Thermoplastic polyurethane elastomer, and preparation method, use and product thereof

Abstract

The present invention discloses a thermoplastic polyurethane elastomer (TPU), and a preparation method, use and product thereof. The thermoplastic polyurethane elastomer comprises the following components with respect to the total weight of TPU: 22-55 wt % of an aromatic diisocyanate and/or alicyclic diisocyanate; 2-16 wt % of a chain extender; and 30-70 wt % of a polyester polyol. The invention can reduce a TPU injection molding shrinkage to 0.2% or less, and can increase the thermal decomposition temperature to up to 300° C., and can obtain elastomeric materials of different hardnesses, thus having a broad prospect of application in 3D printing methods.

Claims

1. A thermoplastic polyurethane elastomer comprising the following components with respect to the total weight of the thermoplastic polyurethane elastomer: (A) 22 to 55 wt % of an aromatic diisocyanate and/or an alicyclic diisocyanate; (B) 2 to 16 wt % of a chain extender; and (C) 30 to 70 wt % of a polyester polyol; wherein the polyester polyol has a number average molecular weight of 800 to 4000 g/mol, and the chain extender has a molecular weight of 60 to 600 g/mol wherein the polyester polyol is a composition of an aliphatic polyester polyol and an aromatic polyester polyol with a mass ratio of 0.11:1 to 8.5:1, and the aromatic polyester polyol is one or two or more selected from the following structural formulas: ##STR00003## wherein R represents a branched alkylidene having 3 to 12 carbon atoms; and the structural formula of the aliphatic polyester polyol is: ##STR00004## wherein R.sub.1 and R.sub.2 are independently a linear alkylidene having 2 to 10 carbon atoms or a branched alkylidene having 3 to 10 carbon atoms.

2. The thermoplastic polyurethane elastomer according to claim 1, characterized in that, in the aliphatic polyester polyol, the linear alkylidene has 2 to 6 carbon atoms and side chains of the branched alkylidene have 3 to 5 carbon atoms; in the aromatic polyester polyol, the branched alkylidene has 3 to 6 carbon atoms.

3. The thermoplastic polyurethane elastomer according to claim 2, characterized in that, the molar ratio of the branched alkylidene to the linear alkylidene in the aliphatic polyester polyol is from 1:1 to 7:1.

4. The thermoplastic polyurethane elastomer according to claim 1, characterized in that the chain extender is one or two or more selected from aliphatic diols, aliphatic alcohol amines, alicyclic diamines, aromatic diols, aromatic alcohol amines and aromatic diamines.

5. The thermoplastic polyurethane elastomer according to claim 1, characterized in that the molar ratio of isocyanato to active hydrogen in the thermoplastic polyurethane elastomer is 0.8:1 to 1.3:1.

6. The thermoplastic polyurethane elastomer according to claim 5, characterized in that the molar ratio of isocyanato to active hydrogen in the thermoplastic polyurethane elastomer is 0.9:1 to 1.1:1.

7. The thermoplastic polyurethane elastomer according to claim 1, characterized in that the thermoplastic polyurethane elastomer has a shrinkage of 0.1% to 0.5% and a thermal decomposition temperature of 280 to 310° C.

8. The thermoplastic polyurethane elastomer according to claim 1, which comprises the following components with respect to the total weight of the thermoplastic polyurethane elastomer: (A) 25 to 50 wt % of an aromatic diisocyanate and/or an alicyclic diisocyanate; (B) 3 to 15 wt % of a chain extender; and (C) 35 to 60 wt % of a polyester polyol; wherein the polyester polyol has a number average molecular weight of 800 to 4000 g/mol, and the chain extender has a molecular weight of 60 to 600 g/mol.

9. The thermoplastic polyurethane elastomer according to claim 1, characterized in that the polyester polyol is a composition of an aliphatic polyester polyol and an aromatic polyester polyol with a mass ratio of 0.2:1 to 4:1.

10. The thermoplastic polyurethane elastomer according to claim 9, characterized in that, the molar ratio of the branched alkylidene to the linear alkylidene in the aliphatic polyester polyol is from 1:1 to 7:1.

11. A 3D printed article, wherein the printing material of the 3D printed article is the thermoplastic polyurethane elastomer according to claim 1.

12. A process for preparing the thermoplastic polyurethane elastomer according to claim 1, characterized in that 22 to 55 wt % of the diisocyanate, 30 to 70 wt % of the polyester polyol and 2 to 16 wt % of the chain extender are used as raw materials to carry out the polymerization reaction to obtain the thermoplastic polyurethane elastomer.

13. The process for preparing the thermoplastic polyurethane elastomer according to claim 12, characterized in that the process comprises the steps of: heating and melting the diisocyanate; adding the polyester polyol and optionally a catalyst to form a stable prepolymer at 70 to 100° C.; mixing the chain extender and the prepolymer evenly; and curing for 20-24 h at 80-120° C., to obtain a thermoplastic polyurethane elastomer; or the process comprises the steps of: adding the diisocyanate, the polyester polyol, the chain extender and optionally a catalyst into a mixing apparatus; carrying out the polymerization reaction directly, to obtain the thermoplastic polyurethane elastomer.

Description

EMBODIMENTS

(1) The method provided by the present invention is further described in details below. However, the present invention is not limited thereto by any means.

(2) The chemical reagents used in the following examples were of analytical grade;

(3) Characterization methods of the relevant parameters are shown in Table 1:

(4) TABLE-US-00001 TABLE 1 Test method Test Test instruments and test conditions Test standards Number average WATERS GPC 2000, Refer to instrument molecular weight DMF was used as the mobile phase manual Hardness Shore A hardness meter ASTM D2240-05 Initial decomposition A thermogravimetric analyzer of NETZSCH Group, Refer to instrument temperature Germany(NETZSCHTGA) manual Test Conditions: Heating rate: 10□/min Termination temperature: 700° C. Tensile Strength Universal material testing machine from Insrron, US GB/T 1040.2-2006 Test conditions for tensile strength and nominal strain at break: Elongation at break Stretching rate 50 mm/min, tensile spline according to GB/T 9341 -2008 the national standard Bending strength test conditions: Shrinkage Haitian SA900II/260 plastic injection molding ASTM D 955-08 standard machine, in the molding machine, the first zone temperature 180° C., the second zone temperature 185° C., the third zone temperature 190° C., the fourth zone temperature 195° C., the fifth zone temperature 190° C., injection pressure 50 bar, back pressure 3 bar

(5) The present invention is further described in details by the following specific embodiments. However, it should not be understood that the scope of the present invention is limited to the following examples. It should be understood that without departing from the idea of the above method of the present invention, various alternations and modifications made according to the ordinary technical knowledge and the common method in the art should be included in the scope of the present invention.

(6) The polyester polyols used in the examples were prepared as follows:

(7) Polyester 1: poly (ethylene glycol adipate) diol, with a number average molecular weight of 600 g/mol

(8) Adipic acid and ethylene glycol, together with tetraisopropyl titanate as a catalyst, were put into a polycondensation autoclave. The molar ratio of alcohol to acid in the raw material was 1.15. From the top of the autoclave was introduced nitrogen 0.1 MPa. The temperature of the reaction mixture in the autoclave was gradually increased to 130 to 140° C., and kept for 0.5 to 1.5 h. The temperature of the reaction product was then gradually increased to 220 to 230° C. for dehydrating the reaction product to a moisture content of 0.3% to 0.5%. The reaction product continued to be dehydrated and dealcoholized by vacuum distillation at 220 to 230° C. so as to control the hydroxyl value of the product to 189 mg KOH/g and obtain a product with a number average molecular weight of 600 g/mol. The product was cooled and withdrawn at room temperature.

(9) Polyester 1-2: poly (ethylene glycol adipate) diol, with a number average molecular weight of 2000 g/mol

(10) The synthesis method was the same as that of polyester 1, except that the hydroxyl value of the product was controlled to 56 mg KOH/g to obtain a product having a number average molecular weight of 2000 g/mol.

(11) Polyester 1-3: poly (ethylene glycol adipate) diol, with a number average molecular weight of 1000 g/mol

(12) The synthesis method was the same as that of polyester 1, except that the hydroxyl value of the product was controlled to 108 mg KOH/g to obtain a product having a number average molecular weight of 1000 g/mol.

(13) Polyester 1-4: poly (ethylene glycol adipate) diol, with a number average molecular weight of 3000 g/mol

(14) The synthesis method was the same as that of polyester 1, except that the hydroxyl value of the product was controlled to 38 mg KOH/g to obtain a product having a number average molecular weight of 3000 g/mol.

(15) Polyester 2: poly (neopentyl glycol phthalate) diol, with a number average molecular weight of 600 g/mol

(16) Phthalic acid and neopentyl glycol, together with tetraisopropyl titanate as a catalyst, were put into a polycondensation autoclave, while the other conditions were the same as those of the synthesis method of the polyester 1. The hydroxyl value of product was controlled to 189 mg KOH/g, to obtain a product having a number average molecular weight of 600 g/mol.

(17) Polyester 2-2: poly (neopentyl glycol phthalate) diol, with a number average molecular weight of 5000 g/mol

(18) The synthesis method was the same as that of polyester 2, except that the hydroxyl value of the product was controlled to 22.4 mg KOH/g to obtain a product having a number average molecular weight of 5000 g/mol.

(19) Polyester 2-3: poly (neopentyl glycol phthalate) diol, with a number average molecular weight of 3000 g/mol

(20) The synthesis method was the same as that of polyester 2, except that the hydroxyl value of the product was controlled to 38 mg KOH/g to obtain a product having a number average molecular weight of 3000 g/mol.

(21) Polyester 2-4: poly (neopentyl glycol phthalate) diol, with a number average molecular weight of 1000 g/mol

(22) The synthesis method was the same as that of polyester 2, except that the hydroxyl value of the product was controlled to 108 mg KOH/g to obtain a product having a number average molecular weight of 1000 g/mol.

(23) Polyester 3: poly (ethylene glycol 2-ethyl-3-propyl-succinate) diol(the molar ratio of branched alkylidene to linear alkylidene is 1:1), with a number average molecular weight of 2500 g/mol

(24) 2-ethyl-3-propyl-succinic acid and ethylene glycol, together with tetraisopropyl titanate as a catalyst, were put into a polycondensation autoclave, while the other conditions were the same as the synthesis method of polyester 1. A product having a number average molecular weight of 2500 g/mol was obtained by controlling the hydroxyl value of the product to 45 mg KOH/g.

(25) Polyester 4: poly ([2-ethyl-3-propyl-succinic acid] [2-ethyl-1,3-hexanediol] [ethylene glycol] ester) diol(the molar ratio of branched alkylidene to linear alkylidene is 3:1), with a number average molecular weight of 2500 g/mol

(26) 2-ethyl-3-propyl-succinic acid, 2-ethyl-1,3-hexanediol and ethylene glycol, together with tetraisopropyl titanate as a catalyst, were put into a polycondensation autoclave. The molar ratio of alcohol to acid in the raw material was 1.15, and the molar ratio of 2-ethyl-1,3-hexanediol and 2-ethyl-3-propyl-succinic acid with branched units to ethylene glycol with linear units was 3:1. From the top of the autoclave was introduced nitrogen 0.1 MPa. The temperature of the reaction mixture in the autoclave was gradually increased to 130 to 140° C., and kept for 0.5 to 1.5 h. The temperature of the reaction product was then gradually increased to 220 to 230° C., for dehydrating the product to a moisture content of 0.3% to 0.5%. The product continued to be dehydrated and dealcoholized by vacuum distillation at 220 to 230° C. so as to control the hydroxyl value of the product to 45 mg KOH/g and obtain a product having a number average molecular weight of 2500 g/mol. The product was cooled and with drawn at room temperature.

(27) Polyester 4-2: poly ([2-ethyl-3-propyl-succinic acid] [2-ethyl-1,3-hexanediol] [ethylene glycol] ester) diol(the molar ratio of branched alkylidene to linear alkylidene is 3:1), having a number average molecular weight of 600 g/mol

(28) The synthesis method was the same as that of polyester 4, except that the hydroxyl value of the product is controlled to 189 mg KOH/g to obtain a product with a number average molecular weight of 600 g/mol.

(29) Polyester 5: poly ([2-ethyl-3-propyl-succinic acid] [2-ethyl-1,3-hexanediol] [ethylene glycol] ester) diol (the molar ratio of branched alkylidene to linear alkylidene is 7:1), with a number average molecular weight of 1000 g/mol

(30) The molar ratio of 2-ethyl-1,3-hexanediol and 2-ethyl-3-propyl-succinic acid that provide branched alkylidene structural units to ethylene glycol that provides linear alkylidene structural units was 7:1, while the other conditions were the same as the synthesis method of polyester 4. The hydroxyl value of the product is controlled to 108 mg KOH/g to obtain a product having a number average molecular weight of 1000 g/mol.

(31) Polyester 6: poly (2-ethyl-1,3-hexanediol terephthalate) diol, with a number average molecular weight 5000 g/mol

(32) Terephthalic acid and 2-ethyl-1,3-hexanediol, together with tetraisopropyl titanate as a catalyst, were put into a polycondensation autoclave, while the other conditions were the same as the synthesis method of polyester 1. The hydroxyl value of the product was controlled to 22.4 mg KOH/g to obtain a product having a number average molecular weight of 5000 g/mol.

(33) Polyester 6-2: poly (2-ethyl-1,3-hexanediol terephthalate) diol, with a number average molecular weight of 1000 g/mol;

(34) The synthesis method was the same as that of polyester 6, except that the hydroxyl value of the product was controlled to 108 mg KOH/g to obtain a product having a number average molecular weight of 1000 g/mol.

(35) Polyester 6-3: poly (2-ethyl-1,3-hexanediol terephthalate) diol, with a number average molecular weight of 600 g/mol;

(36) The synthesis method was the same as that of polyester 6, except that a product having a number average molecular weight of 600 g/mol was obtained by controlling the hydroxyl value of the product to 189 mg KOH/g.

(37) Polyester 7: poly (neopentyl glycol isophthalate)diol, with a number average molecular weight of 2000 g/mol.

(38) Isophthalic acid and neopentyl glycol, together with tetraisopropyl titanate as a catalyst, were put into a polycondensation autoclave, while the other conditions were the same as the synthesis method of polyester 1. The hydroxyl value of the product was controlled to 56 mg KOH/g to obtain a product having a number average molecular weight of 2000 g/mol.

(39) Polyester 7-2: poly (neopentyl glycol isophthalate) diol, with a number average molecular weight of 2500 g/mol

(40) The synthesis method was the same as that of polyester 7, except that the hydroxyl value of the product was controlled to 45 mg KOH/g to obtain a product having a number average molecular weight of 2500 g/mol.

(41) Polyester 7-3: poly (neopentyl glycol isophthalate) diol, with a number average molecular weight of 1000 g/mol

(42) The synthesis method was the same as that of polyester 7, except that the hydroxyl value of the product was controlled to 108 mg KOH/g to obtain a product having a number average molecular weight of 1000 g/mol.

Example 1

(43) a) 304.0 g polyester 1 and 35.9 g polyester 2 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(44) b) 547.4 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 60° C. Then 0.08 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 14.4 wt %;

(45) c) 112.6 g 1,3-propanediol was added into the prepolymer obtained in step b), and well mixed. After about 1 mM, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 1 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 2

(46) a) 527.3 g polyester 1-2 and 122.6 g polyester 7 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(47) b) 237.0 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 80° C. Then 0.03 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 5.5 wt %;

(48) c) 112.9 g hydroquinone dihydroxyethyl ether was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 2 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 3

(49) a) 480 g polyester 4 and 120 g polyester 7-2 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(50) b) 282.0 g diphenylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.1 g bismuth isooctanoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 8.45 wt %;

(51) c) 133.0 g 1,4-cyclohexanediamine was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 3 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 4

(52) a) 331.6 g polyester 2-2 and 118.4 g polyester 6 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(53) b) 428.9 g diphenylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.01 g bismuth isooctanoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 15.5 wt %;

(54) c) 121.04 g 1,3-propanediol was added into the prepolymer obtained in step b), and well mixed. After about 1 mM, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 4 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 5

(55) a) 700 g polyester 6-2 was dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(56) b) 266.3 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.04 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 2.7 wt %;

(57) c) 33.7 g 1,4-cyclohexanediamine was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 5 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 6

(58) a) 443.7 g polyester 2-3 and 66.5 g polyester 1-4 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(59) b) 300.0 g diphenylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.06 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 10.7 wt %;

(60) c) 151.4 g hydroquinone dihydroxyethyl ether was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 6 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 7

(61) a) 100 g polyester 3 and 500 g polyester 7-2 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(62) b) 295.0 g diphenylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.09 g bismuth isooctanoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 8.8 wt %;

(63) c) 133.0 g 1,4-cyclohexanediamine was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 7 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 8

(64) a) 204.0 g polyester 6-3 and 136.0 g polyester 4-2 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(65) b) 547.4 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 60° C. Then 0.08 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 14.4 wt %;

(66) c) 112.6 g 1,3-propanediol was added into the prepolymer obtained in step b), and well mixed. After about 1 mM, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 8 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 9

(67) a) 226.7 g polyester 2-4 and 453.3 g polyester 5 were dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(68) b) 261.3 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.02 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 2.8 wt %;

(69) c) 58.7 g 4′4-diaminodiphenylmethane was added into the prepolymer obtained in step b), and well mixed. After about 1 mM, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 9 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 10

(70) a) 500 g polyester 5 was dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(71) b) 390.4 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.03 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 9.3 wt %;

(72) c) 109.5 g 1,4-cyclohexanediamine was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 10 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 11

(73) a) 700 g polyester 7-3 was dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(74) b) 268.3 g 4,4′-dicyclohexylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.06 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 2.8 wt %;

(75) c) 31.6 g 1,4-butanediol as a chain extender was added into the prepolymer obtained in step b), and well mixed. After about 1 min, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 11 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Example 12

(76) a) 550 g polyester 1-3 was dehydrated for 2 h at a temperature of 100 to 105° C. and a relative vacuum of −0.098 to −0.01 MPa;

(77) b) 369.2 g diphenylmethane diisocyanate was added into a reactor, and heated to 70° C. Then 0.09 g stannous octoate and the product of step a) were added. The reaction was carried out at a temperature of 70 to 80° C., obtaining a storage-stable prepolymer with an NCO content of 8.45 wt %;

(78) c) 80.8 g 1,4-butanediol as a chain extender was added into the prepolymer obtained in step b), and well mixed. After about 1 mM, the mixture was poured into a mold, and then cured for 24 h in an oven at 120° C. The product was cooled and pulverized to obtain 12 # thermoplastic polyurethane elastomer, with the main performances shown in Table 2.

Comparative Example 1

(79) 13 # Polyether TPU product is Wanthane® WHT-8285 (Wanhua Chemical Group Co., Ltd.). The raw materials for synthesis were diphenylmethane diisocyanate and polytetramethylene ether glycol, using 1,4-butanediol as a chain extender. Related parameters are shown in Table 2.

Comparative Example 2

(80) 14 # Polyether TPU product is Wanthane® WHT-8254 (Wanhua Chemical Group Co., Ltd.). The raw materials for synthesis were diphenylmethane diisocyanate and polytetramethylene ether glycol, using 1,4-butanediol as a chain extender. Related parameters are shown in Table 2.

(81) TABLE-US-00002 TABLE 2 Main performances Hard- Initial ness/ Tensile Elongation Shrink- decomposition No. Shore A Strength/MPa at break/% age/% temperature/° C. 1# 60 20.6 169 0.32 283 2# 95 37.3 231 0.51 293 3# 93 37.0 487 0.27 301 4# 80 42.9 564 0.24 310 5# 97 42.9 470 0.23 307 6# 85 45.7 751 0.28 314 7# 93 39.3 460 0.22 310 8# 55 22.3 210 0.20 307 9# 95 35.0 443 0.17 304 10#  90 37.3 381 0.34 304 11#  98 45.7 347 0.45 289 12#  90 32.9 441 0.56 291 13#  85 23 500 0.68 301 14#  96 29 350 0.63 305

Example 13

(82) Pellets of the above #5 thermoplastic polyurethane elastomer were added to a screw extruder. A TPU line was extruded by a screw, and sufficiently cooled to form a wire material. The wire material was rolled up in a towing machine, wherein the size and diameter of the wire material was fixed by a pulling force and the wire material was wound into a reel automatically, obtaining a finished product. The above product was used as a 3D printing material, and the 3D printing was conducted on a Replicator II 3D printer of MakerBot with a printing speed of 40 to 45 mm/s. The printed products obtained show no significant deformation, and the model bases of the printed products have no tilt.