Low-glossiness halogen-free flame-retardant thermoplastic polyurethane elastomer composition and preparation method thereof

Abstract

The invention relates to a low-glossiness halogen-free flame-retardant thermoplastic polyurethane composition and a preparation method thereof. The low-glossiness halogen-free flame-retardant thermoplastic polyurethane composition comprises the following components in parts by mass: 100 parts of a thermoplastic polyurethane elastomer, 5-40 parts of a polyether polyamide block copolymer, 5-40 parts of a halogen-free flame retardant and 2-30 parts of phosphorus-containing epoxy resin. The low-glossiness halogen-free flame-retardant thermoplastic polyurethane elastomer composition provided by the invention has excellent flame retardance and low glossiness, and also has the characteristics of high strength, low temperature resistance and thermal aging resistance.

Description

Technical Field

[0001] The present invention relates to a flame-retardant thermoplastic polyurethane (TPU) elastomer composition, and particularly to a low-gloss halogen-free flame-retardant thermoplastic polyurethane (TPU) elastomer composition and a preparation method thereof, belonging to the field of polyurethane elastomers. Background Art

[0002] Thermoplastic polyurethane (TPU) has been widely used in the fields of wire and cable, pipe and profile, film and general injection-molded products due to its excellent tensile strength, tear strength, abrasion resistance and processing performance. However, due to the disadvantages of poor flame retardancy, low oxygen index and a large amount of dripping during combustion of thermoplastic polyurethane itself, its application in some fields with clear requirements for flame retardancy is limited.

[0003] Traditional halogen-based flame retardant additives such as bromine, chlorine and fluorine have been widely used in TPU compositions to provide flame retardancy. In recent years, with the increasingly strict environmental protection and safety requirements in most countries and industries, it is required that the flame-retardant TPU formulation design adopt other non-halogen flame retardant systems.

[0004] U.S. Patent US20090326108 discloses a flame-retardant polyurethane elastomer composition using one or more components selected from organophosphates, melamine derivatives and dipentaerythritol. The composition disclosed in this patent is halogen-free and environmentally friendly, and has high flame retardancy, but the mechanical properties of the composition are adversely affected.

[0005] Chinese Patent CN 108026328 B discloses a flame-retardant thermoplastic polyurethane made of at least one thermoplastic polyurethane, melamine cyanurate, a first phosphorus-containing flame retardant (F1) selected from at least one of alkyl esters of phosphoric acid and alkyl esters of phosphonic acid, and another phosphorus-containing flame retardant (F2) selected from derivatives of hypophosphorous acid. The combination disclosed in this patent has high flame retardancy, but the addition ratio of the powder flame retardant in the composition is relatively high, and the mechanical properties are still adversely affected.

[0006] In recent years, for applications such as wire and cable, pipe and profile, and film, matte products are increasingly favored by many consumers, giving people a simple, elegant and comfortable feeling. In certain specific occasions, due to aesthetic and technical reasons, there are strict matte requirements for the surface gloss of the products. And the thermoplastic polyurethane elastomer material itself has a shiny surface characteristic after extrusion, and it is very difficult to achieve matte. Therefore, in addition to flame retardancy, it is also necessary to perform matte modification on the thermoplastic polyurethane elastomer.

[0007] For many applications, it is also required that the material has excellent low-temperature resistance and heat aging resistance, which is meaningful for the material to meet long-term use outdoors or under other harsh conditions.

[0008] Chinese Patent CN102199343A discloses a method for achieving the purpose of matting by adding a certain amount of SEBS to TPU, and Chinese Patent CN103450662A discloses a method for achieving the purpose of matting by adding a certain amount of EPDM to TPU; due to the poor compatibility between the matting agent and TPU, its addition amount is relatively high, resulting in a decrease in the mechanical properties of the material, and generally a certain amount of compatibilizer needs to be added; at the same time, the processing performance of rubber powder or crosslinked structure elastomer is poor, the mixing uniformity is poor, the matting effect uniformity is poor, and there are problems such as rough surface and unmelted rubber particles; and the requirements of the use environment for flame retardant performance are not considered.

[0009] Chinese Patent CN107129674A discloses a method for achieving the purpose of matting by adding a blend of thermoplastic polyamide and thermoplastic polyester to TPU, but the blend of thermoplastic polyamide and polyester with strong crystallinity and high glass transition temperature will make the low-temperature flexibility of TPU poor, and the requirements of the material for flame retardant performance are not considered.

[0010] Therefore, it is of great significance to prepare a low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer, which has low gloss, good flame retardant performance, high strength, excellent low-temperature resistance and heat aging resistance at the same time. Summary of the Invention

[0011] To solve the above problems existing in the prior art, the purpose of the present invention is to provide a low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition and a preparation method thereof, and its raw materials include thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant and phosphorus-containing epoxy resin. This low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition not only has low gloss, good flame retardant performance and excellent mechanical properties, but also has excellent low-temperature resistance and heat aging resistance.

[0012] To achieve the above purpose, the technical solutions adopted by the present invention are as follows:

[0013] The present invention provides a low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition, which comprises the following components in parts by mass:

[0014] 100 parts of thermoplastic polyurethane elastomer;

[0015] 5-40 parts of polyether-polyamide block copolymer, for example, it can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts, etc., preferably 10-35 parts, more preferably 15-30 parts;

[0016] The halogen-free flame retardant is 5 to 40 parts, for example, it can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts, etc., preferably 10 to 35 parts, more preferably 15 to 30 parts;

[0017] The phosphorus-containing epoxy resin is 2 to 30 parts, for example, it can be 2 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, etc., preferably 3 to 25 parts, more preferably 5 to 20 parts.

[0018] In the low-gloss halogen-free thermoplastic polyurethane elastomer composition provided by the present invention, a thermoplastic polyurethane elastomer and a polyether-polyamide block copolymer are compounded, and a halogen-free flame retardant and a phosphorus-containing epoxy resin are added; the polyether-polyamide block copolymer has excellent low-temperature resistance, and its glass transition temperature is as low as below -70°C, and it has good compatibility with the thermoplastic polyurethane elastomer. The present invention also unexpectedly discovers that the introduction of the combination of the polyether-polyamide block copolymer, the halogen-free flame retardant and the phosphorus-containing epoxy resin can endow the composition with excellent low-gloss and low-temperature resistance effects. In addition, the combination of the halogen-free flame retardant and the phosphorus-containing epoxy resin unexpectedly plays a flame-retardant synergistic effect, effectively improving the flame-retardant effect of the composition; at the same time, it is found that the introduction of the phosphorus-containing epoxy resin can not only bring an increase in the flame-retardant effect, but also has an effect of chain extension and slight cross-linking on the thermoplastic polyurethane elastomer and the polyether-polyamide copolymer, making the composition have excellent strength and heat aging performance.

[0019] In some specific examples of the present invention, the polyether-polyamide block copolymer is a block copolymer composed of a polyether segment and a polyamide segment, wherein,

[0020] In the polyether segment, the polyether is selected from any one or a combination of at least two of polyethylene oxide ether, polypropylene oxide ether, polytetramethylene ether, tetrahydrofuran-propylene oxide copolymer ether, and tetrahydrofuran-ethylene oxide copolymer ether;

[0021] In the polyamide segment, the polyamide is selected from any one or a combination of at least two of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1111, and polyamide 1212.

[0022] In the present invention, there is no special requirement for the source of the polyether-polyamide block copolymer. A commercially available polyether-polyamide block copolymer can be used, or a polyether-polyamide block copolymer prepared by any method can be used. In some preferred embodiments of the present invention, the polyether in the polyether segment is prepared by reacting an initiator with an epoxide containing 2 to 6 (for example, 2, 3, 4, 5 or 6) carbon atoms;

[0023] Preferably, the initiator is selected from any one or a combination of at least two of water, small molecule polyols, small molecule polyphenols, small molecule polyamines, and small molecule alkanolamines, more preferably any one or a combination of at least two of water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine pentaerythritol, xylitol, triethylenediamine, sorbitol, ethylene glycol, bisphenol A, and toluenediamine, and further preferably any one or a combination of at least two of water, propylene glycol, and glycerol;

[0024] Preferably, the epoxide is selected from any one or a combination of at least two of ethylene oxide, propylene oxide, and tetrahydrofuran (THF).

[0025] In some specific examples of the present invention, in the polyether-polyamide block copolymer, the number average molecular weight (Mn) of the polyether segment is 500 to 10,000, for example, it can be 700, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 5000, 6000, 7000, 8000, or 9000, etc., and further preferably 700 to 4000.

[0026] In some specific examples of the present invention, the polyether-polyamide block copolymer has a Shore hardness of 20D to 80D, for example, it can be 20D, 25D, 30D, 35D, 40D, 45D, 50D, 55D, 60D, 65D, 70D, 75D, or 80D, etc., and is preferably Shore 25D to 65D.

[0027] In the research of the thermoplastic polyurethane elastomer composition of the present invention, it is found that when the polyether-polyamide block copolymer and the thermoplastic polyurethane elastomer are used synergistically, in the molecular chain of the polyether-polyamide block copolymer, due to the good flexibility of the polyether segment, it has good compatibility with the thermoplastic polyurethane elastomer. At the same time, because the polyamide segment has strong crystallinity, it phase-separates from the thermoplastic polyurethane elastomer to form uniformly distributed polyamide crystals. During the process of extruding or injection molding to prepare products, this uniformly dispersed polyamide crystallization will destroy the smooth structure on the surface of the polyurethane elastomer, obtaining a surface effect with low gloss. In addition, the polyether-polyamide elastomer has a low glass transition temperature. Introducing it into the thermoplastic polyurethane elastomer can effectively improve the low-temperature resistance of the thermoplastic polyurethane elastomer composition.

[0028] In some specific examples of the present invention, the thermoplastic polyurethane elastomer is selected from any one or a combination of at least two of polyester-based thermoplastic polyurethane elastomers and polyether-based thermoplastic polyurethane elastomers, and the polyester-based thermoplastic polyurethane elastomers further include polyol ester-based thermoplastic polyurethane elastomers, polycaprolactone thermoplastic polyurethane elastomers, and polycarbonate-based thermoplastic polyurethane elastomers.

[0029] In the present invention, there is no particular requirement for the source of the thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer can be prepared by any method or can be a commercially available thermoplastic polyurethane elastomer that meets the characteristics of the present invention. In some specific examples of the present invention, the thermoplastic polyurethane (TPU) elastomer is prepared by a polymerization reaction of a polyisocyanate, a polyol, and a chain extender.

[0030] Preferably, the polyisocyanate is selected from any one or a combination of at least two of aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates, more preferably any one or a combination of at least two of 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), hexamethylene diisocyanate (HDI), decane-1,10-diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI), and further preferably 4,4'-diphenylmethane diisocyanate and / or hexamethylene diisocyanate.

[0031] Preferably, the polyol is selected from any one or a combination of at least two of polyester polyols, polyether polyols, polylactone polyols, and polycarbonate polyols, more preferably polyether polyols;

[0032] Among them, the polyester polyol is prepared by an esterification or transesterification reaction of a diol with a dicarboxylic acid, a dicarboxylic acid anhydride, or a dicarboxylic acid ester;

[0033] Preferably, the number-average molecular weight (Mn) of the polyester polyol is 500 to 10,000, for example, it can be 600, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, or 9500, etc., further preferably 700 to 5000, and even more preferably 750 to 4000.

[0034] Preferably, the acid value of the polyester polyol is 0 to 1.0 mg KOH / g, for example, it can be 0.1 mg KOH / g, 0.2 mg KOH / g, 0.3 mg KOH / g, 0.4 mg KOH / g, 0.5 mg KOH / g, 0.6 mg KOH / g, 0.7 mg KOH / g, 0.8 mg KOH / g or 0.9 mg KOH / g, etc., and more preferably it is 0.1 to 0.5 mg KOH / g.

[0035] Among them, the polyether polyol is prepared by reacting an initiator with an epoxide containing 2 to 6 (for example, 2, 3, 4, 5 or 6) carbon atoms; preferably, the initiator is selected from any one or a combination of at least two of water, small molecule polyols, small molecule polyphenols, small molecule polyamines, and small molecule alkanolamines, and more preferably it is any one or a combination of at least two of water, propylene glycol, glycerol, trimethylolpropane, ethylene diamine pentaerythritol, xylitol, triethylenediamine, sorbitol, ethylene glycol, bisphenol A, and toluenediamine, and further preferably it is any one or a combination of at least two of water, propylene glycol or glycerol; preferably, the epoxide is selected from any one or a combination of at least two of ethylene oxide, propylene oxide, and tetrahydrofuran (THF).

[0036] Preferably, the polyether polyol is selected from any one or a combination of at least two of polyethylene oxide ether, polypropylene oxide ether, polytetramethylene ether glycol, tetrahydrofuran-propylene oxide copolymer ether, and tetrahydrofuran-ethylene oxide copolymer ether, and more preferably it is polytetramethylene ether glycol.

[0037] Preferably, the number average molecular weight (Mn) of the polyether polyol is 500 to 10,000, for example, it can be 700, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 5000, 6000, 7000, 8000 or 9000, etc., and more preferably it is 700 to 4000.

[0038] Among them, the polylactone polyol is polycaprolactone polyol, which is prepared by reacting ε-caprolactone monomer with an initiator under the initiation of a catalyst;

[0039] Preferably, the number average molecular weight (Mn) of the polycaprolactone polyol is 500 to 3000, for example, it can be 700, 900, 1000, 1200, 1500, 1800, 2000, 2200, 2500 or 2800, etc., and more preferably it is 1000 to 2000.

[0040] Among them, the polycarbonate polyol is prepared by the phosgene method, carbon dioxide regulated copolymerization method, cyclic carbonate ring-opening polymerization method, transesterification method, etc. that have been disclosed in the prior art, and there are no special requirements in the present invention;

[0041] Preferably, the number-average molecular weight (Mn) of the polycarbonate polyol is 500 to 4000, for example, it can be 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000 or 3500, etc., and more preferably 1000 to 3000.

[0042] Among them, the chain extender is selected from polyols having 2 to 10 (such as 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, and preferably any one or at least two combinations of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, hydroquinone bis(2-hydroxyethyl) ether, neopentyl glycol, glycerol monoallyl ether, trimethylolpropane monoallyl ether, glycerol monoacrylate;

[0043] Preferably, the dosage of the chain extender is 3 to 25% of the total mass of the polyisocyanate and the polyol, for example, it can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22% or 24%, etc., and preferably 5 to 20%.

[0044] In some specific examples of the present invention, the thermoplastic polyurethane elastomer has a Shore hardness of 50A to 80D, for example, it can be 55A, 60A, 65A, 70A, 75A, 80A, 85A, 90A, 95A, 60D, 65D, 70D or 75D, etc., and preferably 65A to 65D.

[0045] The preparation methods of the polyether / polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol, etc. described in the above content of the present invention are all conventional preparation processes in the field. The operation parameters such as raw materials, ratios, temperatures, and times that may be involved can be optimized by those skilled in the art based on the prior art, and the present invention does not make specific limitations.

[0046] In some specific examples of the present invention, the halogen-free flame retardant is selected from any one or at least two combinations of phosphorus-based flame retardants or nitrogen-based flame retardants, and preferably any one or at least two combinations of phosphate flame retardants, hypophosphite flame retardants, melamine and its salt flame retardants;

[0047] Preferably, the halogen-free flame retardant is one or at least two of triphenyl phosphate (TPP), cresyl diphenyl phosphate (CDP), tris(xylenyl) phosphate (TXP), tricresyl phosphate (TCP), bisphenol A-bis(diphenyl phosphate) (BDP), resorcinol bis(diphenyl phosphate) (RDP), triisopropylphenyl phosphate (IPPP), diphenyl isodecyl phosphate (DPDP), diphenyl isooctyl phosphate (DPOP), aluminum hypophosphite, aluminum diethylphosphinate, zinc diethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, melamine cyanurate, melamine phosphate, and melamine polyphosphate.

[0048] In some specific examples of the present invention, the phosphorus-containing epoxy resin is an epoxy resin containing phosphorus elements in the main chain or side chain of the molecular chain and having at least one epoxy group on the molecular chain;

[0049] The synthesis method of the phosphorus-containing epoxy resin is known in the prior art. Commercially available products can be used, or it can be prepared with reference to the methods disclosed in CN 102741314A, CN 103360579A, CN 112442165A, etc. There are no special requirements in the present invention;

[0050] Preferably, the epoxy equivalent of the phosphorus-containing epoxy resin is 50 - 1000 g / mol, for example, it can be 50 g / mol, 100 g / mol, 200 g / mol, 300 g / mol, 400 g / mol, 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, or 1000 g / mol, etc., preferably 100 - 750 g / mol, and more preferably 150 - 500 g / mol.

[0051] In some preferred examples of the present invention, the low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition further comprises an epoxy curing agent, a curing accelerator, etc.

[0052] Preferably, the epoxy curing agent is selected from one or more of amino compounds, polyphenolic compounds, and acid anhydride compounds; the dosage of the epoxy curing agent is 0.01 - 5% of the mass of the thermoplastic polyurethane elastomer, for example, it can be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, etc., preferably 0.1 - 3%.

[0053] Preferably, the curing accelerator is selected from one or more of imidazoles, triphenylphosphine and its derivatives, tertiary amines, and quaternary ammonium salts; the dosage of the curing accelerator is 0.001-0.5% of the mass of the thermoplastic polyurethane elastomer, for example, it can be 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%, etc., and preferably 0.005-0.2%.

[0054] There is no special requirement for the preparation method of the halogen-free flame-retardant thermoplastic polyurethane elastomer composition of the present invention. Those skilled in the art can refer to the prior art and combine and screen steps and parameters according to actual needs for preparation.

[0055] Exemplarily, the present invention also provides a preparation method of the halogen-free flame-retardant thermoplastic polyurethane elastomer composition described above, which can be prepared by the steps of the following method (1) or (2) or (3).

[0056] Method (1): After premixing the thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant, phosphorus-containing epoxy resin and the remaining components, they are put into a mixing and kneading device for kneading to obtain the product.

[0057] Method (2): The thermoplastic polyurethane elastomer and the polyether-polyamide block copolymer are first premixed and then put into a mixing and kneading device, and the remaining components are directly added to the mixing and kneading device, and finally obtained by kneading through the mixing and kneading device.

[0058] Method (3): The thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant, phosphorus-containing epoxy resin and the remaining components are respectively added to the mixing and kneading device, and finally obtained by kneading through the mixing and kneading device.

[0059] The specific operation of mixing and extruding in the mixing and kneading device is well-known to those skilled in the art according to the conventional technical means mastered, and will not be elaborated here. The extrusion temperature is, for example, between 150 and 250 °C, or between 150 and 225 °C, or between 150 and 200 °C, and equipment such as a twin-screw extruder can be used.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] 1. The present invention uses a compound of a thermoplastic polyurethane elastomer and a polyether-polyamide block copolymer, and adds a halogen-free flame retardant and a phosphorus-containing epoxy resin, which can make the composition have excellent low gloss and low temperature resistance effects.

[0062] 2. The combination of polyether polyamide block copolymer, halogen-free flame retardant and phosphorus-containing epoxy resin in the present invention also has a flame retardant synergistic effect, enabling the composition to have excellent flame retardant performance. Meanwhile, the introduction of phosphorus-containing epoxy resin not only brings an increase in flame retardant performance, but also can play a role in chain extension and micro-crosslinking of thermoplastic polyurethane elastomer and polyether polyamide block copolymer, endowing the composition with excellent strength and heat aging resistance.

[0063] The low gloss halogen-free flame retardant thermoplastic polyurethane elastomer composition product of the present invention has excellent flame retardant performance, can pass the UL94 1.5mm V-0 test, and has a limiting oxygen index as high as over 31. Meanwhile, it also has excellent low gloss effect and can pass the 136°C / 7-day heat aging test. Detailed Embodiments

[0064] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0065] The performance test parameters and corresponding test methods adopted in the embodiments of the present invention are as follows:

[0066] Hardness test is carried out according to ASTM D2240 standard;

[0067] Tensile strength and elongation at break tests are carried out according to ASTM D412 standard;

[0068] Tear strength test is carried out according to ASTM D624 standard;

[0069] Flame retardant performance test is carried out according to UL94 standard;

[0070] LOI test is carried out according to ASTM D2863 standard;

[0071] Surface glossiness is measured according to ASTM D2457 standard;

[0072] Low temperature resistance (low temperature catalytic temperature) is tested according to ASTM D746 standard;

[0073] Aging test (136°C): Place a 2mm thick dumbbell-shaped test piece in an aging oven at the specified temperature (136°C) for 168h, and then place it in a standard laboratory (23°C, 50% humidity) for 24h, and then test the retention rates of strength and elongation at break.

[0074] The following is the source information of the main raw materials used in the examples and comparative examples. All are commercial chemicals with industrial grade purity. For other raw materials and reagents, unless otherwise specified, they are obtained through commercial channels in the market:

[0075] Wanhua Chemical WHT-1560, polyester-based TPU, Shore hardness 60A;

[0076] Wanhua Chemical WHT-8185, polyether-based TPU, Shore hardness 85A;

[0077] Wanhua Chemical WHT-8264, polyether-based TPU, Shore hardness 64D;

[0078] Wanhua Chemical WHT-7190, polycarbonate-based TPU, hardness 90A;

[0079] Wanhua Chemical WHT-2585, polycaprolactone-based TPU, hardness 85A;

[0080] Wanhua Chemical WHE-4011, polyether-polyamide block copolymer, hardness 40D, polyether segment Mn = 1000 g / mol;

[0081] Wanhua Chemical WHE-2511, polyether-polyamide block copolymer, hardness 25D, polyether segment Mn = 2000 g / mol;

[0082] Wanhua Chemical WHE-7011, polyether-polyamide block copolymer, hardness 70D, polyether segment Mn = 650 g / mol;

[0083] Wansheng Co., Ltd. Resorcinol bis(diphenyl phosphate) (RDP);

[0084] Wansheng Co., Ltd. Bisphenol A-bis(diphenyl phosphate) (BDP);

[0085] Clariant OP935, aluminum diethyl phosphinate;

[0086] Bode BUDIT 3141, melamine cyanurate;

[0087] Qingdao Opure, ammonium polyphosphate melamine MPP;

[0088] Guangdong Guangshan YEP 340, phosphorus-containing epoxy resin, epoxy equivalent 320 g / mol;

[0089] Guangdong Guangshan YEP 301, phosphorus-containing epoxy resin, epoxy equivalent 250 g / mol;

[0090] Wanhua Chemical HMDA, 4'4-diaminodicyclohexylmethane, epoxy curing agent;

[0091] Suzhou Jinyuan, triphenylphosphine, epoxy curing accelerator;

[0092] BASF, PTMEG-2000, polyether polyol, number average molecular weight 2000 g / mol;

[0093] Wanhua Chemical WANAMID-L1000, polyamide 12;

[0094] Celanese Hytrel 3078, polyether-polyester block copolymer, hardness 25D.

[0095] Examples 1-16

[0096] Prepare the low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer compositions of Examples 1-16 according to the raw material formulations in Table 1:

[0097] In Table 1, the thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant, and phosphorus-containing epoxy resin are in parts by mass (parts), and the epoxy curing agent and curing accelerator are in mass percentages (wt%) based on the thermoplastic polyurethane elastomer.

[0098] The preparation process of the compositions of Examples 1-16 is as follows: Premix the thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant, phosphorus-containing epoxy resin, epoxy curing agent, and curing accelerator, and then enter a twin-screw extruder (Riya) for mixing and extrusion. The temperatures of each zone of the extruder are 175°C, 185°C, 195°C, 200°C, 205°C, 210°C, 215°C, 215°C, 210°C, 205°C, 200°C; after mixing and pelletizing by the twin-screw, dry the obtained pellets at 100°C for 6 h, and then injection mold them into test specimens for various performance tests. The results of various performances are listed in Table 2.

[0099] Raw material formulations of Examples 1-16 in Table 1

[0100]

[0101] Comparative Example 1

[0102] Refer to the method of Example 13, the difference is only that: WHE-2511 (polyether-polyamide block copolymer) is not added, and other operations and conditions remain unchanged. Prepare the composition, and the performance results are listed in Table 2.

[0103] Comparative Example 2

[0104] Refer to the method of Example 13, the difference is only that: WHE-2511 (polyether-polyamide block copolymer) is replaced with an equal amount of PTMEG-2000 (polyether), and other operations and conditions remain unchanged. Prepare the composition, and the performance results are listed in Table 2.

[0105] Comparative Example 3

[0106] Referring to the method of Example 13, the difference is only that: WHE-2511 (polyether-polyamide block copolymer) is replaced with an equal amount of WANAMID-L1000 (polyamide), and other operations and conditions remain unchanged. A composition is prepared, and the performance results are listed in Table 2.

[0107] Comparative Example 4

[0108] Referring to the method of Example 13, the difference is only that: WHE-2511 (polyether-polyamide block copolymer) is replaced with a mixture of an equal amount of PTMEG-2000 (polyether) and WANAMID L1000 (polyamide) (mixing mass ratio 3:1), and other operations and conditions remain unchanged. A composition is prepared, and the performance results are listed in Table 2.

[0109] Comparative Example 5

[0110] Referring to the method of Example 13, the difference is only that: WHE-2511 (polyether-polyamide block copolymer) is replaced with an equal amount of HYTREL 3078 (polyether-polyester block copolymer), and other operations and conditions remain unchanged. A composition is prepared, and the performance results are listed in Table 2.

[0111] Comparative Example 6

[0112] Referring to the method of Example 13, the difference is only that: MPP (halogen-free flame retardant) is not added, and other operations and conditions remain unchanged. A composition is prepared, and the performance results are listed in Table 2.

[0113] Comparative Example 7

[0114] Referring to the method of Example 13, the difference is only that: YEP 340 (phosphorus-containing epoxy resin) is not added, and other operations and conditions remain unchanged. A composition is prepared, and the performance results are listed in Table 2.

[0115] Table 2 Performance test results of the compositions prepared in the examples and comparative examples

[0116]

[0117]

[0118] The applicant declares that the present invention uses the above examples to illustrate the polyurethane elastomer composition of the present invention, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition, characterized in that, it comprises the following components in parts by mass: 100 parts of thermoplastic polyurethane elastomer; 5 - 40 parts of polyether-polyamide block copolymer, preferably 10 - 35 parts, more preferably 15 - 30 parts; 5 - 40 parts of halogen-free flame retardant, preferably 10 - 35 parts, more preferably 15 - 30 parts; 2 - 30 parts of phosphorus-containing epoxy resin, preferably 3 - 25 parts, more preferably 5 - 20 parts.

2. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that, the polyether-polyamide block copolymer is a block copolymer composed of a polyether segment and a polyamide segment, wherein, in the polyether segment, the polyether is selected from any one or a combination of at least two of polyethylene oxide ether, polypropylene oxide ether, polytetramethylene ether, tetrahydrofuran-propylene oxide copolymer ether, and tetrahydrofuran-ethylene oxide copolymer ether; in the polyamide segment, the polyamide is selected from any one or a combination of at least two of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1111, and polyamide 1212.

3. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1 or 2, characterized in that, in the polyether-polyamide block copolymer, the number-average molecular weight of the polyether segment is 500 - 10000, preferably 700 - 4000; and / or the polyether-polyamide block copolymer has a Shore hardness of 20D - 80D, preferably 25D - 65D.

4. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that, the thermoplastic polyurethane elastomer is selected from any one or a combination of at least two of polyester-based thermoplastic polyurethane elastomer and polyether-based thermoplastic polyurethane elastomer; preferably, the polyester-based thermoplastic polyurethane elastomer comprises any one or a combination of at least two of polyol acid ester-based thermoplastic polyurethane elastomer, polycaprolactone thermoplastic polyurethane elastomer, and polycarbonate-based thermoplastic polyurethane elastomer.

5. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1 or 4, characterized in that, the thermoplastic polyurethane elastomer has a Shore hardness of 50A - 80D, preferably 65A - 65D.

6. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that, the halogen-free flame retardant is selected from any one or a combination of at least two of phosphorus-based flame retardants or nitrogen-based flame retardants, preferably any one or a combination of at least two of phosphate ester flame retardants, hypophosphite flame retardants, and melamine and its salt flame retardants; Preferably, the halogen-free flame retardant is one or at least two of triphenyl phosphate, tolyldiphenyl phosphate, tris(xylenyl) phosphate, tricresyl phosphate, bisphenol A-bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), triisopropylphenyl phosphate, diphenylisodecyl phosphate, diphenylisodecyl phosphate, aluminum hypophosphite, aluminum diethylphosphinate, zinc diethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, melamine cyanurate, melamine phosphate, and melamine polyphosphate.

7. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, wherein, the phosphorus-containing epoxy resin is an epoxy resin containing phosphorus element in the main chain or side chain of the molecular chain and having at least one epoxy group on the molecular chain; Preferably, the epoxy equivalent of the phosphorus-containing epoxy resin is 50-1000 g / mol, preferably 100-750 g / mol, more preferably 150-500 g / mol.

8. The low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to any one of claims 1-7, wherein, the low-gloss halogen-free flame-retardant thermoplastic polyurethane elastomer composition further comprises an epoxy curing agent and a curing accelerator; Preferably, the epoxy curing agent is selected from one or more of amino compounds, polyphenolic compounds, and acid anhydride compounds; more preferably, the dosage of the epoxy curing agent is 0.01-5% of the mass of the thermoplastic polyurethane elastomer, preferably 0.1-3%. Preferably, the curing accelerator is selected from one or more of imidazoles, triphenylphosphine and its derivatives, tertiary amines, and quaternary ammonium salts; more preferably, the dosage of the curing accelerator is 0.001-0.5% of the mass of the thermoplastic polyurethane elastomer, preferably 0.005-0.2%.

9. The preparation method of the halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to any one of claims 1-8, wherein, the steps of the following method (1) or (2) or (3) can be adopted, Method (1): After premixing thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant, phosphorus-containing epoxy resin and other components, they are put into a mixing equipment for mixing to obtain the product; or Method (2): Thermoplastic polyurethane elastomer and polyether-polyamide block copolymer are premixed and then put into a mixing equipment, and other components are directly added to the mixing equipment, and finally the product is obtained by mixing in the mixing equipment; or Method (3): Thermoplastic polyurethane elastomer, polyether-polyamide block copolymer, halogen-free flame retardant, phosphorus-containing epoxy resin and other components are respectively added to the mixing equipment, and finally the product is obtained by mixing in the mixing equipment.

10. The preparation method according to claim 9, wherein, the extrusion temperature during the mixing process is 150-250 °C, preferably 150-225 °C, more preferably 150-200 °C.

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