, or a blend of TPU particles and functional TPU masterbatch, through processes such as casting, calendering, blown film production, and coating.

[0003] Depending on the processing or application industry requirements, TPU films generally require the addition of corresponding functional additives, such as lubricants, antioxidants, light stabilizers, antistatic agents, flame retardants, and antibacterial agents, to give the film the corresponding functionality. For TPU masterbatches or film materials, especially those containing small-molecule additives, fillers with poor compatibility with TPU, or high-content fillers, ensuring the compatibility between the TPU substrate and the additives / fillers is crucial, directly affecting the performance and appearance of the related products. For example, after a period of storage or use, the prepared film may exhibit powder precipitation or fogging on its surface. However, some existing technologies still do not address the compatibility issue. For instance, invention patent CN118344723A discloses a moisture-permeable TPU film and its processing technology; invention patent CN117777706A discloses a stress-resistant whitening TPU film and its preparation method, neither of which considers compatibility.

[0004] Currently, existing technologies that address compatibility issues mainly use silane coupling agents, maleic anhydride-grafted PE, SEBS, EPDM, PP, POE, etc., as compatibility agents, and indirectly improve the compatibility of additives, fillers, and TPU substrates by adding other components. For example, invention patent CN119463460A discloses a flame-retardant TPU film and its preparation method; invention patent CN113308000A discloses a high-environment-resistant TPU acoustic film and its preparation method, both using silane coupling agents to improve interfacial compatibility; invention patent CN 113337102A discloses a TPU film with good adhesion and its preparation method, using polyethylene grafted with maleic anhydride as a compatibilizer; invention patent CN 115124944A discloses a heat-resistant, high-flow thermoplastic polyurethane hot melt adhesive film and its preparation method, which uses one or more of maleic anhydride grafted polyolefin, styrene-maleic anhydride copolymer, and glycidyl methacrylate grafted polyolefin copolymer as compatibilizers; invention patent CN 116061535A discloses a silver-black dual-color light-blocking film, using polyethylene grafted with maleic anhydride and polypropylene grafted with maleic anhydride as compatibilizers; invention patent CN119241855... A discloses an antibacterial compatibilizer, its preparation method, and its application, which uses POE grafted with maleic anhydride as a compatibilizer. Although the above method can improve compatibility to some extent, the degree of improvement is still limited.

[0005] Therefore, how to further improve the compatibility of TPU substrates with additives and fillers, and obtain TPU masterbatches or films with excellent consistency, remains a key issue of concern for researchers in this field. Summary of the Invention

[0006] This invention aims to overcome the shortcomings of poor compatibility between other components and the TPU substrate in existing TPU films, and provides a TPU compatibilizer, TPU masterbatch, TPU film, its preparation method, and applications. When the TPU compatibilizer of this invention is applied to TPU films, the TPU films exhibit good stability and mechanical properties.

[0007] The present invention provides a TPU compatibilizer, the raw material composition of which includes: a first TPU substrate, a modifier, an initiator and a first antioxidant, wherein the modifier is an organic acid anhydride.

[0008] In this invention, a grafting reaction occurs between the first TPU substrate and the modifier, preferably in the molten state.

[0009] In this invention, the grafting rate of the TPU compatibilizer can be 0.3%-1.5%, preferably 0.5%-1.5%.

[0010] In some specific embodiments, the grafting rate of the TPU compatibilizer may be 0.37%, 0.53%, 0.87%, 1.15%, 1.26%, 1.42%, 1.34%, 1.21%, 1.13%, 0.78%, or 0.63%.

[0011] In this invention, the melt index of the TPU compatibilizer can be 7 g / 10min - 15 g / 10min.

[0012] In some specific embodiments, the melt index of the TPU compatibilizer may be 8.9 g / 10min, 9.5 g / 10min, 10.1 g / 10min, 10.4 g / 10min, 10.6 g / 10min, 11.3 g / 10min, 11.6 g / 10min, 11.9 g / 10min, 12.1 g / 10min, or 13.5 g / 10min.

[0013] In this invention, the Shore hardness of the first TPU substrate can be 80A-95A, for example 85A or 92A.

[0014] In some specific implementations, the product model of the first TPU substrate may be Lubrizol's BF-92 and / or BASF's S685.

[0015] In this invention, the first TPU substrate is a TPU conventionally used in the art, which is a block copolymer made from polyisocyanate, oligomeric polyol and chain extender as the main raw materials, and is a thermoplastic polyurethane elastomer; preferably a polyester-type TPU.

[0016] In this invention, the organic acid anhydride may be a dicarboxylic acid anhydride, such as maleic anhydride and / or phthalic anhydride.

[0017] In this invention, with 100 parts by weight of the first TPU substrate, the organic acid anhydride can be 0.5-5 parts by weight, for example, 0.5 parts, 1 part, 2 parts or 2.5 parts.

[0018] In this invention, the initiator can be a substance commonly used in the art that can initiate a grafting reaction between organic acid anhydrides and TPU substrate, preferably a peroxide, such as one or more of dicumyl peroxide (DCP), di-tert-butyl peroxide, benzoyl peroxide, and tert-butyl peroxide.

[0019] In this invention, based on 100 parts by weight of the first TPU substrate, the initiator can be 0.03-0.5 parts by weight, for example 0.05 parts, 0.1 parts or 0.2 parts.

[0020] In this invention, the first antioxidant can be a substance with antioxidant function commonly used in the art, preferably a hindered phenolic antioxidant and / or a phosphite antioxidant.

[0021] The hindered phenolic antioxidant is preferably triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245) and / or pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010).

[0022] The phosphite antioxidant is preferably tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168).

[0023] When the first antioxidant is a hindered phenolic compound and a phosphite compound, the mass ratio of the hindered phenolic compound to the phosphite compound is preferably (0.5-1.5):1, for example 0.5:1 or 1:1.

[0024] In some specific embodiments, the first antioxidant is a mixture of antioxidant 245, antioxidant 1010 and antioxidant 168; the mass ratio of antioxidant 1010, antioxidant 168 and antioxidant 245 is preferably 1:1:(1-3), for example 1:1:1 or 1:1:2.

[0025] In this invention, with 100 parts by weight of the first TPU substrate, the antioxidant can be 0.1-0.6 parts by weight, for example, 0.3 parts.

[0026] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 0.5 parts of maleic anhydride, and 0.05 parts of an initiator.

[0027] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 1 part of maleic anhydride, and 0.05 parts of an initiator.

[0028] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 1 part of maleic anhydride, and 0.1 parts of an initiator.

[0029] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 1 part of maleic anhydride, and 0.2 parts of an initiator.

[0030] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 2 parts of maleic anhydride, and 0.2 parts of an initiator.

[0031] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 2 parts of maleic anhydride, and 0.3 parts of an initiator.

[0032] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 2.5 parts of maleic anhydride, and 0.2 parts of an initiator.

[0033] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 1 part of maleic anhydride, and 0.1 parts of an initiator.

[0034] In some specific embodiments, the raw material composition of the TPU compatibilizer consists of the following components: 100 parts of a first TPU substrate, 0.3 parts of a first antioxidant, 2 parts of maleic anhydride, and 0.2 parts of an initiator.

[0035] The present invention also provides a method for preparing the TPU compatibilizer as described above, which includes the following steps: reacting and extruding the raw material composition of the TPU compatibilizer as described above to obtain the compatibilizer.

[0036] In this invention, the reaction temperature can be 170℃-200℃, for example 170℃, 185℃ or 200℃.

[0037] In this invention, the TPU compatibilizer can be prepared in a twin-screw extruder.

[0038] The screw speed of the twin-screw extruder can be 20-60 rpm, for example, 30 rpm or 60 rpm.

[0039] The present invention also provides a TPU masterbatch comprising a second TPU substrate and a TPU compatibilizer as described above.

[0040] In this invention, the mass ratio of the second TPU substrate to the TPU compatibilizer can be 100:(1-20), for example 100:3, 100:6, 100:8 or 100:10.

[0041] In this invention, the TPU masterbatch may further include additives and / or fillers.

[0042] The additive may be one or more of the following: a second antioxidant, a light stabilizer, an ultraviolet absorber, a flame retardant, a lubricant, an antibacterial agent, an antistatic agent, and a matting agent, such as an antioxidant or a flame retardant.

[0043] The second antioxidant is preferably a hindered phenolic antioxidant and / or a phosphite antioxidant.

[0044] The hindered phenolic antioxidant is preferably triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245) and / or pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010).

[0045] The phosphite antioxidant is preferably tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168).

[0046] When the second antioxidant is a hindered phenolic compound and a phosphite compound, the mass ratio of the hindered phenolic compound to the phosphite compound is preferably (0.5-1.5):1, for example 0.5:1 or 1:1.

[0047] In some specific embodiments, the second antioxidant is a mixture of antioxidant 245, antioxidant 1010 and antioxidant 168; the mass ratio of antioxidant 1010, antioxidant 168 and antioxidant 245 is preferably 1:1:(1-3), for example 1:1:1 or 1:1:2.

[0048] The flame retardant is preferably a halogen-free flame retardant, and more preferably a diethylaluminum hypophosphite and / or melamine cyanurate.

[0049] In some specific embodiments, the flame retardant is aluminum diethylphosphite and melamine cyanurate in a mass ratio of 1:1.

[0050] The lubricant is preferably a fatty acid salt, such as zinc stearate.

[0051] Based on 100 parts by weight of the second TPU substrate, the amount of the additive can be optionally 0-30 parts by weight, preferably 0.5-10 parts, for example 0.5 parts, 1 part, 3.5 parts, 15 parts or 15.5 parts.

[0052] The filler may be one or more of the following: silica, kaolin, talc, carbon black, calcium carbonate, montmorillonite, glass microspheres, pigments, heat insulation and infrared absorbers, such as silica, montmorillonite or talc.

[0053] With 100 parts by weight of the second TPU substrate, the filler can optionally be 0-60 parts by weight, preferably 5-20 parts, such as 6 parts, 7 parts or 10 parts.

[0054] In some specific embodiments, the TPU masterbatch is composed of a second TPU substrate and the TPU compatibilizer.

[0055] In some specific embodiments, the TPU masterbatch consists of a second TPU substrate, the TPU compatibilizer, and additives.

[0056] In some specific embodiments, the TPU masterbatch consists of a second TPU substrate, the TPU compatibilizer, and fillers.

[0057] In some specific embodiments, the TPU masterbatch consists of a second TPU substrate, the TPU compatibilizer, additives, and fillers.

[0058] In some specific embodiments, the TPU masterbatch is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, and 1 part of a second antioxidant.

[0059] In some specific embodiments, the TPU masterbatch consists of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, and 3.5 parts of lubricant.

[0060] In some specific embodiments, the TPU masterbatch is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, and 10 parts of talc.

[0061] In some specific embodiments, the TPU masterbatch is composed of the following components: 100 parts of a second TPU substrate, 8 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 10 parts of talc.

[0062] In some specific embodiments, the TPU masterbatch is composed of the following components: 100 parts of a second TPU substrate, 10 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 15 parts of a flame retardant.

[0063] In some specific embodiments, the TPU masterbatch is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 7 parts of silica.

[0064] In some specific embodiments, the TPU masterbatch is composed of the following components: 100 parts of a second TPU substrate, 3 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 6 parts of montmorillonite.

[0065] The present invention also provides a method for preparing TPU masterbatch as described above, which includes the following steps: reacting and granulating a mixture comprising a second TPU substrate and the TPU compatibilizer.

[0066] In this invention, the reaction temperature can be 160℃-190℃.

[0067] In this invention, the reaction can be carried out in a twin-screw extruder, preferably with a main extruder speed of 200 rpm to 300 rpm, for example, 250 rpm.

[0068] In this invention, the reaction time is the residence time of the material in the twin-screw extruder, which is mainly related to the rotational speed of the twin-screw extruder. The slower the rotational speed, the shorter the reaction time; conversely, the faster the rotational speed, the shorter the reaction time.

[0069] After granulation, the material is dried.

[0070] The present invention provides a TPU film comprising a second TPU substrate and a TPU compatibilizer.

[0071] In this invention, the mass ratio of the second TPU substrate to the TPU compatibilizer can be 100:(1-20), for example 100:3, 100:6, 100:8 or 100:10.

[0072] In this invention, the TPU film may further include additives and / or fillers.

[0073] The additive may be one or more of the following: a second antioxidant, a light stabilizer, an ultraviolet absorber, a flame retardant, a lubricant, an antibacterial agent, an antistatic agent, and a matting agent, such as an antioxidant or a flame retardant.

[0074] The second antioxidant is preferably a hindered phenolic antioxidant and / or a phosphite antioxidant.

[0075] The hindered phenolic antioxidant is preferably triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245) and / or pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010).

[0076] The phosphite antioxidant is preferably tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168).

[0077] When the antioxidant is a hindered phenolic compound and a phosphite compound, the mass ratio of the hindered phenolic compound to the phosphite compound is preferably (0.5-1.5):1, for example 0.5:1 or 1:1.

[0078] In some specific embodiments, the antioxidant is a mixture of antioxidant 245, antioxidant 1010 and antioxidant 168; the mass ratio of antioxidant 1010, antioxidant 168 and antioxidant 245 is preferably 1:1:(1-3), for example 1:1:1 or 1:1:2.

[0079] The flame retardant is preferably a halogen-free flame retardant, and more preferably a diethylaluminum hypophosphite and / or melamine cyanurate.

[0080] In some specific embodiments, the flame retardant is aluminum diethylphosphite and melamine cyanurate in a mass ratio of 1:1.

[0081] The lubricant is preferably a fatty acid salt, such as zinc stearate.

[0082] Based on 100 parts by weight of the second TPU substrate, the amount of the additive can optionally be 0-30 parts by weight, for example 0.5 parts, 1 part, 3.5 parts, 15 parts or 15.5 parts.

[0083] The filler may be one or more of the following: silica, kaolin, talc, carbon black, calcium carbonate, montmorillonite, glass microspheres, pigments, heat insulation and infrared absorbers, such as silica, montmorillonite or talc.

[0084] With the second TPU substrate comprising 100 parts by weight, the filler may optionally comprise 0-60 parts by weight, for example 6 parts, 7 parts, or 10 parts.

[0085] In some specific embodiments, the TPU film is composed of a second TPU substrate and the TPU compatibilizer.

[0086] In some specific embodiments, the TPU film is composed of a second TPU substrate, the TPU compatibilizer, and additives.

[0087] In some specific embodiments, the TPU film is composed of a second TPU substrate, the TPU compatibilizer, and fillers.

[0088] In some specific embodiments, the TPU film is composed of a second TPU substrate, the TPU compatibilizer, additives, and fillers.

[0089] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, and 1 part of a second antioxidant.

[0090] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, and 3.5 parts of lubricant.

[0091] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, and 10 parts of talc.

[0092] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 8 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 10 parts of talc.

[0093] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 10 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 15 parts of a flame retardant.

[0094] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 6 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 7 parts of silica.

[0095] In some specific embodiments, the TPU film is composed of the following components: 100 parts of a second TPU substrate, 3 parts of the TPU compatibilizer, 0.5 parts of a second antioxidant, and 6 parts of montmorillonite.

[0096] This invention provides a method for preparing a TPU film as described above, wherein the TPU masterbatch as described above is prepared into a TPU film.

[0097] In this invention, the TPU film preparation method can be any film-making method conventionally used in the art, and can be any one of casting, calendering, blow molding and coating.

[0098] In this invention, the TPU film can be prepared on a casting extruder.

[0099] The speed of the cast extruder is preferably 5 rpm to 80 rpm, for example 13 rpm.

[0100] In this invention, the processing temperature during the preparation process can be 140-210℃, preferably 175-200℃.

[0101] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0102] The reagents and raw materials used in this invention are all commercially available.

[0103] The positive and progressive effects of this invention are as follows:

[0104] The TPU compatibilizer provided by this invention has a high grafting rate and good processing performance. When applied to the preparation of TPU films, it can effectively improve the compatibility between additives or fillers and TPU substrates, which is beneficial to improving the stability and uniformity of the TPU film and preventing powder precipitation. Furthermore, it can enable TPU films to have both good tensile strength and tensile elongation at break. Attached Figure Description

[0105] Figure 1 This is a SEM image of the TPU film prepared in Example 6.

[0106] Figure 2 This is a SEM image of the TPU film prepared in Comparative Example 6. Detailed Implementation

[0107] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0108] The types and manufacturers of the raw materials used in the following examples and comparative examples are shown in the table below:

[0109] Raw material name model factory First TPU substrate, second TPU substrate BF-92 Lubrizol dicumyl peroxide Perkadox® BC-FF Noryon Antioxidant 1010 <![CDATA[Pentaerythritol Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], type Irganox ® 1010]]> BASF AG Antioxidant 168 <![CDATA[Tris(2,4-di-tert-butylphenyl) phosphite, type Irgafos ® 168]]> BASF AG Antioxidant 245 <![CDATA[Bis(β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate) of diethylene glycol, model Irganox ® 245]]> BASF AG Zinc stearate Z-60S Qingdao Sainuo New Materials talcum powder DH-10000 Yingkou Dahai Talc Mining Aluminum diethylphosphite Exolit OP935 Clariant melamine cyanurate MCA-25 BASF AG silicon dioxide AEROSIL® R972 Evonik Montmorillonite DK2 Zhejiang Fenghong New Materials SEBS-g-MAH Maleic anhydride-grafted hydrogenated styrene-butadiene-styrene block copolymer, model FG1901 KETEN Polymer Co., Ltd.

[0110] Preparation Example 1

[0111] (1) The first TPU substrate is thoroughly dried using a dehumidifying drying device. 100 parts of the thoroughly dried first TPU substrate, 0.5 parts of the modifier maleic anhydride (MAH), 0.05 parts of the initiator dicumyl peroxide (DCP), and 0.3 parts of the first antioxidant (antioxidant 1010, antioxidant 168 and antioxidant 245 are mixed in a mass ratio of 1:1:1) are weighed according to the proportion and put into a high-speed mixer and stirred evenly. Then the evenly mixed material is put into the hopper of the main feeding system of the twin-screw extruder.

[0112] (2) Start the main feeding system and react and extrude according to the set conditions (screw speed is 30 rpm, feed target flow rate is 6 kg / h, processing temperature is 185℃). After the extrudate is cooled by a cold water tank, it is pelleted to obtain TPU compatibilizer.

[0113] Preparation Examples 2-11

[0114] Based on the preparation example 1, some parameters of the modifier dosage, initiator dosage, and processing temperature were adjusted.

[0115] Preparation Example 12

[0116] Based on the preparation example 1, maleic anhydride was changed to phthalic anhydride.

[0117] The amounts of each component used in the preparation of Examples 2-12, as well as the screw speed and processing temperature of the twin-screw extruder, are shown in Table 1. Other steps are the same as in Example 1.

[0118] Table 1

[0119] serial number Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 Preparation Example 11 Preparation Example 12 First TPU substrate usage 100 100 100 100 100 100 100 100 100 100 100 100 Dosage of the first antioxidant mixture 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Modifier dosage 0.5 1 1 1 2 2 2.5 1 1 2 2 0.5 Initiator dosage 0.05 0.05 0.1 0.2 0.2 0.3 0.2 0.1 0.1 0.2 0.2 0.05 Processing temperature ℃ 185 185 185 185 185 185 185 170 200 170 200 185 screw speed rpm 30 30 30 30 30 30 30 30 30 60 60 30 Grafting rate % 0.53 0.87 1.15 1.26 1.42 1.34 1.21 1.13 0.78 0.63 0.37 0.21 Melt index g / 10min 12.1 11.3 10.6 10.1 8.9 11.9 9.5 10.4 11.6 11.9 13.5 9.7

[0120] Example 1

[0121] (1) Grafting rate test method:

[0122] The grafting rate in the grafted product was calculated by acid-base titration.

[0123] First, the TPU compatibilizer (TPU-g-MAH) prepared in the examples or comparative examples is dissolved in chloroform, then poured into methanol to precipitate. The precipitate is purified by vacuum filtration and then dried under vacuum to obtain the purified TPU-g-MAH sample.

[0124] Accurately weigh 0.2 g of the purified TPU-g-MAH sample and place it in a 100 ml Erlenmeyer flask. Add 25 ml of N,N-dimethylformamide (DMF) to dissolve it, add thymol blue-DMF indicator, titrate with 4 ml of 0.05 mol / L KOH-ethanol solution, and back-titrate with 0.01 mol / L HCl-isopropanol solution. Calculate the grafting rate using the following formula, and record the results in Table 1.

[0125]

[0126] Where: V0——volume of HCl-isopropanol solution consumed when pure TPU is used as a blank sample (ml);

[0127] V1 — Volume (ml) of HCl-isopropanol solution consumed by TPU-g-MAH;

[0128] C—Molar concentration (mol / ml) of HCl-isopropanol solution;

[0129] M – Molar mass of maleic anhydride (g / mol);

[0130] W — The mass (g) of the grafted modified TPU compatibilizer taken.

[0131] (2) Melt index:

[0132] Referring to GB / T3682-2018 standard, the TPU compatibilizer prepared in the preparation example was dried. The dried TPU compatibilizer was then loaded into the barrel of a melt flow index tester with a pre-set temperature of 190℃, and the material was compacted with the piston rod (the operation was completed within 1 minute). After waiting for 5 minutes, a 5 kg load was applied to the piston rod, and the die sealer was activated to allow the melt to flow out of the die. When the lower mark of the piston rod reached the upper edge of the barrel, timing was started, and the extrudate was simultaneously cut off and discarded. Before the upper mark of the piston rod reached the upper edge of the barrel, the extrudate was cut off again, and timing was stopped simultaneously. The time was recorded, and the weight of the sample segment was weighed. The average of 5 sets of data was taken to obtain the average mass m (in g) and the cutting time interval t (in s) of the 5 sets of cut samples. The results are shown in Table 1.

[0133] Melt Flow Index (MFR) = 600 m / t, in grams per 10 minutes (g / 10min).

[0134] The TPU compatibilizers prepared in Examples 1-11 of this invention have a high grafting rate and use TPU substrate as the compatibilizer matrix. The high affinity of homology can effectively improve the stability and uniformity of appearance of TPU products in subsequent preparation. The melt index of the TPU compatibilizer is above 8.5 g / 10 min, indicating that it has high fluidity, which is beneficial to the subsequent processing.

[0135] Example 1

[0136] (1) Six parts of the TPU compatibilizer prepared in Example 5 and 100 parts of the second TPU substrate were put into a mixer and stirred. After being stirred evenly, the mixture was dehumidified and dried, and then fed into the main feeding system barrel of the twin-screw extruder.

[0137] The antioxidant mixture obtained by mixing 1 part of antioxidant 245, antioxidant 1010 and antioxidant 168 (second antioxidant) in a mass ratio of 1:1:2 is vacuum dried and mixed evenly, and then fed into the feed system barrel of the twin-screw extruder.

[0138] (2) According to the mixing ratio, the target flow rate of the main feeding system barrel is set to 53 kg / h, and the target flow rate of the auxiliary feeding system barrel is set to 0.5 kg / h. The feed is fed into the twin-screw extruder, the screw speed is set to 250 rpm, and the processing temperature is 160-190℃. The specific temperature settings of each zone of the twin screw are: 160℃-170℃-180℃-185℃-185℃-170℃-180℃-190℃-190℃-180℃-170℃. Melt blending extrusion is carried out, and the extrudate is cooled by a cooling water tank and then granulated to obtain TPU masterbatch.

[0139] (3) The TPU masterbatch prepared in step (2) is dehumidified and dried and then put into the barrel of the casting extruder. The rotation speed is set to 13 pm and the processing temperature is 175-200℃. The specific temperature settings of each part of the casting extruder are: 175℃-185℃-195℃-195℃-200℃-190℃-185℃. The corresponding TPU film is obtained by casting extrusion.

[0140] Example 2

[0141] Based on Example 1, 1 part of the second antioxidant was adjusted to 3.5 parts of zinc stearate, and other conditions were the same as in Example 1.

[0142] Example 3

[0143] Based on Example 1, 1 part of the second antioxidant was adjusted to 10 parts of talc powder, and other conditions were the same as in Example 1.

[0144] Comparative Example 1

[0145] Based on Example 1, without adding TPU compatibilizer, all other conditions are the same as in Example 1.

[0146] Comparative Example 2

[0147] Based on Example 2, without adding TPU compatibilizer, all other conditions are the same as in Example 2.

[0148] Comparative Example 3

[0149] Based on Example 3, without adding TPU compatibilizer, all other conditions are the same as in Example 3.

[0150] The types and amounts of each component in Examples 1-3 and Comparative Examples 1-3 are shown in Table 2. Other steps are the same as in Example 1.

[0151] Table 2. Precipitates in thin films (Double 85 test * 168h)

[0152] Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 Second TPU substrate usage 100 100 100 100 100 100 TPU compatibilizer dosage 6 / 6 / 8 / Second antioxidant dosage 1 1 / / / / Zinc stearate dosage / / 3.5 3.5 / / Talc dosage / / / / 10 10 Precipitation status No obvious precipitation Precipitation No obvious precipitation Precipitation No obvious precipitation Precipitation

[0153] Note: In Table 2, " / " indicates that the component was not added.

[0154] Example 4

[0155] (1) Eight parts of the TPU compatibilizer prepared in Preparation Example 5 and 100 parts of TPU substrate (second TPU substrate) were put into a mixer and stirred. After stirring evenly, the mixture was dehumidified and dried, and then put into the main feeding system barrel of the twin-screw extruder.

[0156] The antioxidant mixture (second antioxidant) obtained by mixing 0.5 parts of antioxidant 245, antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1:2 and 10 parts of talc powder are vacuum dried and mixed evenly, and then fed into the feed cylinder of the auxiliary feeding system of the twin-screw extruder.

[0157] (2) According to the mixing ratio, the target flow rate of the main feeding system barrel is set to 54 kg / h and the target flow rate of the auxiliary feeding system barrel is set to 5.25 kg / h. The feed is fed into the twin-screw extruder, the screw speed is set to 300 rpm, and the processing temperature is 160-190℃ for melt blending extrusion. The extrudate is cooled by the cooling water tank and then granulated to obtain TPU masterbatch.

[0158] (3) The TPU masterbatch prepared in step (2) is dehumidified and dried and then fed into the barrel of a casting extruder. The rotation speed is set to 13 pm and the processing temperature is 175-200℃. The TPU film is obtained by casting extrusion.

[0159] Example 5

[0160] (1) 10 parts of the TPU compatibilizer prepared in Preparation Example 5 and 100 parts of TPU substrate (second TPU substrate) were put into a mixer and stirred. After stirring evenly, the mixture was dehumidified and dried, and then put into the main feeding system barrel of the twin-screw extruder.

[0161] The antioxidant mixture (second antioxidant) obtained by mixing 0.5 parts of antioxidant 245, antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1:2 and the flame retardant mixture obtained by mixing 15 parts of diethyl aluminum hypophosphite and melamine cyanurate in a mass ratio of 1:1 are vacuum dried and mixed evenly, and then fed into the feed cylinder of the auxiliary feeding system of the twin-screw extruder.

[0162] (2) Same as step (2) in Example 4;

[0163] (3) is the same as step (3) in Example 4.

[0164] Example 6

[0165] (1) Six parts of the TPU compatibilizer prepared in Preparation Example 5 and 100 parts of TPU substrate (second TPU substrate) were put into a mixer and stirred. After stirring evenly, the mixture was dehumidified and dried, and then put into the main feeding system barrel of the twin-screw extruder.

[0166] The antioxidant mixture (second antioxidant) obtained by mixing 0.5 parts of antioxidant 245, antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1:2 and 7 parts of silica are vacuum dried and mixed evenly, and then fed into the feed cylinder of the auxiliary feeding system of the twin-screw extruder.

[0167] (2) Same as step (2) in Example 4;

[0168] (3) is the same as step (3) in Example 4.

[0169] Example 7

[0170] (1) Three parts of the TPU compatibilizer prepared in Preparation Example 5 and 100 parts of TPU substrate (second TPU substrate) were put into a mixer and stirred. After stirring evenly, the mixture was dehumidified and dried, and then put into the main feeding system barrel of the twin-screw extruder.

[0171] Six parts of montmorillonite were vacuum dried and then fed into the feed cylinder of the auxiliary feeding system of a twin-screw extruder.

[0172] (2) Same as step (2) in Example 4;

[0173] (3) is the same as step (3) in Example 4.

[0174] Example 8

[0175] (1) Eight parts of the TPU compatibilizer prepared in Example 12 and 100 parts of TPU substrate (second TPU substrate) were put into a mixer and stirred. After stirring evenly, the mixture was dehumidified and dried, and then put into the main feeding system barrel of the twin-screw extruder.

[0176] The antioxidant mixture (second antioxidant) obtained by mixing 0.5 parts of antioxidant 245, antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1:2 and 10 parts of talc powder are vacuum dried and mixed evenly, and then fed into the feed cylinder of the auxiliary feeding system of the twin-screw extruder.

[0177] (2) Same as step (2) in Example 4;

[0178] (3) is the same as step (3) in Example 4.

[0179] Example 9

[0180] (1) Eight parts of the TPU compatibilizer prepared in Example 1 and 100 parts of TPU substrate (second TPU substrate) were put into a mixer and stirred. After stirring evenly, the mixture was dehumidified and dried, and then fed into the main feeding system barrel of a twin-screw extruder.

[0181] The antioxidant mixture (second antioxidant) obtained by mixing 0.5 parts of antioxidant 245, antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1:2 and 10 parts of talc powder are vacuum dried and mixed evenly, and then fed into the feed cylinder of the auxiliary feeding system of the twin-screw extruder.

[0182] (2) Same as step (2) in Example 4;

[0183] (3) is the same as step (3) in Example 4.

[0184] Comparative Example 4

[0185] Based on Example 4, without adding TPU compatibilizer, all other conditions are the same as in Example 4.

[0186] Comparative Example 5

[0187] Based on Example 5, without adding TPU compatibilizer, all other conditions are the same as in Example 5.

[0188] Comparative Example 6

[0189] Based on Example 6, without adding TPU compatibilizer, all other conditions are the same as in Example 6.

[0190] Comparative Example 7

[0191] Based on Example 7, 3 parts of TPU compatibilizer were replaced with 3 parts of SEBS-g-MAH (maleic anhydride-grafted hydrogenated styrene-butadiene-styrene block copolymer) compatibilizer, and other conditions were the same as in Example 7.

[0192] The types and amounts of each component in Examples 4-7 and Comparative Examples 4-7 are shown in Table 3. Other steps are the same as in Example 4.

[0193] Table 3

[0194] serial number Second TPU substrate quantity Types and amounts of compatibilizer Additives filler Tensile strength (MPa) Elongation at break (%) Precipitation status Example 4 100 copies TPU-g-MAH 8 portions 0.5 parts of the second antioxidant 10 parts talcum powder 48.7 475 No precipitation Comparative Example 4 108 copies / 0.5 parts of the second antioxidant 10 parts talcum powder 42.3 362 Precipitation Example 5 100 copies 10 servings of TPU-g-MAH 0.5 parts secondary antioxidant + 15 parts flame retardant mixture / 57.4 553 No precipitation Comparative Example 5 110 copies / 0.5 parts secondary antioxidant + 15 parts flame retardant mixture / 50.6 409 Precipitation Example 6 100 copies 6 portions of TPU-g-MAH 0.5 parts of the second antioxidant 7 parts silicon dioxide 63.8 577 No precipitation Comparative Example 6 106 copies / 0.5 parts of the second antioxidant 7 parts silicon dioxide 51.5 432 A small amount of precipitates Example 7 100 copies 3 copies of TPU-g-MAH / 6 portions of montmorillonite 31.6 562 No precipitation Comparative Example 7 100 copies SEBS-g-MAH 3 copies / 6 portions of montmorillonite 25.4 538 A small amount of precipitates Example 8 100 copies TPU-g-MAH 8 portions 0.5 parts of the second antioxidant 10 parts talcum powder 38.7 246 A small amount of precipitates Example 9 100 copies TPU-g-MAH 8 portions 0.5 parts of the second antioxidant 10 parts talcum powder 43.5 389 A small amount of precipitates

[0195] Example 2

[0196] Precipitate test in TPU film:

[0197] A sample of the TPU film prepared according to Examples 1-9 and Comparative Examples 1-7 was cut and placed in a constant temperature and humidity chamber (temperature set to 85℃, humidity set to 85%). After 168 hours, the TPU film sample was removed, and the presence of precipitates on the surface of the TPU film was observed. The results are recorded in Tables 2 and 3. If there are no precipitates or very few precipitates, it indicates that the additives or fillers have good compatibility with the TPU substrate; otherwise, it indicates poor compatibility.

[0198] Example 3

[0199] Tensile strength and elongation at break:

[0200] The tensile strength and tensile elongation at break of Examples 4-9 and Comparative Examples 4-7 were tested in accordance with the ISO 527-3-2018 international standard, and the results are recorded in Table 3.

[0201] As can be seen from the data in Tables 2 and 3, the TPU film prepared using the TPU compatibilizer of the present invention has good stability, and no exudate is found on the surface after 168 hours. As can also be seen from the data in Table 3, the TPU film of the present invention has good mechanical properties, with a tensile strength of over 30 MPa and a tensile elongation at break of over 240%.

[0202] Comparative Examples 1-6 did not contain the TPU compatibilizer of the present invention, and as can be seen from the data in Tables 2 and 3, precipitates were generated on their surfaces. Figure 1 This is a SEM image of the TPU film prepared in Example 1. Figure 2 The image shows the SEM image of the TPU film prepared in Comparative Example 1. Comparing the two images, it can be seen that the additives and the TPU substrate exist independently in the TPU film without the addition of TPU compatibilizer and are not tightly bonded, indicating that the compatibility is very poor.

[0203] Comparative Example 7 used SEBS-g-MAH compatibilizer, which also caused filler or additive precipitation, severely affecting the appearance of the TPU film; and according to the data in Table 3, it can be seen that the mechanical properties of Comparative Examples 1-7 are also very poor.

[0204] The only difference between the three sets of technical solutions, namely Comparative Example 4 and Example 4, Comparative Example 5 and Example 5, and Comparative Example 6 and Example 6, is that the TPU compatibilizer of the present invention was not added in the comparative examples. It can be seen that, compared with the examples, the tensile strength of the comparative examples is reduced by more than 11%, and the tensile elongation at break is reduced by more than 23%.

[0205] The difference between Comparative Example 7 and Example 7 lies in the type of compatibilizer. The TPU film using SEBS-g-MAH compatibilizer had a 19.6% lower tensile strength and a lower elongation at break compared to the TPU compatibilizer of the present invention.

[0206] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A TPU compatibilizer characterized in that, The raw material composition thereof comprises: a first TPU base material, a modifier, an initiator and a first antioxidant, wherein the modifier is an organic acid anhydride.

2. The TPU compatibilizer according to claim 1, which satisfies one or more of the following conditions: (a) the grafting rate of the TPU compatibilizer is 0.3%-1.5%; (b) the melt index of the TPU compatibilizer is 7 g / 10 min-15 g / 10 min; (c) the Shore hardness of the first TPU base material is 80A-95A; (d) the first TPU base material is a polyester type TPU; (e) the organic acid anhydride is maleic anhydride and / or phthalic anhydride; (f) the weight fraction of the organic acid anhydride is 0.5-5 parts based on 100 parts of the first TPU base material; (g) the initiator is one or more of dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide and tert-butyl peroxybenzoate; (h) the weight fraction of the initiator is 0.03-0.5 parts based on 100 parts of the first TPU base material; (i) the first antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant; (g) the weight fraction of the first antioxidant is 0.1-0.6 parts based on 100 parts of the first TPU base material.

3. A method for producing the TPU compatibilizer according to claim 1 or 2, characterized by, The method comprises the following steps: reacting and extruding the raw material composition of the TPU compatibilizer according to claim 1 or 2, thereby obtaining the TPU compatibilizer.

4. A TPU masterbatch characterized in that, The method comprises the following steps: reacting and extruding the raw material composition of the TPU compatibilizer according to claim 1 or 2, thereby obtaining the TPU compatibilizer.

5. The TPU masterbatch of claim 4, wherein, The TPU masterbatch satisfies one or more of the following conditions: (a) the mass ratio of the second TPU base material to the TPU compatibilizer is 100:(1-20); (b) the TPU masterbatch comprises a second antioxidant, which is a hindered phenol antioxidant and / or a phosphite antioxidant; the weight fraction of the second antioxidant is 0.5-20 parts based on 100 parts of the second TPU base material; (c) the TPU masterbatch comprises a flame retardant, which is a halogen-free flame retardant; the weight fraction of the flame retardant is 0.5-20 parts based on 100 parts of the second TPU base material; (d) the TPU masterbatch comprises a lubricant, which is a fatty acid salt; the weight fraction of the lubricant is 0.5-20 parts based on 100 parts of the second TPU base material; (e) the TPU masterbatch comprises a filler, which is one or more of silica, montmorillonite and talc powder; the weight fraction of the filler is 5-20 parts based on 100 parts of the second TPU base material.

6. A process for the production of a TPU masterbatch as claimed in claim 4 or 5, characterized in that, The method comprises the following steps: reacting and granulating the mixture comprising the second TPU base material and the TPU compatibilizer.

7. Use of the TPU compatibilizer according to claim 1 or 2 or the TPU masterbatch according to claim 4 or 5 in the preparation of a TPU film.

8. A TPU film characterized by, The method comprises the following steps: reacting and granulating the mixture comprising the second TPU base material and the TPU compatibilizer.

9. The TPU film of claim 8, wherein, The TPU film satisfies one or more of the following conditions: (a) the mass ratio of the second TPU substrate to the TPU compatibilizer is 100:(1-20); (b) the TPU film comprises a second antioxidant, the second antioxidant being a hindered phenol antioxidant and / or a phosphite antioxidant; the weight fraction of the second antioxidant being 0.5-20 parts based on 100 parts by weight of the second TPU substrate; (c) the TPU film comprises a flame retardant, the flame retardant being a halogen-free flame retardant; the weight fraction of the flame retardant being 0.5-20 parts based on 100 parts by weight of the second TPU substrate; (d) the TPU film comprises a lubricant, the lubricant being a fatty acid salt; the weight fraction of the lubricant being 0.5-20 parts based on 100 parts by weight of the second TPU substrate; (e) the TPU film comprises a filler, the filler being one or more of silica, montmorillonite and talc powder; the weight fraction of the filler being 5-20 parts based on 100 parts by weight of the second TPU substrate.

10. A method for preparing the TPU film according to claim 8 or 9, the TPU masterbatch according to claim 4 or 5 being prepared into a film.

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