CN109021541A - TPU elastic composition and preparation method thereof of the wire and cable based on dialkyl dithio hypophosphites composite flame retardant system - Google Patents
TPU elastic composition and preparation method thereof of the wire and cable based on dialkyl dithio hypophosphites composite flame retardant system 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a kind of TPU elastic composition of wire and cable based on dialkyl dithio hypophosphites composite flame retardant system, raw material composition includes: 65~90wt% of TPU basis material；9~30wt% of composite flame retardant system；0.1~5wt% of auxiliary agent；The composite flame retardant system includes dialkyl dithio hypophosphites and at carbon component, shown in dialkyl dithio hypophosphites structural formula such as following formula (I), in formula, and R1、R2Independently selected from straight chained alkyl or branched alkyl, M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4；Have the characteristics that no molten drop, high fire-retardance, resistance to migration, soft abrasion-resistant, oil resistant with the cable material that the TPU elastic composition is prepared.
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, which is used, is based on dialkyl disulfides
The TPU elastic composition and preparation method thereof of generation phosphate composite flame retardant system.
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 TPU bullet of the wire and cable based on dialkyl dithio hypophosphites composite flame retardant system
Elastomeric composition, the cable material being prepared have the characteristics that no molten drop, high fire-retardance, resistance to migration, soft abrasion-resistant, oil resistant.It can
The cable field required applied to the high fire-retardances such as new-energy automobile, oil resistant, soft abrasion-resistant.
Specific technical solution is as follows:
A kind of TPU elastic composition of the wire and cable based on dialkyl dithio hypophosphites composite flame retardant system,
By weight percentage, raw material composition includes:
TPU basis material 65~90%；
Composite flame retardant system 9~30%；
Other auxiliary agents 0.1~5%；
The composite flame retardant system includes dialkyl dithio hypophosphites and at carbon component；
The dialkyl dithio hypophosphites, shown in structural formula such as following formula (I):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1
~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m be 1~
4；
It is described to be divided into insoluble insoluble cross-linked polymer at carbon group, shown in Crosslink structure such as following formula (II):
The present invention relates to the exploitations of halogen-free flameproof TPU elastomer, using novel low aqueous solubility dialkyl disulfides generation phosphorus
Hydrochlorate is cooperateed with by special low aqueous solubility carbonific, forms the expansion type flame-retarding mechanism for being directed to TPU elastomer, is solved existing
Have flame-retardant system additive amount it is big, with TPU substrate compatibility is poor, the easy moisture absorption forms droplet, easy to migrate is precipitated and the defect of molten drop.It should
Novel flame-retardant system can be well adapted for TPU elastomeric material, and the resistance to migration of the halogen-free flameproof being had excellent performance is without molten drop
TPU cable material.
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 dialkyl dithio hypophosphites cooperates with and special can be well solved this problem at carbon component.
Shown in the structural formula such as above formula (I) of the dialkyl dithio hypophosphites；Preferably, the dialkyl dithio
Hypophosphites, R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, just
Hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
Further preferably, the dialkyl dithio hypophosphites is selected from diethyl-dithio hypo-aluminum orthophosphate or diisobutyl
Dithiophosphlic acid aluminium.
The invention also discloses a kind of preparation processes of the dialkyl dithio hypophosphites, to prepare dialkyl disulfides
For generation aluminum phosphate, specifically:
(1) dialkyl dithio sodium hypophosphite solution is reacted in acid condition with aluminum sulfate solution, obtains dialkyl group
The suspension of dithiophosphlic acid aluminum precipitation object；
(2) suspension will be filtered, washed and dry, pulverize at 120 DEG C to certain partial size, obtain dialkyl disulfides
For hypo-aluminum orthophosphate combustion inhibitor.
It wherein, can be by commercially available acquisition, or by the following method as the dialkyl dithio sodium hypophosphite of raw material
Preparation:
(a) linear alkene and hydrogen phosphide exist in initiator and free radical can occur under certain temperature and pressure
Addition reaction generates dialkyl group hydrogen phosphide；
(b) dialkyl group hydrogen phosphide and sulfur reaction are generated into dialkyl dithio hypophosphorous acid；
(c) dialkyl dithio hypophosphorous acid is reacted with sodium hydroxide and generates dialkyl dithio hypophosphorous acid soluble easily in water
Sodium salt.
Dialkyl dithio hypophosphites is characterized in phosphorus content height, there are also the collaboration of element sulphur, good flame resistance, have compared with
High temperature of initial decomposition, water-soluble extremely low, resistance to migration is nonhygroscopic, is that a kind of novel can be applied to the engineerings such as nylon, polyester
In plastics, especially in the engineering plastics of fiberglass reinforced.It is not in inhale since water solubility is extremely low applied to polyurethane material
Tide and there is water stain problem, but due to being condensed phase fire retardant mechanism, so that polyurethane material is easy drippage, reduction in burning again
Flame retardant property, if reaching flame-retardancy requirements by improving additive amount, can not can be caused by flame-retardancy requirements as defined in standard
The reduction of material property.
Inventors discovered through research that being added in the presence of dialkyl dithio hypophosphites suitably at carbon
Component becomes expansion type flame-retarding to the fire retardant mechanism of TPU elastomeric material at this time, and under the action of expanding carbon-coating, material
Molten drop be also 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, can go out after being applied to TPU elastomer cable material
The problem of existing moisture absorption, the problem of causing surfaces of tacky and droplet.
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 association having had with dialkyl dithio hypophosphites
The same sex, there are phosphorus and nitrogen in molecular structure, can reduce the additive amount of dialkyl dithio hypophosphites, same to molecular configurational
In since there is no water suction group, it is nonhygroscopic, 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.
To further increase cooperative flame retardant effect, the composite flame retardant system, by weight percentage, raw material composition are wrapped
It includes:
50~90wt% of dialkyl dithio hypophosphites；
At 10~50wt% of carbon component.
Average grain diameter D50 < 5 μm of the dialkyl dithio hypophosphites are also crushed to average grain diameter D50 at carbon component
<5μm。
The TPU basis material, is thermoplastic polyurethane, it can passes through the similar processing side of thermoplastic macromolecule material
Method, for example squeeze out, be molded etc., and the material with polyurethane elastomer performance, use, including the poly- ammonia of polyester-type can be formed repeatedly
Ester, polyether polyurethane, polycarbonate polyurethane, polycaprolactone-type urethane, in aliphatic anti-yellowing polyurethane at least
It is a kind of.
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, described based on dialkyl dithio hypophosphites composite flame retardant system
The raw material of TPU elastic composition forms
TPU basis material 75~85%；
Composite flame retardant system 14~22%；
Auxiliary agent 1~5%；
The composite flame retardant system, by weight percentage, raw material composition includes:
55~78wt% of dialkyl dithio hypophosphites；
At 22~45wt% of carbon component.
Still further preferably, the dialkyl dithio hypophosphites and the mass ratio at carbon component are 1.25~3.5:1,
Dialkyl dithio hypophosphites is selected from diisobutyl dithiophosphlic acid aluminium.
The TPU elastomer combination based on dialkyl dithio hypophosphites composite flame retardant system that the invention also discloses described
The preparation method of object, comprising:
After mixing by each component, extruding pelletization is carried out.
The TPU elastic composition completes extruding pelletization in double screw extruder, since fire retardant is thermal sensitivity object
Matter, 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
Extruding pelletization is completed in double screw extruder, there is certain requirement to extrusion equipment, and the draw ratio of double screw extruder is not small
In 44, preferably it is not less than 48, more preferably 52.The composition completes extruding pelletization in double screw extruder, can be used
Water cooling bracing mode, water ring pelletizing or underwater cutpellet.
According to TPU elastic composition prepared by the above method, the sheath material or insulating materials of cable can be used as, lead to
It crosses extrusion molding process and prepares cable on existing cable apparatus.
Compared with prior art, the present invention has the advantage that
The present invention provides a kind of TPU bullet of wire and cable based on dialkyl dithio hypophosphites composite flame retardant system
Elastomeric composition, comprising being prepared by dialkyl dithio hypophosphites and the special novel flame-retardant system being grouped as at carbon group
The cable material arrived has the characteristics that no molten drop, high fire-retardance, resistance to migration, soft abrasion-resistant, oil resistant, can reach the fire-retardant mark of VW-1
It is quasi-.
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:
1, fire-retardant and melt-dropping property
Testing standard according to cable material VW-1 is tested, and pays close attention to molten drop.
2, 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.
Using diisobutyl dithiophosphlic acid aluminium as raw material in the present embodiment, preparation process is as follows:
The sulphur of diisobutyl the dithiophosphlic acid sodium water solution 1392g and concentration 30wt% of compound concentration 20wt% respectively
Desalted water 1500g is added into reactor, and the sulfuric acid solution 75g of concentration 25wt% is added by sour aluminum solutions 228g, is warming up to 80
DEG C, start to synchronize dropwise addition diisobutyl dithiophosphlic acid sodium water solution and aluminum sulfate solution in proportion into reaction kettle, obtain
Diisobutyl dithiophosphlic acid aluminum precipitation object, is added dropwise to complete for 2 hours, keeps the temperature 1 hour, is then filtered, washed, dries, obtain
Diisobutyl dithiophosphlic acid aluminium fire retardant 254g (yield 97%).
After tested, 350 DEG C of the initial decomposition temperature of product, solubility is 0.02% in water；
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, slightly below calculated value), solubility < 0.1%, 1% weightlessness decomposition temperature is 320 DEG C.
Unless otherwise instructed, the diisobutyl dithiophosphlic acid aluminium in following embodiment and this is all made of at carbon component
The product of embodiment preparation.
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 diisobutyl dithiophosphlic acid aluminium and at the ratio adjustment of carbon component,
The ratio of diisobutyl dithiophosphlic acid aluminium is improved, keeps flame-retardant system total amount constant.Other materials and proportion are shown in Table 1, institute
Obtained material the results are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, in addition to diisobutyl dithiophosphlic acid aluminium and at the ratio adjustment of carbon component,
The ratio of carbon component is improved into, keeps flame-retardant system total amount constant.Other materials and proportion are shown in Table 1, obtained material result
It is shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, in addition to the adjustment of the ratio 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 ratio 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 diisobutyl dithiophosphlic acid aluminium.Other materials and match
Than being 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, does not use diisobutyl dithiophosphlic acid
Aluminium 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, in addition to diisobutyl dithiophosphlic acid aluminium is substituted for diethyl hypophosphorous acid
Aluminium.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 TPU elastic composition of wire and cable based on dialkyl dithio hypophosphites composite flame retardant system,
It is characterized in that, by weight percentage, raw material composition includes:
TPU basis material 65~90%；
Composite flame retardant system 10~30%；
Other auxiliary agents 0~5%；
The composite flame retardant system includes dialkyl dithio hypophosphites and at carbon component；
The dialkyl dithio hypophosphites, shown in structural formula such as following formula (I):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4；
It is described to be divided into insoluble insoluble cross-linked polymer at carbon group, shown in Crosslink structure such as following formula (II):
2. TPU of the wire and cable according to claim 1 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that the composite flame retardant system, by weight percentage, raw material composition includes:
50~90wt% of dialkyl dithio hypophosphites；
At 10~50wt% of carbon component.
3. TPU of the wire and cable according to claim 1 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that the dialkyl dithio hypophosphites, R1、R2Independently selected from methyl, ethyl, positive third
Base, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
4. TPU of the wire and cable according to claim 1 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that the dialkyl dithio hypophosphites, average grain diameter D50 < 5 μm.
5. TPU of the wire and cable according to claim 1 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that the preparation process at carbon 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.
6. TPU of the wire and cable according to claim 5 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that
The phase transfer catalyst is selected from quaternary ammonium salt；
It is described to vacuumize, until vacuum degree is not higher than 50KPa；
The crushing, until average grain diameter D50 < 5 μm.
7. TPU of the wire and cable according to claim 1 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that the TPU basis material is selected from polyester polyurethane, polyether polyurethane, polycarbonate
At least one of type polyurethane, polycaprolactone-type urethane, aliphatic anti-yellowing polyurethane.
8. TPU of the wire and cable according to claim 1 based on dialkyl dithio hypophosphites composite flame retardant system
Elastic composition, which is characterized in that other described auxiliary agents include at least one of lubricant, antioxidant, pigment.
9. a kind of wire and cable any according to claim 1~8, which is used, is based on the compound resistance of dialkyl dithio hypophosphites
The preparation method of the TPU elastic composition of combustion system characterized by comprising after mixing by each component, squeezed out
It is granulated.
10. TPU of the wire and cable according to claim 9 based on dialkyl dithio hypophosphites composite flame retardant system
The preparation method of elastic composition, which is characterized in that the extruding pelletization carries out in double screw extruder, and extrusion temperature is not
Higher than 230 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810684867.1A CN109021541B (en) | 2018-06-28 | 2018-06-28 | TPU (thermoplastic polyurethane) elastomer composition based on dialkyl dithiophosphate composite flame-retardant system for wires and cables and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810684867.1A CN109021541B (en) | 2018-06-28 | 2018-06-28 | TPU (thermoplastic polyurethane) elastomer composition based on dialkyl dithiophosphate composite flame-retardant system for wires and cables and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN109021541A true CN109021541A (en) | 2018-12-18 |
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| CN114008102A (en) * | 2019-06-24 | 2022-02-01 | 巴斯夫欧洲公司 | Water-emulsifiable isocyanates having improved properties |
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