A stain-resistant thermoplastic polyurethane elastomer composite and a method of making the same

Abstract

The present application relates to a kind of resistant to dirt thermoplastic polyurethane composite material, it includes thermoplastic polyurethane elastomer 100 parts by weight, polyol 0.01-20 parts by weight, porous material 0.1-20 parts.The thermoplastic polyurethane composite material of the present application has excellent resistance to Mark pen, resistance to oil stain, resistance to cosmetics etc.Characteristics, product can be applied to watch, bracelet etc.Intelligent wearing field.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of thermoplastic elastomer composite materials, in particular to a stain-resistant thermoplastic polyurethane elastomer composite material and a preparation method thereof. BACKGROUND

[0002] Thermoplastic polyurethane elastomer (TPU) is a kind of thermoplastic elastomer that can be melt processed. It has high elasticity in a wide range of hardness, good mechanical strength and excellent wear resistance, in addition, TPU also has excellent oil resistance, aging resistance and low temperature resistance. However, the intermolecular polarity of TPU is large, which leads to poor performance in resisting cosmetics, Mark pens and the like.

[0003] Research focuses on modifying TPU with fluorine-containing polymers. Although the introduction of fluorine-containing polymers can reduce the surface tension of TPU, the performance of the material in resisting Mark pens, cosmetics and the like has not been improved.

[0004] Patent CN106832184 A relates to a thermoplastic silicone polyurethane elastomer and a preparation method thereof. The raw materials of the elastomer include the following components: macromolecular polyol 25-80 parts; silicone oil or liquid silicone rubber 0-60 parts; diisocyanate 10-50 parts; chain extender small molecule diol 3-20 parts; and auxiliary 0.1-3 parts. The macromolecular polyol is a non-silicon polyol with a molecular weight of 1000-4000 g / mol and a polyol modified by copolymerization or grafting with silicone. The chain extender small molecule diol refers to a small molecule diol with 10 carbons or less. However, the addition of silicone oil or liquid silicone rubber can lead to poor compatibility of the material and easy delamination of the surface.

[0005] Patent CN108641057 A relates to a silicone rubber polyurethane thermoplastic elastomer and a preparation method thereof. The silicone rubber polyurethane thermoplastic elastomer includes the following components in parts by weight: polyol 50-80 parts, two-component liquid silicone glue 10-30 parts, diisocyanate 15-40 parts, chain extender 3-10 parts, and auxiliary 0.1-2 parts. The addition amount of two-component liquid silicone glue is high, the compatibility is poor, and the stability of the product is poor. SUMMARY

[0006] The technical problem to be solved by the present application is to solve the problem of TPU not being resistant to stains, to broaden its application field, and to provide a stain-resistant thermoplastic polyurethane elastomer (TPU) composite material.

[0007] In order to solve the above technical problems, the present application adopts the following technical solutions, all in parts by weight unless otherwise specified:

[0008] A stain-resistant TPU composite material, the composite material comprising:

[0009] thermoplastic polyurethane elastomer 100 parts by weight;

[0010] polyol 0.01-20 parts by weight, preferably 0.1-5 parts by weight, more preferably 0.5-3 parts by weight;

[0011] As a preferred solution, the TPU composite further comprises 0.1-20 parts by weight, preferably 1-5 parts by weight, porous material;

[0012] The porous material is at least one of porous silicon and porous carbon;

[0013] The porous carbon is at least one of microporous carbon (<2 nm), mesoporous carbon (2-50 nm), macroporous carbon (>50 nm), preferably microporous carbon; the porous silicon is at least one of microporous silicon (<2 nm), mesoporous silicon (2-50 nm), macroporous silicon (>50 nm), preferably mesoporous silicon.

[0014] The polyol is one or more of polyester polyol, polyether polyol, silicon-containing polyol and fluorine-containing polyol;

[0015] The polyester polyol is preferably one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol; the polyether polyol is preferably one or more of polyoxypropylene polyol, polytetrahydrofuran polyol and copolyether polyol;

[0016] The silicon-containing polyol is a dihydric alcohol containing dimethylsiloxane fragments in the molecular chain;

[0017] The fluorine-containing polyol is a dihydric alcohol containing -CF2- fragments in the molecular backbone;

[0018] The number average molecular weight of the polyol is 500-4000, preferably 1000-2000.

[0019] The hardness of the thermoplastic polyurethane elastomer is 60A-80D, preferably 70A-60D, more preferably 80A-55D;

[0020] The hard segment phase of the thermoplastic polyurethane elastomer is composed of diisocyanate and chain extender:

[0021] Among them, the diisocyanate is one or more of TDI, MDI, HMDI, HDI, PPDI, IPDI, NDI, XDI and TODI, preferably one or more of TDI, MDI, HMDI, HDI and IPDI;

[0022] The chain extender is a small molecule diamine and / or a small molecule diol, wherein the small molecule diamine is preferably one or more of 3,3'-dichloro-4,4'-diaminodiphenyl methane, 3,5-diamino-p-chlorobenzoic acid isobutyl ester, diethyl toluene diamine and 3,5-dimethylthio toluene diamine, and the small molecule diol is preferably one or more of 1,4-butanediol, ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1,4-cyclohexanediol and neopentyl glycol;

[0023] The soft segment phase of the thermoplastic polyurethane elastomer is composed of a polyester polyol and / or a polyether polyol;

[0024] The number average molecular weight of the polyol is 500-4000, the polyester polyol is preferably one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol, and the polyether polyol is preferably one or more of polyoxypropylene polyol, polytetrahydrofuran polyol and copolyether polyol.

[0025] The preparation method of the composite material is to melt mix the raw materials, and the mixing temperature is 120-230 DEG C, preferably 150-210 DEG C.

[0026] The composite material can be applied to the field of smart wear such as bracelet and watch.

[0027] By adopting the technical scheme, the application has the following beneficial effects:

[0028] 1. The TPU composition preparation process is simple and easy to operate.

[0029] 2. The prepared TPU composition has good material compatibility and good mixing effect with the matrix.

[0030] 3. The prepared TPU composition has good stain resistance and can be used in the field of smart wear. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The material stain resistance test results of Comparative Example 1-2 and Example 1-6. DETAILED DESCRIPTION

[0032] The application will be further described through specific examples. In this application, parts and % are usually by weight, and the materials used in the examples are as follows:

[0033] TPU with hardness of 60A, WHT-1560, commercially available;

[0034] TPU with hardness of 80A, WHT-4075, commercially available;

[0035] TPU with hardness of 80A, WHT-1185, commercially available;

[0036] TPU with hardness of 90A, WHT-1190, commercially available;

[0037] TPU with hardness of 60D, WHT-8164, commercially available;

[0038] TPU with hardness of 80D, WHT-8280H, commercially available;

[0039] PBA (Mn: 1000), commercially available;

[0040] PCDL (Mn: 2000), commercially available;

[0041] PEBA (Mn: 3000), commercially available;

[0042] PCL (Mn: 1500), commercially available;

[0043] PTMEG (Mn: 2500), commercially available;

[0044] PEG (Mn: 1000), commercially available;

[0045] Silica, commercially available;

[0046] Mesoporous silica, commercially available;

[0047] Macroporous silica, commercially available;

[0048] Microporous carbon, commercially available;

[0049] Macroporous carbon, commercially available.

[0050] Composite material preparation method:

[0051] The polyol, porous material and TPU granules were melt-mixed, and then added to an extruder for melt extrusion, granulation, to obtain a composite material. The specific parameters are shown in Table 1.

[0052] Table 1.

[0053]

[0054]

[0055] Stain resistance of the material:

[0056] The surface of the material was marked with a marker (two rows of marks, the brand of the marker was Zebra); after standing at room temperature for 60 minutes, the lower row of marks on the surface of the material was wiped with non-woven fabric soaked with ethanol, it could be seen that the surface W of Comparative Examples 1 and 2 was difficult to wipe clean, the trace of W on the surface of Examples 1-6 became smaller, and even could be completely wiped clean.

Claims

1. A stain-resistant TPU composite material, prepared from the following raw materials: 100 parts by weight of a thermoplastic polyurethane elastomer; 1-10 parts by weight of a polyol, the number average molecular weight of the polyol being 500-4000, the polyol being selected from one or more of a polyester polyol, a polyether polyol, a silicon-containing polyol, and a fluorine-containing polyol; 3-20 parts by weight of a porous material, the porous material being at least one of porous silicon and porous carbon; The composite material is prepared by melt mixing the polyol, the porous material, and the thermoplastic polyurethane elastomer granules, then adding them to an extruder, melt extruding, and granulating to obtain the composite material.

2. The composite material of claim 1, wherein, The hardness of the thermoplastic polyurethane elastomer is 60A-80D.

3. The composite material of claim 1, wherein, The polyester polyol is selected from one or more of an alkyd polyester polyol, a polycaprolactone polyol, and a polycarbonate polyol, and the polyether polyol is selected from one or more of a polypropylene oxide polyol, a polytetrahydrofuran polyol, and a copolyether polyol.

4. The composite material of claim 1, wherein, The porous carbon is at least one of microporous carbon, mesoporous carbon, and macroporous carbon, and the porous silicon is at least one of microporous silicon, mesoporous silicon, and macroporous silicon. 5.Use of the composite material according to any one of claims 1-4 in the field of smart wear.

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