CN117430786B - High-strength TPU material for charging pile cable and preparation method thereof - Google Patents

High-strength TPU material for charging pile cable and preparation method thereof Download PDF

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Publication number
CN117430786B
CN117430786B CN202311777673.3A CN202311777673A CN117430786B CN 117430786 B CN117430786 B CN 117430786B CN 202311777673 A CN202311777673 A CN 202311777673A CN 117430786 B CN117430786 B CN 117430786B
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charging pile
tpu material
pile cable
double
flame retardant
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CN117430786A (en
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管永
马超
董良
宋小娜
罗杰
鞠伟坦
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Shandong Inov Polyurethane Co Ltd
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Shandong Inov Polyurethane Co Ltd
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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Abstract

The invention relates to the technical field of polyurethane, in particular to a high-strength TPU material for a charging pile cable and a preparation method thereof. The raw materials of the high-strength TPU material for the charging pile cable comprise: mixing polyol, isocyanate, a composite chain extender, an antioxidant, a hydrolysis inhibitor, a catalyst, a dispersing agent, a synergistic flame retardant and an ultraviolet absorber; the mixed polyol is at least one of polycaprolactone diol and polytetramethylene ether glycol and is mixed with terminal-hydroxybutyl-terminated polydimethylsiloxane; the compound chain extender is prepared by compounding 1, 4-butanediol and trimethylolpropane; the synergistic flame retardant is silane coupling agent modified nano Sb 2O3 powder. The invention solves the problem of poor compatibility between the flame retardant and the matrix, and improves the flame retardant effect, heat resistance and mechanical property of the TPU material.

Description

High-strength TPU material for charging pile cable and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to a high-strength TPU material for a charging pile cable and a preparation method thereof.
Background
Compared with the traditional cable material, the charging pile cable is an important supporting facility of a new energy automobile, and has higher requirements on the use environment and safety, so that higher requirements are also put forward on the coating material of the charging pile cable.
At present, two main materials are used for coating the charging pile cable: one is an elastomeric material based on polyvinyl chloride (PVC), such as: the PVC elastomer material for the electric automobile charging pile disclosed in the patent CN104194220A has better performance, can basically meet the use requirement of a charging pile cable and has lower price; however, the PVC elastomer has large smoke generation amount during combustion, does not accord with the trend of environmental protection, and greatly limits the use of PVC-based elastomer materials.
The other is an elastic material which takes thermoplastic polyurethane elastomer (TPU) as a base material, and the material is easy to process, has wide hardness range and excellent performance, and meets the requirement of environmental protection; however, TPU itself belongs to inflammable materials, and in order to achieve a sufficient flame retardant effect, a large amount of halogen-free flame retardant is required to be added, which can inhibit combustion or slow down flame propagation speed, but the addition of a large amount can have great influence on mechanical properties of the materials, and compatibility between filler and polymer is generally poor, and liquid flame retardant is easy to separate out. In addition, the heat resistance and mechanical properties of the TPU material also need to be further improved.
Disclosure of Invention
The invention aims to provide a high-strength TPU material for a charging pile cable, which is characterized in that flame retardant groups are grafted onto polyurethane molecular chains through reaction, so that the problem of poor compatibility between a flame retardant and a matrix is fundamentally solved, the flame retardant effect of the TPU material is improved, and the heat resistance and mechanical property of the TPU material are improved through the addition of end-hydroxybutyl-terminated polydimethylsiloxane, the crosslinking reaction and a two-section screw connection extrusion process; the invention also provides a preparation method of the composite.
The high-strength TPU material for the charging pile cable comprises the following raw materials in parts by mass:
50-70 parts of mixed polyol,
25-40 Parts of isocyanate and the like,
5-10 Parts of composite chain extender,
0.1 To 0.3 part of antioxidant,
0.05 To 0.2 part of hydrolysis resistant agent,
0.02-0.1 Part of catalyst,
0.01 To 0.03 part of dispersing agent,
0.005-0.01 Part of synergistic flame retardant,
0.05-0.3 Part of ultraviolet absorber;
The mixed polyol is at least one of polycaprolactone diol (PCL) and polytetramethylene ether glycol (PTMG) and is mixed with terminal hydroxybutyl-terminated Polydimethylsiloxane (PDMS);
the compound chain extender is a compound of 85-99wt.% 1, 4-Butanediol (BDO) and 1-15wt.% Trimethylolpropane (TMP);
The isocyanate is a mixture of 90-95wt.% diphenylmethane diisocyanate (MDI) and 5-10wt.% dicyclohexylmethane diisocyanate (HMDI);
The synergistic flame retardant is silane coupling agent modified nano Sb 2O3 powder.
Preferably, the number average molecular weight of the polycaprolactone diol and the polytetramethylene ether glycol is 500 to 2000.
Preferably, the number average molecular weight of the end-hydroxybutyl-terminated polydimethylsiloxane is 1500-2000, and the structural formula is as follows:
。
Preferably, in the mixed polyol, the mass percentage of the end-hydroxybutyl-terminated polydimethylsiloxane is 5-15%.
Preferably, in the silane coupling agent modified nano Sb 2O3 powder, the average particle size of the nano Sb 2O3 powder is between 30 and 50 nm.
The purpose of the silane coupling agent modification is to improve the dispersibility and compatibility of the nano Sb 2O3 powder. The silane coupling agent can be commercially available silane coupling agents, such as silane coupling agent KH-550, silane coupling agent KH-560 and the like, and the modification of the types has no obvious influence on the modification effect; the usage amount of the silane coupling agent is 0.05-0.2% of the mass of the nano Sb 2O3 powder, and the better modification effect can be achieved within the usage amount range.
In one embodiment, the preparation method of the silane coupling agent modified nano Sb 2O3 powder comprises the following steps:
The nanometer Sb 2O3 powder with the average particle size of 30-50nm, the silane coupling agent KH-550 and absolute ethyl alcohol are placed in a ball milling tank together according to the mass ratio of 1:0.05:2, ball milling is carried out for 10 hours under the condition of rotating speed of 500r/min, and then vacuum drying is carried out, so that the silane coupling agent modified nanometer Sb 2O3 powder is obtained.
Preferably, the antioxidant is phosphite antioxidant; further preferred is tris (2, 4-di-tert-butylphenyl) phosphite.
Preferably, the hydrolysis resistance agent is carbodiimide.
Preferably, the catalyst is an organotin catalyst; stannous octoate is further preferred.
Preferably, the dispersing agent is at least one of glyceryl monostearate, glyceryl tristearate, barium stearate and calcium stearate; further preferred is a mixture of glyceryl monostearate and glyceryl tristearate in a mass ratio of 1:1.5.
Preferably, the ultraviolet absorber is at least one of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylamidine (UV-1), N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine (UV-2), phenyl O-hydroxybenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (UV-P), 2, 4-dihydroxybenzophenone (UV-O), 2-hydroxy-4-methoxybenzophenone (UV-9), 2-hydroxy-4-N-octoxybenzophenone (UV-531); further preferred is N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylamidine (UV-1).
The preparation method of the high-strength TPU material for the charging pile cable comprises the following steps:
Adopting a two-section double-screw extruder connected with a middle double-shaft double-screw and a long double-shaft double-screw to carry out continuous polymerization reaction, firstly adding an antioxidant, a hydrolysis-resistant agent, a dispersing agent, a synergistic flame retardant and an ultraviolet absorbent into mixed polyol, and carrying out prepolymerization reaction with partial isocyanate and a catalyst in the middle double-shaft double-screw to obtain a prepolymer; and then conveying the prepolymer into a long double-shaft double-screw rod, carrying out polymerization reaction with the residual isocyanate and the composite chain extender, and carrying out underwater cutting granulation to obtain the high-strength TPU material for the charging pile cable.
Preferably, the medium double-shaft double-screw is divided into four temperature zones, and the temperatures from the first zone to the fourth zone are 180 ℃, 185 ℃ and 190 ℃ in sequence; the rotating speed of the host machine is 180r/min.
Preferably, the long biaxial twin screw is divided into fourteen temperature zones, and the temperatures from the first zone to the fourteenth zone are 190 ℃, 195 ℃, 200 ℃, 205 ℃, 200 ℃, 195 ℃, 185 ℃, 180 ℃, 165, 180 ℃, 190 ℃ in sequence; the die outlet temperature was 215 ℃; the rotation speed of the host machine is 210r/min.
In one embodiment, the preparation method of the high-strength TPU material for the charging pile cable specifically comprises the following steps:
(1) Adding an antioxidant, a hydrolysis inhibitor, a dispersing agent, a synergistic flame retardant and an ultraviolet absorbent into mixed polyol, mixing by a stirring head, pouring the mixture into a first area of a middle double-shaft double-screw rod by a mixer, continuously pouring and pouring a catalyst into the mixer of the middle double-shaft double-screw rod by another piece of equipment, pouring 1/2 amount of isocyanate into the first area of the middle double-shaft double-screw rod, and carrying out prepolymerization reaction in the middle double-shaft double-screw rod to obtain a prepolymer; the temperature of the middle double-shaft double-screw is 180 ℃, 185 ℃ and 190 ℃ from the first zone to the fourth zone in sequence, and the rotating speed of the main machine is 180r/min;
(2) The prepolymer is conveyed to a first area of a long double-shaft double-screw main machine barrel through a medium double-shaft double-screw, a chain extender is poured into the first area of the long double-shaft double-screw main machine barrel, the rest 1/2 amount of isocyanate is poured into a second area of the long double-shaft double-screw main machine barrel, polymerization reaction is carried out in the long double-shaft double-screw, and the high-strength TPU material for the charging pile cable is obtained through underwater cutting, granulating and drying; the temperature of each zone is controlled by heating, and the temperatures from the first zone to the fourteenth zone are 190 ℃, 195 ℃, 200 ℃, 205 ℃, 200 ℃, 195 ℃, 185 ℃, 180 ℃, 165 ℃, 180 ℃, 190 ℃, the die outlet temperature is 215 ℃ and the host rotating speed is 210r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts at least one of polycaprolactone diol and polytetramethylene ether glycol and terminal hydroxybutyl-terminated polydimethylsiloxane to be mixed as a soft segment to synthesize silicon-containing block TPU, so as to promote microphase separation of polyurethane and improve the water resistance and mechanical property of polyurethane materials;
(2) According to the invention, the silane coupling agent modified nano Sb 2O3 powder is added to serve as a synergistic flame retardant, so that the flame retardance of the polyurethane material is effectively improved, and the silane coupling agent modified nano Sb 2O3 powder and polyurethane can be grafted to a polyurethane molecular chain through reaction, so that the problem of poor compatibility between the flame retardant and a matrix is fundamentally solved, and meanwhile, the heat resistance and flame retardant effect of the polyurethane material are improved;
(3) According to the invention, the small molecular diol and the trimethylolpropane are mixed to serve as a chain extender, and the mechanical properties of the polyurethane material are further improved through a crosslinking reaction;
(4) The invention adopts a small amount of HMDI and MDI to mix, and can improve the transparency and yellowing resistance of the TPU material on the basis of ensuring the mechanical property of the TPU material;
(5) The invention adopts the production process of connecting the medium double-shaft double screw and the long double-shaft double screw, carries through the prepolymerization reaction of the medium double-shaft double screw, carries through the mixing polymerization reaction of the long double-shaft double screw, and carries out continuous production, thereby greatly improving the stability and the processing performance of the material, having high production efficiency, safety and environmental protection, and simultaneously, the two-section screw extrusion process ensures that the molecular chain segments of polyurethane are distributed more uniformly, the molecular chain of the obtained polyurethane is longer, and the mechanical property of the material is improved.
Detailed Description
The invention is further illustrated below with reference to examples.
The raw materials used in the examples, unless otherwise specified, were all commercially available conventional raw materials; the process used in the examples, unless otherwise specified, is conventional in the art.
The preparation method of the silane coupling agent modified nano Sb 2O3 powder adopted in the embodiment is as follows:
The nanometer Sb 2O3 powder with the average particle size of 30-50nm, the silane coupling agent KH-550 and absolute ethyl alcohol are placed in a ball milling tank together according to the mass ratio of 1:0.05:2, ball milling is carried out for 10 hours under the condition of rotating speed of 500r/min, and then vacuum drying is carried out, so that the silane coupling agent modified nanometer Sb 2O3 powder is obtained.
PTMG-1500 and PTMG-2000 adopted in the examples have number average molecular weights of 1500 and 2000 in sequence and are manufactured by phosphor chemical industry (Jiaxing) Co., ltd;
The PCL-1500 and PCL-500 adopted in the examples have number average molecular weights of 1500 and 500 in sequence and are produced by Hunan kernel new material Co., ltd;
The PDMS used in the examples has a number average molecular weight of 1500-2000 and the structural formula is as follows:
。
Example 1
The high-strength TPU material for the charging pile cable comprises the following raw materials in parts by mass:
60 parts of polyol (PTMG-1500 and PDMS in a mass ratio of 90:10) are mixed,
30 Parts of isocyanate (mass ratio of 95:5 MDI and HMDI),
10 Parts of composite chain extender (BDO and TMP with the mass ratio of 96:4),
0.2 Part of antioxidant (tri (2, 4-di-tert-butylphenyl) phosphite),
0.15 Part of hydrolysis resistance agent (carbodiimide),
0.07 Part of catalyst (stannous octoate),
0.02 Part of dispersing agent (glyceryl monostearate and glyceryl tristearate with the mass ratio of 1:1.5),
0.01 Part of synergistic flame retardant (silane coupling agent modified nano Sb 2O3 powder),
0.15 Part of ultraviolet absorber (UV-1).
The preparation method comprises the following steps:
(1) Adding an antioxidant, a hydrolysis inhibitor, a dispersing agent, a synergistic flame retardant and an ultraviolet absorbent into mixed polyol, mixing by a stirring head, pouring the mixture into a first area of a middle double-shaft double-screw rod by a mixer, continuously pouring and pouring a catalyst into the mixer of the middle double-shaft double-screw rod by another piece of equipment, pouring 1/2 amount of isocyanate into the first area of the middle double-shaft double-screw rod, and carrying out prepolymerization reaction in the middle double-shaft double-screw rod to obtain a prepolymer; the temperature of the middle double-shaft double-screw is 180 ℃, 185 ℃ and 190 ℃ from the first zone to the fourth zone in sequence, and the rotating speed of the main machine is 180r/min;
(2) The prepolymer is conveyed to a first area of a long double-shaft double-screw main machine barrel through a medium double-shaft double-screw, the composite chain extender is poured into the first area of the long double-shaft double-screw main machine barrel, the rest 1/2 amount of isocyanate is poured into a second area of the long double-shaft double-screw main machine barrel, polymerization reaction is carried out in the long double-shaft double-screw, and the high-strength TPU material for the charging pile cable is obtained through underwater cutting granulation and drying; the temperature of each zone is controlled by heating, and the temperatures from the first zone to the fourteenth zone are 190 ℃, 195 ℃, 200 ℃, 205 ℃, 200 ℃, 195 ℃, 185 ℃, 180 ℃, 165 ℃, 180 ℃, 190 ℃, the die outlet temperature is 215 ℃ and the host rotating speed is 210r/min.
Example 2
This example differs from example 1 only in that the mass ratio of PTMG-1500 to PDMS in the mixed polyol is 95:5.
Example 3
This example differs from example 1 only in that the mass ratio of PTMG-1500 to PDMS in the mixed polyol is 85:15.
Example 4
The high-strength TPU material for the charging pile cable comprises the following raw materials in parts by mass:
70 parts of mixed polyol (PCL-500, PTMG-2000 and PDMS with the mass ratio of 45:45:10),
25 Parts of isocyanate (mass ratio 92:8 MDI and HMDI),
5 Parts of composite chain extender (BDO and TMP with the mass ratio of 90:10),
0.3 Part of antioxidant (tri (2, 4-di-tert-butylphenyl) phosphite),
0.1 Part of hydrolysis resistance agent (carbodiimide),
0.05 Part of catalyst (stannous octoate),
0.03 Part of dispersing agent (glyceryl tristearate),
0.005 Part of synergistic flame retardant (silane coupling agent modified nano Sb 2O3 powder),
0.1 Part of ultraviolet absorber (UV-P).
The preparation method is the same as in example 1.
Example 5
The high-strength TPU material for the charging pile cable comprises the following raw materials in parts by mass:
65 parts of mixed polyol (PCL-1500 and PDMS in a mass ratio of 90:10),
28 Parts of isocyanate (mass ratio of 95:5 MDI and HMDI),
7 Parts of composite chain extender (BDO and TMP with the mass ratio of 99:1),
0.2 Part of antioxidant (tri (2, 4-di-tert-butylphenyl) phosphite),
0.2 Part of hydrolysis resistance agent (carbodiimide),
0.1 Part of catalyst (stannous octoate),
0.01 Part of dispersing agent (magnesium stearate),
0.01 Part of synergistic flame retardant (silane coupling agent modified nano Sb 2O3 powder),
0.3 Parts of ultraviolet absorber (UV-O).
The preparation method is the same as in example 1.
Example 6
The high-strength TPU material for the charging pile cable comprises the following raw materials in parts by mass:
50 parts of a polyol (PCL-1500 and PDMS in a mass ratio of 90:10) are mixed,
40 Parts of isocyanate (MDI and HMDI in a mass ratio of 90:10),
10 Parts of composite chain extender (BDO and TMP with the mass ratio of 85:15),
0.1 Part of antioxidant (tri (2, 4-di-tert-butylphenyl) phosphite),
0.05 Part of hydrolysis resistance agent (carbodiimide),
0.02 Part of catalyst (stannous octoate),
0.03 Part of dispersing agent (stearic acid monoglyceride),
0.01 Part of synergistic flame retardant (silane coupling agent modified nano Sb 2O3 powder),
0.05 Part of ultraviolet absorber (UV-2).
The preparation method is the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that the mixed polyol was replaced with equal parts by weight of PTMG-1500.
Comparative example 2
The present comparative example differs from example 1 only in that a synergistic flame retardant (silane coupling agent modified nano Sb 2O3 powder) was not added.
Comparative example 3
The only difference between this comparative example and example 1 is that the mass ratio of BDO and TMP in the complex chain extender is 80:20.
Comparative example 4
This comparative example differs from example 1 only in that the composite chain extender is replaced with equal parts by mass of BDO.
Comparative example 5
This comparative example differs from example 1 only in that the isocyanate used MDI and HMDI in a mass ratio of 80:20.
Comparative example 6
The comparative example uses the same raw material composition as example 1, except that the preparation method only uses a long biaxial twin screw, specifically as follows:
Adding an antioxidant, a hydrolysis inhibitor, a dispersing agent, a synergistic flame retardant and an ultraviolet absorbent into mixed polyol, mixing the mixed polyol by a stirring head, pouring the mixed polyol into a first area of a long double-shaft double-screw main machine barrel by a mixer, pouring a composite chain extender into the first area of the long double-shaft double-screw main machine barrel, continuously pouring a catalyst into the mixer of the long double-shaft double-screw by another device, pouring isocyanate into the first area of the long double-shaft double-screw main machine barrel, performing polymerization reaction in the long double-shaft double-screw, and performing underwater cutting granulation and drying to obtain the high-strength TPU material for the charging pile cable.
The TPU materials prepared in the examples and comparative examples were subjected to performance tests in which:
tensile strength, elongation at break, 100% tensile stress were tested with reference to standard ASTM-D412;
tear strength is tested against standard ASTM-D624;
the light transmittance testing method comprises the following steps: injecting TPU material into a test piece with the thickness of 2mm, and testing the light transmittance of the test piece by adopting a color spectrum spectrocolorimeter CS-820;
the flame retardant level is tested according to the UL94 vertical burning test method, and the flame retardant level is V-0, V-1 and V-2 from high to low in sequence;
The conditions for testing the precipitation condition are as follows: placing the sample at 60 ℃ for 120 hours, taking out, standing for 3 hours at room temperature, observing and recording the precipitation condition of the surface of the sample, and dividing the sample into three grades of no precipitation, slight precipitation and obvious precipitation according to the precipitation amount;
the high temperature aging resistance test conditions are as follows: placing the sample at 100 ℃ for 168 hours, taking out, standing for 2 hours at room temperature, and testing the tensile strength and the elongation at break;
the water resistance test conditions were: the test piece was placed in 80 ℃ water for 168 hours, taken out and left at room temperature for 1 hour, and the tensile strength and elongation at break were tested.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, examples 1 to 6 of the present invention use PDMS to synthesize the block TPU, and the TPU material prepared by the continuous production process of reaction flame retardance and synergistic flame retardance, chain extender crosslinking, medium double-shaft double-screw and long double-shaft double-screw connection has high flame retardance, good mechanical property, high transparency, good heat resistance and water resistance, and no precipitation. Compared with the example 1, the mechanical property of the TPU material is improved but the heat resistance, the water resistance and the flame retardant grade are reduced without adding PDMS into the polyol of the comparative example 1; comparative example 2 does not add a synergistic flame retardant, has slightly higher mechanical properties, but has a reduced flame retardant rating; the TMP content in the chain extender of the comparative example 3 exceeds a critical value, so that the mechanical properties of the TPU material are reduced; TMP is not added into the chain extender of comparative example 4, so that the mechanical properties of the TPU material are poor; the isocyanate of comparative example 5 increases the content of HMDI, the mechanical properties of the TPU material are reduced, and the light transmittance of the TPU material is increased; the isocyanate of comparative example 6 uses a single component MDI, and the light transmittance of the TPU material is reduced; comparative example 7 only used a long biaxial twin screw production process, the mechanical properties of the TPU material were degraded.

Claims (8)

1. A high strength TPU material for a charging pile cable, characterized by: the material comprises the following raw materials in parts by weight:
50-70 parts of mixed polyol,
25-40 Parts of isocyanate and the like,
5-10 Parts of composite chain extender,
0.1 To 0.3 part of antioxidant,
0.05 To 0.2 part of hydrolysis resistant agent,
0.02-0.1 Part of catalyst,
0.01 To 0.03 part of dispersing agent,
0.005-0.01 Part of synergistic flame retardant,
0.05-0.3 Part of ultraviolet absorber;
the mixed polyol is at least one of polycaprolactone diol and polytetramethylene ether glycol, and is mixed with end-hydroxybutyl-terminated polydimethylsiloxane; in the mixed polyol, the mass percentage of the end-hydroxybutyl-terminated polydimethylsiloxane is 5-15%;
The compound chain extender is prepared by compounding 85-99wt.% of 1, 4-butanediol and 1-15wt.% of trimethylolpropane;
the isocyanate is a mixture of 90-95wt.% diphenylmethane diisocyanate and 5-10wt.% dicyclohexylmethane diisocyanate;
the synergistic flame retardant is silane coupling agent modified nano Sb 2O3 powder;
the preparation method of the high-strength TPU material for the charging pile cable comprises the following steps of:
adopting a two-section double-screw extruder connected with a middle double-shaft double-screw and a long double-shaft double-screw to carry out continuous polymerization reaction, firstly adding an antioxidant, a hydrolysis-resistant agent, a dispersing agent, a synergistic flame retardant and an ultraviolet absorbent into mixed polyol, and carrying out prepolymerization reaction with partial isocyanate and a catalyst in the middle double-shaft double-screw to obtain a prepolymer; and then conveying the prepolymer into a long double-shaft double-screw rod, carrying out polymerization reaction with the residual isocyanate and the composite chain extender, and carrying out underwater cutting granulation to obtain the high-strength TPU material for the charging pile cable.
2. The high strength TPU material for a charging pile cable according to claim 1, wherein: the number average molecular weight of the polycaprolactone diol and the polytetramethylene ether glycol is 500-2000; the number average molecular weight of the end-hydroxybutyl-terminated polydimethylsiloxane is 1500-2000.
3. The high strength TPU material for a charging pile cable according to claim 1, wherein: in the silane coupling agent modified nano Sb 2O3 powder, the average particle size of the nano Sb 2O3 powder is between 30 and 50 nm.
4. The high strength TPU material for a charging pile cable according to claim 1, wherein: the antioxidant is phosphite antioxidant.
5. The high strength TPU material for a charging pile cable according to claim 1, wherein: the hydrolysis resistance agent is carbodiimide.
6. The high strength TPU material for a charging pile cable according to claim 1, wherein: the catalyst is an organotin catalyst.
7. The high strength TPU material for a charging pile cable according to claim 1, wherein: the dispersing agent is at least one of glyceryl monostearate, glyceryl tristearate, barium stearate and calcium stearate.
8. The high strength TPU material for a charging pile cable according to claim 1, wherein: the ultraviolet absorbent is at least one of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylamidine, N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine, phenyl o-hydroxybenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371684A (en) * 1978-04-21 1983-02-01 Bayer Aktiengesellschaft Thermoplastic polyurethanes for processing in extruders and/or on calenders
JP2004244443A (en) * 2003-02-10 2004-09-02 Ito Seiyu Kk Urethane polyol composition and polyurethane composition
JP2010248346A (en) * 2009-04-14 2010-11-04 Ito Seiyu Kk Polyol composition and polyurethane resin obtained using the same
CN106565933A (en) * 2016-10-19 2017-04-19 万华化学集团股份有限公司 Preparation method of organosilicon thermoplastic polyurethane
CN106866922A (en) * 2015-12-10 2017-06-20 上海凯众材料科技股份有限公司 The preparation method of microporous polyurethane elastomer
CN108034038A (en) * 2017-12-26 2018-05-15 东莞市雄林新材料科技股份有限公司 A kind of high abrasion TPU for cable jacket and preparation method thereof
CN110498899A (en) * 2019-08-29 2019-11-26 山东一诺威聚氨酯股份有限公司 Hydrophobic solvent resistant corrosion TPU material and preparation method thereof
CN110552205A (en) * 2019-07-30 2019-12-10 湖北大学 preparation method of fabric heat-insulating finishing agent and fabric heat-insulating finishing agent
WO2022062245A1 (en) * 2020-09-22 2022-03-31 何建雄 High transparent tpu film for electronic products and preparation method therefor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10326575A1 (en) * 2003-06-12 2005-01-20 Wacker-Chemie Gmbh Organopolysiloxane / polyurea / polyurethane block copolymers
KR102381011B1 (en) * 2016-03-21 2022-04-04 바스프 에스이 cross-linked polyurethane
BR112020017350A2 (en) * 2018-02-26 2020-12-15 Lubrizol Advanced Materials, Inc. COMPOSITION OF THERMOPLASTIC POLYURETHANE, ARTICLE WITH REDUCED COMPRESSION SET, AND, METHOD TO REDUCE THE COMPRESSION SET OF A THERMOPLASTIC POLYURETHANE

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371684A (en) * 1978-04-21 1983-02-01 Bayer Aktiengesellschaft Thermoplastic polyurethanes for processing in extruders and/or on calenders
JP2004244443A (en) * 2003-02-10 2004-09-02 Ito Seiyu Kk Urethane polyol composition and polyurethane composition
JP2010248346A (en) * 2009-04-14 2010-11-04 Ito Seiyu Kk Polyol composition and polyurethane resin obtained using the same
CN106866922A (en) * 2015-12-10 2017-06-20 上海凯众材料科技股份有限公司 The preparation method of microporous polyurethane elastomer
CN106565933A (en) * 2016-10-19 2017-04-19 万华化学集团股份有限公司 Preparation method of organosilicon thermoplastic polyurethane
CN108034038A (en) * 2017-12-26 2018-05-15 东莞市雄林新材料科技股份有限公司 A kind of high abrasion TPU for cable jacket and preparation method thereof
CN110552205A (en) * 2019-07-30 2019-12-10 湖北大学 preparation method of fabric heat-insulating finishing agent and fabric heat-insulating finishing agent
CN110498899A (en) * 2019-08-29 2019-11-26 山东一诺威聚氨酯股份有限公司 Hydrophobic solvent resistant corrosion TPU material and preparation method thereof
WO2022062245A1 (en) * 2020-09-22 2022-03-31 何建雄 High transparent tpu film for electronic products and preparation method therefor

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘厚钧.《聚氨酯弹性体手册》.化学工业出版社,2012,83,295. *
刘益君.《聚氨酯树脂及其应用》.化学工业出版社,2011,176. *
郑水林.《粉体表面改性》.中国建材工业出版社,2019,8-9. *

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