阅读说明：本技术 一种无卤阻燃空气纤维材料及其制备方法和应用 (Halogen-free flame-retardant air fiber material and preparation method and application thereof ) 是由 孙刚伟 何晓东 于 2021-07-22 设计创作，主要内容包括：本发明公开了一种无卤阻燃空气纤维材料及其制备方法和应用,其制备方法包括以下步骤：按照重量份称取70-90份热塑性弹性体、5-20份含磷阻燃剂、2-10份含氮阻燃剂和1-10份偶联剂于110℃-150℃混合30min-120min,并抽真空后,降温至80℃-110℃,获得第一预混料；按照重量份称取0.2-2份抗氧剂和1-5份复合加工助剂,加入至所述第一预混料中,于80℃-110℃混合0.5h-1h,并抽真空后,获得第二预混料；将所述第二预混料经熔融、挤出造粒,制得无卤阻燃空气纤维材料。该无卤阻燃空气纤维材料具有优异的阻燃性、中空弹性和加工性,且能够一次性三维成型,可广泛应用。(The invention discloses a halogen-free flame-retardant air fiber material and a preparation method and application thereof, wherein the preparation method comprises the following steps: weighing 70-90 parts by weight of thermoplastic elastomer, 5-20 parts by weight of phosphorus-containing flame retardant, 2-10 parts by weight of nitrogen-containing flame retardant and 1-10 parts by weight of coupling agent, mixing for 30-120 min at 110-150 ℃, vacuumizing, and cooling to 80-110 ℃ to obtain a first premix; weighing 0.2-2 parts of antioxidant and 1-5 parts of composite processing aid according to parts by weight, adding into the first premix, mixing at 80-110 ℃ for 0.5-1 h, and vacuumizing to obtain a second premix; and melting and extruding the second premix to prepare the halogen-free flame-retardant air fiber material. The halogen-free flame-retardant air fiber material has excellent flame retardance, hollow elasticity and processability, can be subjected to one-step three-dimensional forming, and can be widely applied.)

1. The preparation method of the halogen-free flame-retardant air fiber material is characterized by comprising the following steps of:

weighing 70-90 parts by weight of thermoplastic elastomer, 5-20 parts by weight of phosphorus-containing flame retardant, 2-10 parts by weight of nitrogen-containing flame retardant and 1-10 parts by weight of coupling agent, mixing for 30-120 min at 110-150 ℃, vacuumizing, and cooling to 80-110 ℃ to obtain a first premix;

weighing 0.2-2 parts of antioxidant and 1-5 parts of composite processing aid according to parts by weight, adding into the first premix, mixing at 80-110 ℃ for 0.5-1 h, and vacuumizing to obtain a second premix;

and melting and extruding the second premix to prepare the halogen-free flame-retardant air fiber material.

2. The method of claim 1, wherein the thermoplastic elastomer has a shore hardness of between 25D and 72D.

3. The method of claim 1, wherein the phosphorus-containing flame retardant is selected from at least one of aluminum hypophosphite, diethyl aluminum hypophosphite, phenoxy polyphosphazene, hexaphenoxycyclotriphosphazene, n-butyl bis (hydroxypropyl) phosphine oxide), trishydroxypropyl phosphine oxide, cyclooctyl hydroxypropyl phosphine oxide, p-bis (2, 2-cyanoethylphosphineomethyl) tetramethylbenzene, bis (p-carboxyphenyl) phenylphosphine oxide, and phenyldihydroxyphenylphosphine oxide.

4. The process according to claim 1, wherein the nitrogen-containing flame-retardant grade is selected from triazine flame-retardants selected from melamine or its salts.

5. The method of claim 1, wherein the coupling agent is selected from epoxy silane coupling agents.

6. The preparation method of claim 1, wherein the composite processing aid is obtained by compounding at least two of ethyl bis-oleamide, a primary unsaturated amide derivative compound, a fatty acid ester, a mixture of various amide compounds and soap salts, glycerol-stearate, calcium stearate, zinc stearate, ethylene stearamide (EBS), polyethylene wax, talc, white carbon black, polytetrafluoroethylene, erucamide and a coupling agent.

7. The preparation method of claim 6, wherein the composite processing aid is prepared by mixing 15-30 parts of polytetrafluoroethylene, 30-60 parts of talcum powder, 10-20 parts of white carbon black and 5-15 parts of titanate coupling agent according to parts by weight, and the preparation method specifically comprises the following steps:

mixing talcum powder, polytetrafluoroethylene, white carbon black and titanate coupling agent at 100-150 ℃ for 30-120 min according to the proportion, vacuumizing until the vacuum degree is less than 1000Pa, and cooling to obtain the composite processing aid.

8. The method of claim 1 wherein in said steps of obtaining a first premix and a second premix, the vacuum is less than 1000 Pa;

the melting and extrusion granulation adopt a double-screw extruder, the working temperature of the double-screw extruder is 180-;

the fast meshing combination of the twin-screw extruder is medium and low shear strength.

9. A halogen-free flame-retardant air fiber material, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.

10. Use of the halogen free flame retardant air fibre material according to claim 9 for the manufacture of living homes, medical articles, infant products or leisure and recreation products.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a halogen-free flame-retardant air fiber material and a preparation method and application thereof.

Background

The thermoplastic elastomer TPE/TPR is also called artificial rubber or synthetic rubber, and the product has the excellent performances of high elasticity, aging resistance and oil resistance of the traditional cross-linked vulcanized rubber, and has the characteristics of convenient processing and wide processing mode of common plastics. The nozzle can be produced by processing modes such as injection molding, extrusion, blow molding and the like, and 100 percent of the nozzle corners are directly used for the second time after being crushed. The processing process is simplified, and the processing cost is reduced, so that the thermoplastic elastomer TPE/TPR material becomes a latest material for replacing the traditional rubber, is environment-friendly, nontoxic, comfortable in hand feeling and exquisite in appearance, and makes the product more creative. Therefore, the material is a novel synthetic material with more humanization and high grade, and is a worldwide standard environment-friendly material.

Among thermoplastic elastomers, thermoplastic polyester elastomer (TPEE) is a block copolymer comprising a high melting point, high hardness, crystalline polyester hard segment and an amorphous polyether or polyester soft segment having a lower glass transition temperature, and is in a two-phase association structure, the hard segment is crystallized to perform a physical crosslinking function, stabilize the size of the article, and the soft segment is amorphous to impart high resilience to the polymer. The thermoplastic elastomer belongs to a thermoplastic elastomer with excellent comprehensive performance, has the advantages of high mechanical strength, good elasticity, impact resistance, creep resistance, cold resistance, bending fatigue resistance, oil resistance, chemical corrosion resistance, solvent corrosion resistance and the like, has good processability, can be filled, reinforced and alloyed for modification, is widely applied to the fields of automobile parts, hydraulic hoses, cables and wires, electronic and electric products, industrial products, stationery products, living homes, biological materials and the like, and has continuously increased dosage in recent years. In addition, the application field of the thermoplastic polyester elastomer is continuously expanding, and particularly, along with the rapid development of high-speed rails, the application field of the thermoplastic polyester elastomer is expanding; novel automobile seats and backrests; 3D polymer medical products for old people and infant breathable materials; life house and leisure entertainment article: the halogen-free flame-retardant high-elastic breathable air fiber material is used for mattresses, yoga mats, pillows, beach chairs and the like. The products are mostly made of foamed polyurethane, latex or springs in the market. The foaming polyurethane product has the defects that the user experiences the hardness in the initial compression stage in the use process, the foaming polyurethane product is lack of air permeability, poor in resilience after long-term compression, easy to turn yellow after long-term use and the like; although the spring product has good air permeability, the soft spring product has insufficient support degree, the product with the sufficient support degree has insufficient softness, and the spring product is easy to damage and consume quickly after long-term use; and the disadvantages of latex products: firstly, the latex itself cannot prevent the oxidation process, especially the oxidation process is faster when exposed to ultraviolet rays, thereby causing yellowing, shrinkage and deformation of the product. Secondly, the real latex cannot be formed, the purity of the latex rubber in the natural latex is only 20-40%, most latex rubber is protein and saccharide, the latex can be stored for a prolonged time only by adding alkali, the absorption and utilization of mineral substances by a human body can be influenced by contacting the alkali for a long time, and the absorbed vitamin is also damaged. And thirdly, the latex rubber has an allergy-causing effect, and most people have allergy to the latex. And fourthly, the cervical vertebra is too soft and cannot be supported by the head, so that the cervical vertebra is sore and painful. The thermoplastic polyester elastomer can completely overcome the defects of the material product. Meanwhile, the product is closely related to the life of people, and particularly in the use in the closed environment of high-speed rails, the product is required to be green and environment-friendly, recyclable and good in comfort. The material has the advantages of meeting the requirements of V0-grade halogen-free flame retardance, low smoke, no toxicity and hollow resilience, and further requiring stable processing fluidity in the spinning process, thereby ensuring that the product can be three-dimensionally formed at one time in the processing. TPEE is a particularly good choice as an elastomer with excellent comprehensive performance, particularly as a product with better rebound resilience for a halogen-free flame-retardant air fiber material. Because the oxygen limiting index (LOI) of the TPEE is only about 20 percent, the TPEE is easy to ignite and burns quickly, and the processing stability of the conventional TPEE can not completely meet the requirement of air fibers. Therefore, the flame retardant and processing stability modification of TPEE is of great significance for improving the flame retardant and processing stability.

Disclosure of Invention

In view of the above, the present invention needs to provide a halogen-free flame retardant air fiber material, and a preparation method and an application thereof, wherein the halogen-free flame retardant air fiber material has excellent processing flowability, high-efficiency flame retardancy and hollow resilience.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of a halogen-free flame-retardant air fiber material, which comprises the following steps:

weighing 70-90 parts by weight of thermoplastic elastomer, 5-20 parts by weight of phosphorus-containing flame retardant, 2-10 parts by weight of nitrogen-containing flame retardant and 1-10 parts by weight of coupling agent, mixing for 30-120 min at 110-150 ℃, vacuumizing, and cooling to 80-110 ℃ to obtain a first premix;

weighing 0.2-2 parts of antioxidant and 1-5 parts of composite processing aid according to parts by weight, adding into the first premix, mixing at 80-110 ℃ for 0.5-1 h, and vacuumizing to obtain a second premix;

and melting and extruding the second premix to prepare the halogen-free flame-retardant air fiber material.

According to the preparation method, the first premix is obtained in the vacuum environment of 110-150 ℃, so that on one hand, moisture is completely removed, degradation in the subsequent extrusion granulation process is avoided, and meanwhile, under the action of the coupling agent, better compatibility is formed between the thermoplastic elastomer and the flame retardant, so that a more uniform halogen-free flame retardant elastomer is obtained. The antioxidant and the composite processing aid are added into the first premix, so that the air fiber material is ensured to have proper fluidity, and the air fiber material can be subjected to one-time three-dimensional forming in the processing process. Therefore, the prepared halogen-free flame-retardant air fiber material has excellent flame retardance, hollow elasticity and processability.

Further, the term "thermoplastic elastomer" as used herein refers to an elastomer or synthetic rubber (TPE/TPR) conventionally used in the art, which is composed of various resin segments and rubber segments by chemical bonds, wherein the resin segments form physical cross-linking points by virtue of inter-chain forces, and the rubber segments are highly elastic segments and contribute to elasticity. The thermoplastic elastomer used as the matrix resin in the present invention has specific parameters which are not particularly limited, and can be selected or adjusted according to the needs, and the thermoplastic elastomer can be obtained commercially or by self-manufacturing, and the preparation method thereof is only referred to the prior art, and the shore hardness of the thermoplastic elastomer is between 25D and 72D in one or more embodiments of the present invention, because the prior art is not specifically described herein.

Further, the "phosphorus-containing flame retardant" described herein refers to a flame retardant containing phosphorus in the chemical composition, and generally includes organic phosphate esters, phosphonate esters, phosphite esters, organic phosphorus salts, phosphine oxides, phosphorus-containing polyols, phosphorus-nitrogen compounds, inorganic microencapsulated red phosphorus, ammonium polyphosphate, and the like, and specific examples that may be mentioned include, but are not limited to, at least one of aluminum hypophosphite, diethyl hypophosphite, phenoxypolyphosphazene, hexaphenoxycyclotriphosphazene, n-butyl bis (hydroxypropyl) phosphine oxide, trishydroxypropyl phosphine oxide, cyclooctyl hydroxypropyl phosphine oxide, p-bis (2, 2-cyanoethylphosphinomethyl) tetramethylbenzene, bis (p-carboxyphenyl) phenylphosphine oxide, phenyldihydroxyphenylphosphine oxide; preferably aluminium hypophosphite, diethyl aluminium hypophosphite or hexaphenoxycyclotriphosphazene, more preferably diethyl aluminium hypophosphite. In addition, the particle size of the phosphorus-containing flame retardant in the present invention is not particularly limited, and a particle size conventionally used in the art may be employed, and D95 is preferably 5 to 100. mu.m, and D95 is more preferably 5 μm.

Further, the "nitrogen-containing flame retardant" as referred to herein refers to a flame retardant containing nitrogen in the chemical components, and conventionally used in the art are triazine flame retardants selected from melamine or a salt thereof, wherein specific examples of melamine salts include, but are not limited to, cyanurate, phosphate, guanidine, or dicyandiamide salts. In one or more embodiments of the present invention, melamine phosphonate is preferred, wherein the particle size of the nitrogen-containing flame retardant is not particularly limited, and is conventional in the art, preferably the D95 is 5-50 μm, and more preferably the D95 is 5 μm.

Further, the coupling agent in the present invention may be conventionally selected in the art, and specific examples that may be submitted include, but are not limited to, aminosilane (3-aminopropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane), epoxysilane (3- (2, 3-epoxypropyl) propyltrimethoxysilane, 3- (2, 3-epoxypropyl) propyltriethoxysilane), acyloxysilane (methacryloxysilane), vinylsilane (vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. beta. -methoxyethoxy) silane), chlorosilanes, alkylsilanes, phenylsilanes, thiosilanes, silicates, isocyanatosilanes, fluorosilanes, hydroxysilanes, etc., in one or more embodiments of the present invention, the coupling agent is selected from epoxy silane coupling agents.

Further, the antioxidant in the present invention is not particularly limited, and may be of a type conventional in the art, and specific examples include, but are not limited to, dodecathiopropyl pentaerythritol (dodecathiopropyl pentaerythritol)412S), 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine (A)445) Bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (ULTRANOX627A), pentaerythritol tetrakis (BETA- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate) (1010), tris (2, 4-di-tert-butylphenyl) phosphite (168), N, n' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (1098), pentaerythritol distearate phosphite (619), (N-octadecyl-3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tetramethylene (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl ester, bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl).]2,2 oxamide, dioctadecyl tetraol diphosphite.

In a further scheme, the composite processing aid is obtained by compounding at least two of ethyl bis-oleamide, a primary unsaturated amide derivative compound, fatty acid ester, a mixture of a plurality of amide compounds and soap salt, glycerol-stearate, calcium stearate, zinc stearate, ethylene stearamide (EBS), polyethylene wax, talcum powder, white carbon black, polytetrafluoroethylene, erucamide and a coupling agent. The proper fluidity of the material is ensured by adding the composite processing aid, so that the material can be three-dimensionally molded at one time in the processing process.

Preferably, in some embodiments of the present invention, the composite processing aid is prepared by mixing, by weight, 15 to 30 parts of polytetrafluoroethylene, 30 to 60 parts of talc, 10 to 20 parts of white carbon black, and 5 to 15 parts of titanate coupling agent, the polytetrafluoroethylene in the composite processing aid can prevent flame retardant dripping, but the polytetrafluoroethylene in the composite processing aid has an expansion phenomenon during extrusion, which is not beneficial to extrusion molding, and the talc and the white carbon black are used to adjust the extrusion continuity, and the titanate coupling agent is used to maintain uniform fluidity during extrusion, and the composite processing aid is specifically prepared by the following steps:

mixing talcum powder, polytetrafluoroethylene, white carbon black and titanate coupling agent at 100-150 ℃ for 30-120 min according to the proportion, vacuumizing until the vacuum degree is less than 1000Pa, and cooling to obtain the composite processing aid.

In the step of obtaining the first premix and the second premix, the vacuum degrees are both less than 1000 Pa;

the melting and extrusion granulation adopt a double-screw extruder, the working temperature of the double-screw extruder is 180-;

the combination of the meshing blocks of the twin-screw extruder is of medium and low shear strength, and can be realized by adjusting the screw combination, and in one or more embodiments of the invention, the screw combination is as follows: plasticizing section 45 °/5/32, 5 blocks; dispersing the distribution section at 45 DEG/5/32, 3 blocks; 22/11L, 1 block.

The invention also provides a halogen-free flame-retardant air fiber material prepared by the preparation method of any one of the above materials.

The invention further provides the application of the halogen-free flame-retardant air fiber material in the preparation of living homes, medical products, infant products or leisure and entertainment products, such as high-speed rail cushions and back pillows, novel automobile seats and backrests, 3D polymer old-age medical products and infant breathable materials; the product can be used as a daily life, household and leisure entertainment product, such as a mattress, a yoga mat, a pillow, a beach chair and the like.

Compared with the prior art, the invention has the following beneficial effects:

the invention prepares the halogen-free flame-retardant air fiber material with the flame-retardant grade reaching V0 grade by adding superfine nitrogen phosphorus flame retardant; the thermoplastic elastomer, the nitrogen-phosphorus flame retardant and the coupling agent are mixed in vacuum at the temperature of 110-150 ℃ for 30-120 min, so that on one hand, moisture is completely removed, degradation in the subsequent extrusion granulation process is avoided, and meanwhile, under the action of the coupling agent, better compatibility is formed between the thermoplastic elastomer and the flame retardant, and thus the more uniform halogen-free flame retardant elastomer is obtained.

The air fiber material is ensured to have proper fluidity by adding the composite processing aid, so that one-time three-dimensional forming in the processing process is ensured.

According to the invention, through reasonable adjustment of the formula and combination of an improved raw material treatment process, good combination of flame retardance, elasticity and processability is ensured, and the V0-grade halogen-free flame-retardant air fiber material with excellent processability is finally obtained, and can be widely used for living homes, medical products, infant products or leisure and entertainment products.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise specified, "parts" as used herein means parts by weight.

Examples 1 to 3 and comparative examples 1 to 10

The specific information of the adopted raw materials is as follows:

and (2) component A: self-made TPEE with Shore hardness of 35D, tensile strength of 20MPa, elongation at break of 700 percent and melt index of 13g/10min (230 ℃, 2.16 kg). The specific preparation method comprises the following steps: adding 10-25 parts of dimethyl terephthalate, 8-20 parts of 1, 4-butanediol, 10-30 parts of polyether ester polyol, 0.1 part of antioxidant 4, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine (Naugard N445), 0.25 part of catalyst tetrabutyl titanate, 0.2 part of cross-linking agent triglycidyl acrylate and 0.3 part of anti-yellowing agent bis (N, N-dimethyl hydrazido-4-phenyl) methane into a polymerization reaction kettle according to the parts by weight, carrying out polycondensation reaction at 250 ℃, and preparing the polyester elastomer substrate with the intrinsic viscosity meeting the requirement (the intrinsic viscosity is more than 1.3 dL/g) according to the change of stirring current of the reaction kettle.

And (B) component: aluminum diethyl hypophosphite available from Claien

B1: the grain diameter D95 is 60 μm;

b2: the grain diameter D95 is 30 μm;

b3: the particle size D95 was 5 μm.

And (C) component: melamine phosphate, 10 μm in particle size D95, was purchased from Wuhan Yuanchong Co-creation science and technology, Inc.

And (B) component D: the silane coupling agent, vinyltriethoxysilane, was purchased from ipax materials technology, inc.

And (E) component E: antioxidant agent

E1: antioxidant n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, trade name Irganox1098, available from Pasv, Germany;

e2: antioxidant 4, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, available under the trade designation Naugard N445, available from kepi ltd;

e3: pentaerythritol distearate phosphite (619), available from Keppen, Inc.;

e4: the antioxidant tris (2, 4-di-tert-butyl) phosphite (168), available from Keepene, Inc.

And (F): the composite processing aid is prepared by the following specific steps: adding 25 parts by weight of polytetrafluoroethylene, 50 parts by weight of talcum powder, 15 parts by weight of white carbon black and 10 parts by weight of titanate coupling agent into a 120 ℃ double-cone dryer, mixing for 60min, vacuumizing until the vacuum degree is less than 1000Pa, and cooling to normal temperature to obtain the composite processing aid.

All the raw materials or the auxiliary agents are conventional products sold in the market.

It is understood that the above raw material reagents are only examples of some specific embodiments of the present invention, so as to make the technical scheme of the present invention more clear, and do not represent that the present invention can only adopt the above reagents, particularly, the scope of the claims is subject to.

Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.

The components of comparative examples 1 to 10 and examples 1 to 3 were added in the amounts shown in Table 1 in parts by weight, and the preparation methods were as follows:

weighing the component A, the component B, the component C and the component D according to the table 1, adding the components into a 120-DEG C double-cone mixer for mixing for 1h, simultaneously vacuumizing to below 1000Pa, and then cooling to 100 ℃ to obtain a first premix;

weighing the component E and the component F according to the table 1, adding the components into the first premix, mixing for 0.5h in a double-cone mixer at 100 ℃, and simultaneously vacuumizing to below 1000Pa to obtain a second premix;

and adding the second premix through a main feeding hopper of a double-screw extruder, wherein the temperature of a material cylinder of the extruder is 220 ℃, the rotating speed of a screw is 200r/min, and the vacuum degree is-0.08 MPa. The halogen-free flame-retardant air fiber material is obtained through melting and extrusion, wherein the meshing block combination has medium and low shear strength, and the screw combination specifically has a plasticizing section of 45 DEG/5/32, 5 blocks; dispersing the distribution section at 45 DEG/5/32, 3 blocks; 22/11L, 1 block.

TABLE 1 addition amounts of components in comparative examples 1-10 and examples 1-3

Composition of	A	B1	B2	B3	C	D	E1	E2	E3	E4	F
												Comparative example 1	84	10			3	2	0.2	0.4		0.4
Comparative example 2	84	10			3	2	0.2	0.4	0.4
												Comparative example 3	84		10		3	2	0.2	0.4	0.4
Comparative example 4	84			10	3	2	0.2	0.4	0.4
												Comparative example 5	79	15			3	2	0.2	0.4	0.4
Comparative example 6	79		15		3	2	0.2	0.4	0.4
												Comparative example 7	79			15	3	2	0.2	0.4	0.4
Comparative example 8	76	18			3	2	0.2	0.4	0.4
												Comparative example 9	76		18		3	2	0.2	0.4	0.4
Comparative example 10	76			18	3	2	0.2	0.4	0.4
												Example 1	84			10	3	2	0.2	0.4	0.4		1.5
Example 2	79			15	3	2	0.2	0.4	0.4		1.5
												Example 3	76			18	3	2	0.2	0.4	0.4		1.5

The halogen-free flame-retardant air fiber materials prepared in comparative examples 1 to 10 and examples 1 to 3 were tested for tensile strength, elongation at break, melt index, flame retardancy, and apparent melt strength, and the test results are shown in table 2.

Table 2 results of performance testing of comparative examples and examples

Note: the apparent melt strength test in table 2 was performed as follows: the prepared material is put into a single-screw extruder, in order to simulate hollow air fibers, a die head is changed into a hollow die head with the diameter of 3mm and the wall thickness of 1mm for testing, a tractor is arranged in front of the extruder, the speed of the tractor is fixed at 3000mm/min, and under the condition that the hollow tube is ensured to be continuous, the lowest extrusion speed of the extruder is lower, the lower the speed is, the higher the apparent melt strength is, namely, the format is 3000/R, and R represents the single-screw extrusion speed.

The melt continuity test was carried out as follows: the prepared material was placed in a melt index apparatus, 2.16kg of weight was added to allow the material to flow out, and the continuity of the material flow out was observed.

As can be seen from the test results in table 2: the thinner the particle size of the diethyl aluminum hypophosphite is, the higher the flame retardant efficiency is, the more than 0.8mm thick sample strips can reach V0 grade flame retardant by adding 10% of superfine diethyl aluminum hypophosphite and 3% of melamine phosphate, and the higher the relative strength and elasticity are kept due to the better compatibility; the proper antioxidant is selected, so that the stability of the melt during processing can be kept, and the melt is not separated out; it can be seen from the examples that the addition of the composite processing resist increases the apparent melt strength of the material, thereby ensuring the stability of the processing. The material prepared by extrusion traction of an extruder and simulation of a melt index meter can completely meet the requirement of primary continuous forming of the air fiber 3D fabric material.

The test results show that the material with V0 grade halogen-free flame retardant and excellent processing performance can be obtained by the preparation method. The material obtained by the modification of the method completely meets the requirements of a cushion and a back cushion for high-speed rail; the halogen-free flame retardant standard EN45545-2 of the automobile seat and backrest can meet the requirements of preparing 3D polymer aged medical products and infant breathable materials; life house and leisure entertainment article: the air fiber 3D fabric products of mattresses, yoga mats, pillows and beach chairs open up a new application field for thermoplastic polyester elastomers.

On the basis of the above tests, the invention carries out proper adjustment and expansion of the components and the proportion of the raw materials, thereby carrying out other parallel embodiments as follows:

example 4

Weighing 70 parts of thermoplastic elastomer TPEE (with Shore hardness of 25D), 5 parts of aluminum hypophosphite (D95 of 7 mu m), 2 parts of melamine (with the particle size of D95 of 5 mu m) and 1 part of 3- (2,3 epoxypropyl) propyl trimethoxy silane according to parts by weight, adding the materials into a double-cone mixer at 110 ℃, mixing for 30min, simultaneously vacuumizing to below 1000Pa, and then cooling to 80 ℃ to obtain a first premix;

weighing 0.2 part of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (ULTRANOX627A) and 1 part of a composite processing aid, adding the materials into a first premix, mixing the materials in a double-cone mixer at 80 ℃ for 0.5h, and vacuumizing to below 1000Pa to obtain a second premix, wherein the composite processing aid is prepared by mixing 15 parts of polytetrafluoroethylene, 30 parts of talcum powder, 10 parts of white carbon black and 5 parts of titanate coupling agent at 100 ℃ for 120min, vacuumizing to the vacuum degree of less than 1000Pa, and cooling;

and adding the second premix through a main feeding hopper of a double-screw extruder, wherein the temperature of a material cylinder of the extruder is 180 ℃, the rotating speed of a screw is 100r/min, and the vacuum degree is-0.04 MPa. The halogen-free flame-retardant air fiber material is obtained through melting and extrusion, wherein the meshing block combination has medium and low shear strength, and the screw rod combination has a plasticizing section of 45 DEG/5/32 and 5 blocks; dispersing the distribution section at 45 DEG/5/32, 3 blocks; 22/11L, 1 block.

The test shows that the flame retardant property can reach UL940.8mm V0 level, the melt is continuous, the melt strength is high, and the surface is smooth.

Example 5

Weighing 90 parts by weight of thermoplastic elastomer TPEE (with Shore hardness of 72D), 20 parts by weight of hexaphenoxycyclotriphosphazene (D95 is 8 mu m), 10 parts by weight of melamine (with particle size of D95 of 6 mu m) and 10 parts by weight of vinyltriethoxysilane, adding the weighed materials into a 150 ℃ double-cone mixer, mixing for 120min, simultaneously vacuumizing to below 1000Pa, and then cooling to 110 ℃ to obtain a first premix;

weighing 2 parts of tetra (BETA- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid) pentaerythritol ester and 5 parts of composite processing aid, adding the weighed materials into a first premix, mixing for 1h in a double-cone mixer at 110 ℃, and simultaneously vacuumizing to below 1000Pa to obtain a second premix, wherein the composite processing aid is prepared by mixing 30 parts of polytetrafluoroethylene, 60 parts of talcum powder, 20 parts of white carbon black and 15 parts of titanate coupling agent at 150 ℃ for 30min, vacuumizing to the vacuum degree of less than 1000Pa, and cooling;

and adding the second premix through a main feeding hopper of a double-screw extruder, wherein the temperature of a material cylinder of the extruder is 200 ℃, the rotating speed of a screw is 300r/min, and the vacuum degree is-1 MPa. The halogen-free flame-retardant air fiber material is obtained through melting and extrusion, wherein the meshing block combination has medium and low shear strength, and the screw rod combination has a plasticizing section of 45 DEG/5/32 and 5 blocks; dispersing the distribution section at 45 DEG/5/32, 3 blocks; 22/11L, 1 block.

The test shows that the flame retardant property can reach UL940.8mm V0 level, the melt is continuous, the melt strength is high, and the surface is smooth.

Example 6

Weighing 80 parts by weight of thermoplastic elastomer TPEE (with Shore hardness of 30D), 10 parts by weight of aluminum hypophosphite (D95 of 60 mu m), 5 parts by weight of melamine (with particle size of D95 of 20 mu m) and 2 parts by weight of 3-aminopropyltrimethoxysilane, adding the components into a 120-DEG C double-cone mixer, mixing for 50min, simultaneously vacuumizing to below 1000Pa, and then cooling to 90 ℃ to obtain a first premix;

weighing 1 part of (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and 2 parts of a composite processing aid, adding the mixture into a first premix, mixing for 0.5h in a double-cone mixer at 100 ℃, and simultaneously vacuumizing to below 1000Pa to obtain a second premix, wherein the composite processing aid is prepared by mixing 22 parts of polytetrafluoroethylene, 40 parts of talcum powder, 12 parts of white carbon black and 7 parts of titanate coupling agent at 100 ℃ for 120min, vacuumizing to the vacuum degree of less than 1000Pa, and cooling;

and adding the second premix through a main feeding hopper of a double-screw extruder, wherein the temperature of a material cylinder of the extruder is 180 ℃, the rotating speed of a screw is 100r/min, and the vacuum degree is-0.04 MPa. The halogen-free flame-retardant air fiber material is obtained through melting and extrusion, wherein the meshing block combination has medium and low shear strength, and the screw rod combination has a plasticizing section of 45 DEG/5/32 and 5 blocks; dispersing the distribution section at 45 DEG/5/32, 3 blocks; 22/11L, 1 block.

Through the same test mode as that of the examples 1 to 3, the halogen-free flame-retardant air fiber materials indicated in the examples 5 to 6 have the same technical effects as those of the examples 1 to 3, and can realize 0.8mm V0-grade halogen-free flame retardance and excellent processability and elasticity.

Comparative example 11

This comparative example uses the same embodiment as example 6 except that: in the comparative example, all the raw material components are put into a high-speed mixer and then extruded and granulated, namely the same formula composition as in example 6 is adopted, but the preparation method adopts the conventional extrusion and granulation after mixing. Tests prove that the prepared material cannot meet the VO-grade flame retardant requirement of 0.8mm, has very poor processability and cannot meet the requirement of primary continuous forming of the air fiber 3D plant material.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.