CN107892808B - A kind of wire and cable halogen-free flameproof TPU elastic composition and preparation method thereof - Google Patents
A kind of wire and cable halogen-free flameproof TPU elastic composition and preparation method thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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Abstract
The invention discloses a kind of wire and cable halogen-free flameproof TPU elastic compositions, and by weight percentage, raw material composition includes: TPU basis material 65~90%;Phosphorus nitrogen composite flame retardant system 10~30%;Auxiliary agent 1~5%;The phosphorus nitrogen composite flame retardant system includes diethyl hypo-aluminum orthophosphate and at carbon component, described to be divided into insoluble insoluble cross-linked polymer at carbon group, shown in Crosslink structure such as following formula (I);The present invention develops a kind of wire and cable halogen-free flameproof TPU elastic composition, which has the characteristics that no molten drop, high fire-retardance, resistance to migration, soft abrasion-resistant, oil resistant.It can be applied to the cable field that the high fire-retardances such as new-energy automobile, oil resistant, soft abrasion-resistant require.
Description
Technical field
The present invention relates to the technical fields of halogen-free flameproof TPU, and in particular to a kind of wire and cable halogen-free flameproof TPU elasticity
Body composition and preparation method thereof.
Background technique
Polyurethane is a quasi polymer of main chain constitutional repeating unit Han-NHCOO-, english abbreviation PU, by isocyanates
(monomer) is polymerized with hydroxy compounds.Due to not dissolving in nonpolar solvent containing highly polar carbamate groups, have good
Good oil resistivity, toughness, wearability, resistance to ag(e)ing etc., is widely used multi-field.Polyurethane includes two class materials
Material, one kind is thermosetting property PU, and thermosetting property PU is typically used in the fields such as synthetic leather, foaming;One kind is thermoplastic polyurethane, letter
Claiming TPU, this kind of material has the processing method of thermoplastic material, and the performance characteristics with thermosetting property PU, quickly grows at present,
It is mainly used in the fields such as sole, cable.Especially novel electric car and charge cable field, it is soft to have given full play to its
The characteristics such as soft, wear-resisting, oil resistant, and be concerned.
For TPU in the application of cable field, relevant criterion proposes requirement to fire-retardant, and polyurethane is a kind of combustibles,
Oxygen index (OI) is lower, and TPU its molten drop phenomenon in high-temp combustion is serious, it is difficult to reach the flame-retardancy requirements of prescribed by standard, institute
It is larger with its fire-retardant difficulty.
Currently, including the basic flame-retardant system of two classes: halogen system flame-retardant system and non-halogen for the fire-retardant of TPU elastomer
Flame-retardant system.Halogen system flame-retardant system is usually brominated flame-retardant collaboration antimony oxide, a large number of studies show that, it is hindered added with bromine system
The TPU material for firing agent can produce thick smoke and the harmful substances such as hydrogen bromide in burning, human body can be caused to suffocate.It therefore, is TPU bullet
The safe and environment-friendly, halogen-free flame-retardant system of elastomer material exploitation has become a hot topic of research, and occurs novel being applied to TPU bullet in recent years
The halogen-free flame retardants of elastomer material.
It according to the literature, mainly include two major classes primary structure applied to the halogen-free flame retardants of TPU elastomeric material: a kind of
It is inorganic hydroxide system, including magnesium hydroxide and aluminium hydroxide;Another kind of is phosphorus nitrogen system flame-retardant system.For inorganic hydrogen-oxygen
Compound system, fire retardation is limited, and in order to reach the requirement of various codes and standards, usual additive amount is very high, sometime up to
The 80% of entire formula system is with a kind of side of filler due to inorganic hydroxide fire retardant and matrix resin and incompatible
Formula is scattered in matrix resin, and therefore, high filler loading capacity will substantially reduce the mechanical property of material.Sometimes for the inorganic hydrogen-oxygen of reduction
The additive amount of compound, also by the way of red phosphorus collaboration, but the application of red phosphorus can have the appearance color of material, Er Qiehong
The burning of phosphorus is easy to produce the toxic gases such as hydrogen phosphide and a large amount of smog, therefore this is also not optimal solution.
For phosphorus nitrogen system flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency, additive amount is substantially
It reduces and is able to achieve high flame retardant, be the hot spot studied at present.Apply more at present, high polymerization degree APP
(APP) and organophosphorus compounds, high polymerization degree APP (APP) flame-retardant system, it belongs to a kind of Intumscent Flame Retardant System, by
Stronger in its anti-flammability, additive amount will be substantially reduced compared to inorganic hydroxide system, but APP is due to its surface hydrophilic spy
Property, and have certain water solubility, it is still incompatible with basis material, therefore the power of the fire-retardant TPU elastomeric material of APP system
It is still lower to learn intensity, while being easy migration precipitation, the albinism being precipitated is generated in cable surface, not only influences appearance,
The flame retardant property that will lead to cable is gradually decreased with precipitation.Further, since the presence of ammonium ion, APP is easy the moisture absorption, one section
TPU cable surface reduces the insulation performance of material with the presence of droplet after time, and there are great security risks;And it is organic phosphorus
Acid esters, some still have water solubility, although some are water-soluble small, the problem of overcoming the moisture absorption, its fire retardant mechanism belongs to cohesion
It is mutually fire-retardant, belong to non-expansion type, non-expansion type flame-retardant system is for TPU elastomeric material, and drippage easy to form, draws in kindling
Other combustibles are fired, molten drop will affect flame retardant effect, be extremely difficult to the requirement of standard.
Generally speaking, at present applied to cable TPU material flame-retardant system existing for major defect be: poor fire, easily
The problems such as molten drop, the easy moisture absorption and migration albefaction.Therefore, it is necessary to research and develop the novel novel nothing applied to TPU elastomeric material
Halogen flame-retardant system.
Summary of the invention
The present invention develops a kind of wire and cable halogen-free flameproof TPU elastic composition, TPU elastic composition tool
The features such as whether there is or not molten drop, high fire-retardance, resistance to migrations, soft abrasion-resistant, oil resistant.It can be applied to high fire-retardances such as new-energy automobile, oil resistant, soft
The cable field of soft wear-resisting requirement.
Specific technical solution is as follows:
A kind of wire and cable halogen-free flameproof TPU elastic composition, by weight percentage, raw material composition includes:
TPU basis material system 65~90%;
Phosphorus nitrogen composite flame retardant system 10~30%;
Auxiliary agent 1~5%;
The phosphorus nitrogen composite flame retardant system includes diethyl hypo-aluminum orthophosphate and at carbon component, described can not be divided into carbon group
Molten insoluble cross-linked polymer, shown in Crosslink structure such as following formula (I):
The present invention relates to the exploitations of halogen-free flameproof TPU elastomer to lead to using novel low aqueous solubility diethyl hypo-aluminum orthophosphate
Special low aqueous solubility carbonific collaboration is crossed, the expansion type flame-retarding mechanism for being directed to TPU elastomer is formed, solves existing fire retardant
It is the defect that additive amount is big and TPU substrate compatibility is poor, the easy moisture absorption forms droplet, precipitation and molten drop easy to migrate.By the diethyl
The novel flame-retardant system of hypo-aluminum orthophosphate and special carbonific composition can be well adapted for TPU elastomeric material, obtaining property
Excellent resistance to TPU cable material of the migration without molten drop of halogen-free flameproof of energy.
It will elaborate below to the present invention.
The present invention is the invention for the purpose of solving various defects existing for existing halogen-free flameproof TPU elastomer cable material
People has made extensive and intensive studies.Existing flame-retardant system aiming at the problem that fire-retardant TPU elastomeric material, investigate newly
Flame-retardant system, as a result, it has been found that diethyl hypo-aluminum orthophosphate cooperates with and special can be well solved this problem at carbon component.
Shown in the chemical structure of diethyl hypo-aluminum orthophosphate such as following formula (II):
Diethyl hypo-aluminum orthophosphate is characterized in phosphorus content height, good flame resistance, temperature of initial decomposition with higher, water solubility
Low, resistance to migration is nonhygroscopic, and more application is in the engineering plastics such as nylon, PBT at present, especially engineering plastics of fiberglass reinforced
In.Applied to TPU elastomeric material, due to water-soluble extremely low, be not in the moisture absorption and have the problem of droplet, but due to being cohesion
Phase fire retardant mechanism reduces flame retardant property, can not pass through VW-1's so that TPU elastomeric material is easy drippage in burning again
Flame-retardancy requirements, and reach flame-retardancy requirements by improving additive amount, the reduction of material property can be caused.
Inventors discovered through research that in the presence of diethyl hypo-aluminum orthophosphate, it is added suitably into carbon component, this
When expansion type flame-retarding is become to the fire retardant mechanism of TPU elastomeric material, and under the action of expanding carbon-coating, the molten drop of material
It is under control, it is shown that the flame-retardancy requirements of VW-1 may be implemented in good anti-flammability.
As at charcoal component, the usually compounds such as compound of polyhydroxy, such as pentaerythrite, but these compounds by
In the presence of hydroxyl, although have it is good at carbon effect, it is water-soluble higher, will appear asking for the moisture absorption after being applied to polyurethane
The problems such as inscribing, surfaces of tacky, water stain and insulating properties caused to reduce.
It is studied through inventor, discovery is by two kinds of compounds of methylphosphonic acid and trihydroxyethyl isocyanuric ester in equivalent
Under the conditions of carry out polycondensation reaction, obtain heat cured carboxylate, when application is crushed to the carboxylate in the powder of certain particle size range
End, it is as described at carbon component.This at carbon component had at carbon effect, the concertedness having had with diethyl hypo-aluminum orthophosphate,
There are phosphorus and nitrogen in molecular structure, can reduce the additive amount of diethyl hypo-aluminum orthophosphate, in molecular configurational due to not depositing
It is nonhygroscopic in water suction group, it not will form water stain, surfaces of tacky will not be caused.
The preparation method at carbon component, specifically:
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, 150~
4~8h is reacted at 220 DEG C, and esterification prepolymer is made;
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed
It arrives.
In the preparation process of step (1) prepolymer, in order to accelerate reaction speed, need using phase transfer catalyst.Make
To be preferred, the phase transfer catalyst is selected from quaternary ammonium salt, such as tetrabutylammonium bromide.
In step (2), high-temperature polycondensation solidification is carried out to prepolymer, needs high vacuum, hot conditions.Preferably, taking out true
Sky to vacuum degree is not higher than 50KPa.The reaction can carry out in an oven, also can be used with the high-power of agitating function
Kneader.
It is block by the fire retardant obtained after condensation curing, in order to be added in basis material, it is also necessary to carry out powder
Broken processing controls average grain diameter D50 < 5 μm of fire retardant using mechanical crushing equipment.
Meanwhile also the water that esterification generates is drained in time.Prepolymer changes colour in order to prevent, and reaction can be in nitrogen
Atmosphere carries out.
Preferably, the diethyl hypo-aluminum orthophosphate is white powder, average grain diameter D50 < 5 μm.
The TPU basis material, is thermoplastic polyurethane, it can passes through the similar processing of thermoplastic macromolecule material
Method, for example squeeze out, be molded etc., and the material with polyurethane elastomer performance, use can be formed repeatedly, including polyester-type gathers
Urethane, polyether polyurethane, polycarbonate polyurethane, polycaprolactone-type urethane, in aliphatic anti-yellowing polyurethane extremely
Few one kind.
In halogen-free flameproof TPU elastomeric material of the invention, in the premise for the physical property and flame retardant property for not influencing TPU
Under, other auxiliary agents, such as anti-mildew agent, antistatic agent, lubricant, anti-UV agent, antioxidant can be added.
Further preferably, by weight percentage, the raw material of wire and cable halogen-free flameproof TPU elastic composition
Composition includes:
TPU basis material 65~80%;
Phosphorus nitrogen composite flame retardant system 20~30%;
Auxiliary agent 1~5%;
In the phosphorus nitrogen composite flame retardant system, diethyl hypo-aluminum orthophosphate and the mass ratio at carbon component are 1.15~5:1.
Still further preferably, described in carbon component, nitrogen content 10.4%, phosphorus content 11.5%.Through further
Application test discovery, applied in TPU elastomer after being compounded at carbon component with diethyl hypo-aluminum orthophosphate of the content of nitrogen and phosphorous,
More preferably flame retardant effect can be obtained.
The invention also discloses the wire and cable preparation methods of halogen-free flameproof TPU elastic composition, comprising:
After mixing by each component, it squeezes out through double screw extruder, obtained after granulation;
The halogen-free flameproof TPU elastic composition completes extruding pelletization in double screw extruder, due to fire retardant
It is heat-sensitive substance, it is necessary to control processing temperature, the maximum temperature of twin-screw is no more than 230 DEG C, preferably at 220 DEG C or less.
The composition completes extruding pelletization in double screw extruder, there is certain requirement to extrusion equipment, double screw extruder
Draw ratio is not less than 44, is preferably not less than 48, more preferably 52.The composition is completed to squeeze out in double screw extruder and be made
Grain, can be used water cooling bracing mode, water ring pelletizing or underwater cutpellet.
According to halogen-free flameproof TPU elastic composition prepared by the above method, the sheath material or exhausted of cable can be used as
Edge material prepares cable on existing cable apparatus by extrusion molding process.
Compared with prior art, the present invention has the advantage that
The present invention provides a kind of wire and cable halogen-free flameproof TPU elastic compositions, comprising by diethyl hypophosphorous acid
The novel flame-retardant system of aluminium and special carbonific composition, the TPU elastic composition with no molten drop, high fire-retardance, resistance to move
The features such as shifting, soft abrasion-resistant, oil resistant.It can reach the flame-retardant standard of VW-1 using it as the cable material of raw material preparation.
Specific embodiment
Embodiment 1
(1) mixture of halogen-free flameproof TPU system
In advance drying TPU, height stir in machine be added according to the ratio (unless otherwise stated, the present invention in proportion be weight
Percentage) TPU, compounding flame retardant and the other auxiliary agents that weigh up in advance, start high-speed stirred, stir 10min, completes Halogen resistance
Fire the mixture of TPU system, discharging.
(2) extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature (210 DEG C of spiro rod plasticizing section maximum temperature), to temperature
After stablizing 20min, the uniform halogen-free flameproof TPU system of mixture is added from hopper, starts host and feeder, completes material
Extruding pelletization.The material for having made grain is sent into feed bin by blast system, and dries.
(3) application and test of material
The material dried is molded by the standard sample of various testing standard defineds in injection molding machine, and carries out correlation
The test of material property.Qualified cable is prepared on wire and cable guy-line equipment, samples and carries out relevant wire and cable
Test.It is primarily upon following performance indicator:
Fire-retardant and melt-dropping property
Testing standard according to cable material VW-1 is tested, and pays close attention to molten drop.
Resistance to migration experiment
It is put into the fire-retardant TPU cable sample of certain length in climatic chamber, is arranged 85 DEG C of temperature, relative humidity
85%, the state of specimen surface of the visual observations after 168 hours.
Preparation process in the present embodiment at carbon component is as follows:
In the flask of 1L, 522 grams of (2 moles) trihydroxyethyl isocyanuric esters are added, leads to nitrogen protection, is heated to 150
DEG C trihydroxyethyl isocyanuric ester is melted, 2.7 grams of tetrabutylammonium bromide and 288g (3 moles) methylphosphonic acid is then added,
Strong stirring mixture, heating is raised to 210 DEG C from 150 DEG C within 6 hours, the water in reaction process is discharged, and condense metering,
210 DEG C keep the temperature 1 hour, are cooled to 150 DEG C, and melt is discharged to a metal tray, obtains a kind of faint yellow hair after melt is cooling
Crisp solids, for melting range from 100~120 DEG C, residual acid value is 7 milligrams of KOH/g.
Prepolymer is placed into vacuum drying oven together with pallet, is vacuumized, vacuum degree keeps 50KPa, is heated to 270
DEG C, it is kept for 2 hours, completes solidification, cooling discharge.Crushing material is stand-by to average grain diameter D50 < 5 micron.
Through analyzing:
It is manufactured in the present embodiment at carbon component, phosphorus content are as follows: 10.5%, nitrogen content are as follows: 10.1% (phosphorus, nitrogen content are
Actual measured value, the slightly below calculated value in specification), solubility < 0.1%, 1% weightlessness decomposition temperature is 320 DEG C.
Unless otherwise instructed, product manufactured in the present embodiment is all made of at carbon component in following embodiment.
Each material and proportion are shown in Table 1 in embodiment, and the performance test results of obtained material are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, in addition to diethyl hypo-aluminum orthophosphate and at the proportion adjustment of carbon component, improves diethyl
The proportion of base hypophosphorous acid keeps flame-retardant system total amount constant.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table
1。
Embodiment 3
Implementation process is same as Example 1, in addition to diethyl hypo-aluminum orthophosphate and at the proportion adjustment of carbon component, improves into carbon
The proportion of component keeps flame-retardant system total amount constant.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, in addition to the adjustment of the proportion of formula, reduces flame-retardant system sum-rate.Other objects
Material and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 5
Implementation process is same as Example 1, in addition to the adjustment of the proportion of formula, improves flame-retardant system sum-rate.Other objects
Material and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, in addition to not using into carbon group exceptionally.Other materials and proportion are shown in Table 1, acquired
Material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than without using diethyl hypo-aluminum orthophosphate.Other materials and proportion are shown in Table 1,
Obtained material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than only using ammonium polyphosphate, without using diethyl hypo-aluminum orthophosphate and at carbon
Component.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, other than only using aromatic phosphoric acid ester, without using diethyl hypo-aluminum orthophosphate and at
Carbon component.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.Table 1
Claims (10)
1. a kind of wire and cable halogen-free flameproof TPU elastic composition, which is characterized in that by weight percentage, raw material group
At including:
TPU basis material 65~90%;
Phosphorus nitrogen composite flame retardant system 10~30%;
Auxiliary agent 1~5%;
The phosphorus nitrogen composite flame retardant system includes diethyl hypo-aluminum orthophosphate and at charcoal component, it is described at charcoal group be divided into it is insoluble not
Molten cross-linked polymer, shown in Crosslink structure such as following formula (I):
2. wire and cable according to claim 1 halogen-free flameproof TPU elastic composition, which is characterized in that described
In phosphorus nitrogen composite flame retardant system, by weight percentage, raw material composition includes:
50~90wt% of diethyl hypo-aluminum orthophosphate;
At 10~50wt% of charcoal component.
3. wire and cable according to claim 1 halogen-free flameproof TPU elastic composition, which is characterized in that described
At charcoal component using the trihydroxyethyl isocyanuric ester of equivalent and methylphosphonic acid as raw material, it is prepared after polycondensation reaction.
4. wire and cable according to claim 3 halogen-free flameproof TPU elastic composition, which is characterized in that it is described at
The preparation method of charcoal component, specifically:
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, at 150~220 DEG C
Esterification prepolymer is made in 4~8h of lower reaction;
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed.
5. wire and cable according to claim 4 halogen-free flameproof TPU elastic composition, which is characterized in that step (1)
In, the phase transfer catalyst is selected from quaternary ammonium salt.
6. wire and cable according to claim 4 halogen-free flameproof TPU elastic composition, which is characterized in that step (2)
In, vacuum degree is evacuated to not higher than 50KPa;It is crushed to average grain diameter D50 < 5 μm.
7. wire and cable according to claim 1 halogen-free flameproof TPU elastic composition, which is characterized in that described
TPU basis material is selected from polyester polyurethane, polyether polyurethane, polycarbonate polyurethane, aliphatic anti-yellowing polyurethane
At least one of.
8. wire and cable according to claim 1 halogen-free flameproof TPU elastic composition, which is characterized in that described
Diethyl hypo-aluminum orthophosphate, average grain diameter D50 < 5 μm.
9. any wire and cable halogen-free flameproof TPU elastic composition according to claim 1~8, which is characterized in that
By weight percentage, raw material composition includes:
TPU basis material system 65~80%;
Phosphorus nitrogen composite flame retardant system 20~30%;
Auxiliary agent 1~5%;
In the phosphorus nitrogen composite flame retardant system, diethyl hypo-aluminum orthophosphate and the mass ratio at charcoal component are 1.15~5:1.
10. a kind of preparation of the wire and cable halogen-free flameproof TPU elastic composition any according to claim 1~9
Method characterized by comprising
After mixing by each component, it squeezes out through double screw extruder, obtained after granulation;
The extrusion temperature of the double screw extruder is not higher than 230 DEG C.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0584567A2 (en) * | 1992-08-01 | 1994-03-02 | Hoechst Aktiengesellschaft | Fire retardant polymer compositions with increased stability |
CN103923347A (en) * | 2014-04-01 | 2014-07-16 | 常州大学 | Triazine ring hexaphenyl phosphate-containing flame retardant and preparation method thereof |
CN105175735A (en) * | 2015-07-24 | 2015-12-23 | 常州大学 | Branched phosphorus-nitrogen type flame retardant and preparation method therefor |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0584567A2 (en) * | 1992-08-01 | 1994-03-02 | Hoechst Aktiengesellschaft | Fire retardant polymer compositions with increased stability |
CN103923347A (en) * | 2014-04-01 | 2014-07-16 | 常州大学 | Triazine ring hexaphenyl phosphate-containing flame retardant and preparation method thereof |
CN105175735A (en) * | 2015-07-24 | 2015-12-23 | 常州大学 | Branched phosphorus-nitrogen type flame retardant and preparation method therefor |
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