CN112876839B - Anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition and preparation method thereof - Google Patents

Anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition and preparation method thereof Download PDF

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CN112876839B
CN112876839B CN202110133185.3A CN202110133185A CN112876839B CN 112876839 B CN112876839 B CN 112876839B CN 202110133185 A CN202110133185 A CN 202110133185A CN 112876839 B CN112876839 B CN 112876839B
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flame retardant
halogen
phosphate
free flame
elastomer composition
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CN112876839A (en
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裘雪阳
王益锦
朱峰
施寅斌
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HANGZHOU JLS FLAME RETARDANTS CHEMICAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention discloses an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition and a preparation method thereof.

Description

Anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition and preparation method thereof
Technical Field
The invention relates to the field of flame-retardant materials and cable sheath materials, in particular to an anti-aging hydrolysis-resistant halogen-free flame-retardant polyurethane thermoplastic elastic composition and a preparation method thereof.
Background
The thermoplastic polyurethane elastomer (TPU) is a high molecular material formed by jointly reacting and polymerizing diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), etc., with macromolecular polyol and low molecular polyol (chain extender). The rubber-plastic composite material is a material between rubber and plastic, has the characteristics of high elasticity of rubber and high strength of plastic, is soft, wear-resistant, oil-resistant, ozone-resistant, aging-resistant, radiation-resistant and low-temperature-resistant, and is widely applied to the fields of new energy, robots, war industry, aerospace, medical treatment and the like.
In the field of electric wires and cables, TPU has excellent strength, low-temperature flexibility, wear resistance, environment resistance and weather resistance as a cable sheath material, and is very suitable for occasions with frequent movement, bending or extreme environment, such as new energy charging cables, communication cables such as wind power cables, spring cables, data, military and optical fiber cables, exploration cables such as land and ocean, robot cables, cables for airplanes and ships and subways, and the like. Most of the applications require that the cable meets a certain flame-retardant grade, so the cable can be used after the TPU is subjected to flame-retardant modification, the TPU can be degraded when meeting water, acid and alkali at high temperature from the perspective of a chemical structure, and the mechanical property, the ageing resistance, the hydrolysis resistance, the flexibility and the like of the TPU are greatly reduced due to the addition of the phosphorus-containing halogen-free flame retardant, so the final application range of the product is influenced. Therefore, how to make the TPU achieve high flame retardance, keep higher mechanical properties and flexibility, and achieve the requirements of good aging resistance and hydrolysis resistance is the direction of continuous research in the field.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition; it is a further object of the present invention to provide a process for the preparation of the aforementioned composition.
The technical scheme is as follows: in order to realize the aim, the invention discloses an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane thermoplastic elastic composition which comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000011
wherein the metal ion modified piperazine polyphosphate is prepared by adding metal phosphate when piperazine reacts with polyphosphoric acid.
Specifically, the metal ion modified piperazine polyphosphate is prepared by the following method:
salifying: adding piperazine into a reaction vessel, slowly adding polyphosphoric acid preheated to 80-100 ℃ under stirring, after stirring reaction, adding metal phosphate, stirring uniformly, continuously heating to 140-150 ℃ for reaction for a period of time, cooling and crushing to obtain a primary product;
polycondensation: and heating the primary product to 190-210 ℃ under the protection of nitrogen to perform polycondensation reaction, dehydrating, cooling and crushing after reacting for a period of time to obtain the metal ion modified polyphosphoric acid piperazine.
The metal ion modified piperazine polyphosphate is beneficial to improving the physical properties of products, especially the piperazine polyphosphate is processed into master batches firstly and then mixed with the polyether polyurethane elastomer, so that the dispersibility of the flame-retardant master batches in TPU can be improved, and the flame-retardant coating has a better flame-retardant effect and high mechanical strength and flexibility.
Wherein, the metal phosphate is selected from phosphates of any one metal element including but not limited to Mg, Ca, Al, Zn, Fe, Ba and Cu. As a preferred embodiment thereof, the metal phosphate is aluminum dihydrogen phosphate or calcium dihydrogen phosphate.
The mass fraction of polyphosphoric acid added in the salifying step is 79.5-85.5%; furthermore, the molar ratio of the metal ions to the piperazine in the reaction system is 0.05-0.1: 1; the molar ratio of phosphorus atoms to piperazine is 1.6-3: 1, more preferably the molar ratio of phosphorus atoms to piperazine is 2-2.1: 1.
The metal ion modified piperazine polyphosphate prepared by the method is a white flowable powder product, the whiteness is greater than or equal to 95, the particle size D50 is 1.0-3.0 mu m, the particle size D98 is 7.0-18.0 mu m, the metal ion modified piperazine polyphosphate can be used as a flame retardant for preparing a halogen-free flame retardant composition, and the addition amount of the metal ion modified piperazine polyphosphate is 18-25 wt% of the total mass.
Further, the polyether polyol in the polyether polyurethane elastomer includes, but is not limited to, any one of polyethylene glycol or polytetrahydrofuran ether glycol. More preferably, the polyether polyurethane elastomer is required to have any one or a combination of more than one of hardness Shore up to 70-95A and tensile strength more than or equal to 40 Mpa.
The phosphate comprises any one or the combination of more of cresyldiphenyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate, tricresyl phosphate and triisopropylphenyl phosphate. The phosphate is mainly used for reducing the viscosity of TPU in the subsequent extrusion molding process, the pH value of the product is reduced by combining metal ion modified polyphosphoric acid piperazine as a flame retardant, and the gas phase flame retardant efficiency of the product can be synergistically improved; among them, tolyldiphenyl phosphate or triphenyl phosphate is more preferably used.
Further, the acrylate elastomer is a calcium carbonate isolated acrylate copolymer, and the raw materials at least comprise butyl acrylate, styrene and acrylonitrile. The person skilled in the art can produce them on the basis of the prior art, and can also purchase commercially available products of this type, for example Sunigum P95 from ELIOKEM, France. The acrylate elastomer and the polyether polyurethane elastomer can be well mixed, the polar polymer and the flame retardant have good compatibility, the addition of the polar polymer and the flame retardant improves the compatibility and the dispersibility of the flame retardant in the polymer, on one hand, the flame retardant effect of the flame retardant is fully exerted, and on the other hand, the influence of the added flame retardant on the system strength is reduced.
The antioxidant comprises any one or combination of more of hindered phenol antioxidant, arylamine antioxidant and phosphite antioxidant.
The ultraviolet light absorber comprises any one or combination of benzotriazole and derivatives thereof, benzophenone and derivatives thereof.
The invention also provides a preparation method of the anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane thermoplastic elastic composition, which comprises the steps of uniformly mixing the metal ion modified piperazine polyphosphate, the acrylate elastomer and the phosphate, and granulating to obtain flame retardant master batches; and then uniformly mixing the flame-retardant master batch, the polyether polyurethane elastomer, the antioxidant and the ultraviolet absorber, granulating, extruding, cooling by water, and granulating to obtain a finished product.
The Shore hardness of the finished product is in the range of 75-95, the flame retardant grade of UL 94-V01.0 mm is achieved, meanwhile, the high mechanical property and flexibility of TPU are kept, and the tensile strength is more than or equal to 25 Mpa; can meet the requirement of long-term use temperature of 105 ℃, and the change rate of the stretching performance after aging of 136 ℃ for 168h is less than or equal to +/-30 percent; has excellent hydrolysis resistance, and the retention rate of the tensile property is more than or equal to 80 percent after 80 ℃ and 168 hours of water immersion; tear resistance, oil resistance, low temperature resistance, no halogen and environmental protection.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The preparation method of the metal ion modified piperazine polyphosphate comprises the following steps:
1. salifying: adding piperazine into a reaction vessel, and slowly adding polyphosphoric acid (P) preheated to 80-100 ℃ under stirring2O5The mass percent of the phosphorus atoms is 79.5-86.8%), and the molar ratio of the phosphorus atoms to the piperazine in the system is about 1.6-3: 1; stirring deviceAfter the stirring reaction is carried out for 0.2-0.8 h, adding metal phosphate, stirring uniformly, keeping the molar ratio of metal ions to piperazine at 0.05-0.1: 1, continuing to heat to 140 ℃ and 150 ℃ for reaction for 2-3 h, cooling and crushing to obtain a metal ion modified polyphosphoric acid piperazine primary product; wherein the metal phosphate is selected from aluminum dihydrogen phosphate or calcium dihydrogen phosphate.
2. A polycondensation step: heating the primary metal ion modified piperazine polyphosphate to 190-210 ℃ under the protection of nitrogen, reacting for 3-4 hours, cooling and crushing to obtain the metal ion modified piperazine polyphosphate, wherein the whiteness is not less than 95, the particle size D50 is 1.0-3.0 mu m, the particle size D98 is 7.0-18.0 mu m, the metal ion modified piperazine polyphosphate is a flame retardant and can be used for preparing a halogen-free flame retardant composition, and the addition amount is 25-40 wt% of the total mass.
Example 2 calcium ion modified piperazine polyphosphate flame retardant
The embodiment provides a calcium ion modified piperazine polyphosphate flame retardant, and a preparation method thereof comprises the following steps:
1. salifying: 8.62Kg of piperazine is put into a horizontal reaction vessel, and polyphosphoric acid (P) preheated to 90 plus or minus 10 ℃ is slowly added into the reaction vessel within 30 plus or minus 5 minutes under stirring2O584.03 percent by mass), keeping the temperature at 60 +/-5 ℃, stirring for reaction for 0.5 hour, adding 1.17Kg of monocalcium phosphate, stirring uniformly, heating to 150 ℃, continuing to react for 3 hours, cooling and crushing to obtain a calcium ion modified piperazine polyphosphate primary product;
2. a polycondensation step: heating the calcium ion modified piperazine polyphosphate primary product to 210 ℃ under the protection of nitrogen, reacting for 3 hours, cooling and crushing to obtain the calcium ion modified piperazine polyphosphate.
Example 3 aluminum ion modified piperazine polyphosphate flame retardant
The embodiment provides an aluminum ion modified piperazine polyphosphate flame retardant, and a preparation method thereof comprises the following steps:
1. salifying: 8.62Kg of piperazine is put into a horizontal reaction vessel, and polyphosphoric acid (P) preheated to 90 plus or minus 10 ℃ is slowly added into the reaction vessel within 30 plus or minus 5 minutes under stirring2O584.03 percent by mass), keeping the temperature at 60 +/-5 ℃, stirring for reaction for 0.5 hour, and then adding the dihydrogen phosphateUniformly stirring 0.74Kg of aluminum, heating to 150 ℃, continuously reacting for 3 hours, cooling and crushing to obtain an aluminum ion modified polyphosphoric acid piperazine primary product;
2. a polycondensation step: heating the aluminum ion modified piperazine polyphosphate primary product to 210 ℃ under the protection of nitrogen, reacting for 3 hours, cooling and crushing to obtain the aluminum ion modified piperazine polyphosphate.
Example 4 calcium ion modified piperazine polyphosphate flame retardant
This example provides another calcium ion-modified piperazine polyphosphate flame retardant, and the preparation method thereof includes the following steps:
1. salifying: 8.62Kg of piperazine is put into a horizontal reaction vessel, and polyphosphoric acid (P) preheated to 90 plus or minus 10 ℃ is slowly added into the reaction vessel within 30 plus or minus 5 minutes under stirring2O582.56 percent by mass), keeping the temperature at 60 +/-5 ℃, stirring for reaction for 0.5 hour, adding 1.67Kg of monocalcium phosphate, stirring uniformly, heating to 150 ℃, continuing to react for 4 hours, cooling and crushing to obtain a calcium ion modified piperazine polyphosphate primary product;
2. a polycondensation step: heating the calcium ion modified piperazine polyphosphate primary product to 200 ℃ under the protection of nitrogen, reacting for 3 hours, cooling and crushing to obtain the calcium ion modified piperazine polyphosphate.
Example 5
An anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane thermoplastic elastic composition comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000041
the preparation method of the metal ion modified piperazine polyphosphate is shown as example 1. The components are prepared by the following method:
step one, preparing flame-retardant master batches:
1.1) uniformly mixing the metal ion modified piperazine polyphosphate flame retardant and the acrylate elastomer according to the weight percentage of the formula;
1.2) adding phosphate according to the weight percentage, and mixing uniformly;
1.3) adding the materials into a double-screw extruder, extruding, air-cooling, grinding the surface and granulating to obtain flame-retardant master batches, and drying for later use; the temperature of the double-screw extruder is set to 130-160 ℃.
Step two, a finished product preparation step:
2.1) carrying out pre-drying treatment on the polyether polyurethane elastomer in an oven at the temperature of 80-90 ℃ until the moisture content is less than or equal to 0.03 percent;
2.2) pre-drying the flame-retardant master batch prepared in the first step in an oven at the temperature of 80-90 ℃ until the moisture content is less than or equal to 0.05 percent;
2.3) uniformly mixing the dried flame-retardant master batch, the polyether polyurethane elastomer, the antioxidant and the ultraviolet absorber according to the weight percentage of the formula;
2.4) adding the uniformly mixed materials into a double-screw extruder, extruding, water-cooling, bracing and granulating to obtain the anti-aging, hydrolysis-resistant and high-performance halogen-free flame-retardant polyurethane thermoplastic elastomer composition; the set temperature of the double-screw extruder is 150 ℃ and 200 ℃.
Wherein, the polyether polyol in the polyether type polyurethane elastomer is any one of polyethylene glycol or polytetrahydrofuran ether glycol, and the physical strength is required to at least reach 70-95 Shore A hardness and the tensile strength is more than or equal to 40 Mpa. E1185A10, hardness 85A, available from BASF of Germany may be selected.
The phosphate is selected from any one of cresyldiphenyl phosphate, triphenyl phosphate and triisopropylphenyl phosphate.
The acrylate elastomer is acrylate copolymer separated by calcium carbonate, and the raw materials at least comprise butyl acrylate, styrene and acrylonitrile. The person skilled in the art can produce them on the basis of the prior art, or can purchase commercially available products of this type, for example SunigumP95 from ELIOKEM, France.
The antioxidant comprises one or more of hindered phenol antioxidant, arylamine antioxidant, and phosphite antioxidant, such as pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite.
The ultraviolet light absorber comprises any one or combination of benzotriazole and derivatives thereof, benzophenone and derivatives thereof.
Example 6
The embodiment provides an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition, which comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000051
Figure BDA0002924578990000061
the above composition was prepared according to the procedure of example 5.
Example 7
The embodiment provides an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition, which comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000062
the above composition was prepared according to the procedure of example 5.
Example 8
The embodiment provides an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition, which comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000063
the above composition was prepared according to the procedure of example 5.
Example 9
The embodiment provides an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition, which comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000071
the above composition was prepared according to the procedure of example 5.
Example 10
The embodiment provides an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition, which comprises the following raw materials in percentage by mass:
Figure BDA0002924578990000072
the above composition was prepared according to the procedure of example 5.
Example 11
The embodiment provides an anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane elastomer composition, which is flame retardant without a combined flame retardant of aluminum ion modified polyphosphoric acid piperazine and calcium ion modified polyphosphoric acid piperazine; the raw materials comprise the following components in percentage by mass:
Figure BDA0002924578990000073
Figure BDA0002924578990000081
the above composition was prepared according to the procedure of example 5.
Comparative example 1
This example provides a polyurethane elastomer composition in which the flame retardant is not modified with metal ions and in which alumina is added during the mixing and extrusion of the components, according to the prior art; the raw materials comprise the following components in percentage by mass:
Figure BDA0002924578990000082
the above composition was prepared according to the procedure of example 5.
Comparative example 2
This example provides a polyurethane elastomer composition substantially the same as example 6, except that melamine cyanurate was used instead of tolylene dimethyl phosphate:
Figure BDA0002924578990000083
Figure BDA0002924578990000091
the above composition was prepared according to the procedure of example 5.
Comparative example 3
The polyurethane elastomer composition provided by the embodiment adopts the combination of piperazine pyrophosphate and alumina, and the raw materials of the composition comprise the following components in percentage by mass:
Figure BDA0002924578990000092
the above composition was prepared according to the procedure of example 5.
Test examples
The polyurethane elastomer compositions obtained in the above examples 6 to 11 and comparative examples 1 to 3 were subjected to injection molding by an injection molding machine at an injection molding temperature of 170 to 185 ℃, and cooled and cut into dumbbell pieces, flame retardant strips and other samples for relevant tests.
And (3) high-temperature heat aging resistance, wherein the sample strip is aged in a blast oven at the temperature of 136 +/-2 ℃ and is placed for 168 hours. And standing the sample at room temperature for more than or equal to 24 hours, and then testing.
And (3) soaking the sample strip in hot water at 80 +/-2 ℃ for 168h, changing the deionized water once every day, sucking surface water by using filter paper after soaking is finished, and airing at room temperature for more than or equal to 24 hours for testing.
The physical properties and aging resistance of each sample were measured according to the following test methods, and the results are shown in table 1:
TABLE 1 Performance test of examples and comparative examples
Figure BDA0002924578990000093
Figure BDA0002924578990000101
TABLE 1
Figure BDA0002924578990000102
Remarking: [*]: comparative example 2 after the 80 ℃ 168h soaking test, the surface of the sample dried and whitened with powder.
The above examples show that the flame retardant property of the polyurethane elastomer material prepared by the invention can reach UL 94V 0(1.0mm), and the polyurethane elastomer material has high-temperature aging resistance, hydrolysis resistance and high mechanical properties.
As is well known, polyurethane is afraid of acid and alkali in the high-temperature extrusion processing process and is very easy to degrade, the mechanical performance of flame retardance of piperazine polyphosphate and piperazine pyrophosphate cannot meet the requirement, and the piperazine pyrophosphate is better. The polyphosphoric piperazine has more residual phosphorus hydroxyl in the structure due to the increase of the polymerization degree. The piperazine pyrophosphate has simple structure and high purity, but the end group still has phosphorus hydroxyl group from the view of molecular structure, and has certain acidity. Although comparative examples 1 and 3 had the acid acceptor alumina added to the formulation, sufficient contact could not be ensured because both were solid. The piperazine polyphosphate flame retardant obtained by modifying metal ions overcomes the problems, reduces acidity, improves the dispersion of the flame retardant in TPU by a master batch method, and can still maintain high mechanical strength and flexibility of TPU elastomers, high-temperature aging resistance, hydrolysis resistance, halogen free and environmental protection while meeting the high flame retardant requirement. On the other hand, in comparative example 2, Melamine Cyanurate (MCA) was used instead of phosphate, and there was a problem that precipitation occurred mainly after immersion in water; the invention can reduce the extrusion viscosity and improve the product molding rate by adopting the phosphate.

Claims (11)

1. An anti-aging hydrolysis-resistant halogen-free flame retardant polyurethane thermoplastic elastic composition comprises the following raw materials in percentage by mass:
Figure FDA0003529621220000011
wherein the metal ion modified piperazine polyphosphate is prepared by adding metal phosphate when piperazine reacts with polyphosphoric acid.
2. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 1, wherein: the metal ion modified piperazine polyphosphate is prepared by the following method:
salifying: adding piperazine into a reaction vessel, slowly adding polyphosphoric acid preheated to 80-100 ℃ under stirring, after stirring reaction, adding metal phosphate, stirring uniformly, continuously heating to 140-150 ℃ for reaction for a period of time, cooling and crushing to obtain a primary product;
polycondensation: and heating the primary product to 190-210 ℃ under the protection of nitrogen to perform polycondensation reaction, dehydrating, cooling and crushing after reacting for a period of time to obtain the metal ion modified polyphosphoric acid piperazine.
3. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 2, wherein: the metal phosphate is selected from phosphate of any one of Mg, Ca, Al, Zn, Fe, Ba and Cu.
4. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 3, wherein: the molar ratio of metal ions to piperazine in the reaction system in the salifying step is 0.05-0.1: 1; the molar ratio of phosphorus atoms in the system to piperazine before the metal phosphate is added is 1.6-3: 1.
5. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 1, wherein: the polyether polyol in the polyether polyurethane elastomer is selected from any one of polyethylene glycol or polytetrahydrofuran ether glycol; the hardness of the polyether polyurethane elastomer is Shore 70-95A, and the tensile strength is not less than 40 Mpa.
6. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 1, wherein: the phosphate comprises any one or more of cresyldiphenyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate and tricresyl phosphate.
7. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 1, wherein: the acrylate elastomer is a calcium carbonate partitioned acrylate copolymer.
8. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 1, wherein: the antioxidant comprises any one or combination of more of hindered phenol antioxidant, arylamine antioxidant and phosphite antioxidant.
9. The halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 8, wherein: the ultraviolet light absorber comprises any one or combination of benzotriazole and derivatives thereof, benzophenone and derivatives thereof.
10. The method for preparing the halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance as claimed in claim 1, wherein the halogen-free flame retardant polyurethane thermoplastic elastomer composition with aging resistance and hydrolysis resistance is prepared by the following steps: uniformly mixing metal ion modified piperazine polyphosphate, an acrylate elastomer and phosphate, and granulating to obtain a flame-retardant master batch; and then uniformly mixing the flame-retardant master batch, the polyether polyurethane elastomer, the antioxidant and the ultraviolet absorber, granulating, extruding, cooling by water, and granulating to obtain a finished product.
11. The method of claim 10, wherein: the shore hardness range of the finished product is 75-95, the UL 94-V01.0mm flame retardant rating and the tensile strength is more than or equal to 25 Mpa; can meet the requirement of long-term use temperature of 105 ℃, and the change rate of the stretching performance after aging of 136 ℃ for 168h is less than or equal to +/-30 percent; has excellent hydrolysis resistance, and the retention rate of the tensile property is more than or equal to 80 percent after 80 ℃ and 168 hours of water immersion.
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