CN106065062A - A kind of flame retarding type thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
A kind of flame retarding type thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention provides a kind of flame retarding type thermoplastic polyurethane elastomer and preparation method thereof, this flame retarding type thermoplastic polyurethane elastomer is by weight mainly prepared by following raw material: polyhexamethylene adipate glycol 22 38 parts；Polyether polyol 26 42 parts；Methyl diphenylene diisocyanate 32 45 parts；Chain extender 48 parts；Catalyst 0.005 0.012 parts；Nitrogen system bittern-free fire retardant 5 12 parts；Expended microsphere 10 16 parts；Age resister 0.5 1 parts；Described catalyst be mass ratio be (3 5): the organotin of 1 and organo-bismuth.The Polyurethane Thermoplastic Elastomer that the present invention prepares has microcellular structure, and nitrogen system bittern-free fire retardant and the mutual synergism of expended microsphere, make the Polyurethane Thermoplastic Elastomer prepared have the anti-flammability of excellence, also there is good combination property and relatively low tensile set characteristic.
Description
Technical field
The invention belongs to technical field of polyurethane elastomer, be specifically related to a kind of flame retarding type thermoplastic polyurethane elastomer and
Its preparation method.
Background technology
Thermoplastic polyurethane elastomer (TPU) is a polyurethane material that class heating can plastify, solvent can dissolve, tool
There is the soft or hard section block copolymer structure of uniqueness, there is the elasticity of rubber and the machinability of plastics because of it, at many necks simultaneously
Territory is used widely.But the effect of TPU stress to be stood, the compression gone round and begun again or stretching shape
State makes goods be easy to deform, even if external force eliminates, goods also are difficult to return to original state, thus a certain amount of, nothing occur
The residual deformation that method is recovered, i.e. permanent deformation.TPU high permanent deformation makes it receive limit in the application as elastomeric material field
System.
CN 104387560A discloses a kind of Polyurethane Thermoplastic Elastomer and preparation method thereof, described thermoplastic poly ammonia
Ester elastomer is made up of the raw material of following percentage by weight: PEPA 61-69%, diisocyanate 24-30%, chain extender
4-8%, catalyst 0.005-0.012%, age resister 0.3-1%.Although described Polyurethane Thermoplastic Elastomer has preferably
The characteristic of low tensile set, but its anti-flammability is poor, limits its application in real life.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide a kind of flame retarding type thermoplastic polyurethane elastomer
And preparation method thereof, described flame retarding type thermoplastic polyurethane elastomer not only has low tensile set characteristic and good machine
Tool performance and processability also have fire resistance and the elasticity of excellence.
For reaching this purpose, the present invention provides following technical scheme:
A kind of flame retarding type thermoplastic polyurethane elastomer, described flame retarding type thermoplastic polyurethane elastomer percentage by weight contains
Amount is mainly prepared by following raw material:
Described catalyst be mass ratio be (3-5): the organotin of 1 and organo-bismuth.
The flame retarding type thermoplastic polyurethane elastomer (TPU) that the present invention provides mainly is prepared by following raw material: poly-own
Diacid hexanediol esterdiol 22-38 part, such as 23 parts, 24 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts or 36 parts etc.；Polyether polyols
Alcohol 26-42 part, such as 27 parts, 29 parts, 31 parts, 32 parts, 38 parts or 38 parts etc.；Methyl diphenylene diisocyanate (MDI-100) 32-
45 parts, such as 35 parts, 38 parts, 40 parts, 41 parts, 42 parts or 44 parts etc.；Chain extender 4-8 part, such as 4 parts, 5 parts, 6 parts, 7 parts or 8 parts etc.；
Catalyst 0.005-0.012 part, such as 0.005 part, 0.006 part, 0.008 part, 0.009 part or 0.011 part etc.；Nitrogen system bittern-free is fire-retardant
Agent 5-12 part, such as 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or 11 parts etc.；Expended microsphere 10-16 part, as 11 parts, 12 parts, 13 parts, 14
Part, 15 parts or 15.5 parts etc.；Age resister 0.5-1 part, such as 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part etc..
The mass ratio of described organotin and organo-bismuth is 3:1,4:1 or 5:1 etc..
As preferred technical scheme, described flame retarding type thermoplastic polyurethane elastomer percentage composition by weight is mainly by such as
Lower raw material prepares:
As preferred technical scheme, described flame retarding type thermoplastic polyurethane elastomer percentage composition by weight mainly by
Following raw material prepares:
The degree of functionality of described polyether polyol is 2.02-2.10, such as 2.05,2.06,2.07,2.08 or 2.09 etc..
Preferably, the molecular weight of described polyether polyol is 200-1000, such as 280,300,400,500,550,700,
900 or 950 etc..
Described nitrogen system bittern-free fire retardant is the one in tripolycyanamide, dicyandiamide or melamine cyanurate or at least
The combination of two kinds, typical but non-limiting tripolycyanamide and dicyandiamide, melamine cyanurate and the dicyandiamide of being combined as, three
Poly cyanamid, dicyandiamide and melamine cyanurate etc..
Described expended microsphere is the microcapsule of heat expandable, by polymer shell and the foaming agent group wrapped up by it
Become.
Preferably, described polymer shell is acrylonitrile copolymer.
The addition of described expended microsphere enables to thermoplastic polyurethane and has microcellular structure, simultaneously itself and nitrogen system bittern-free
Fire retardant is mutually collaborative plays flame retardant effect so that prepared Polyurethane Thermoplastic Elastomer has the anti-flammability of excellence.
It addition, the shell of expended microsphere is acrylonitrile copolymer, it has the good compatibility with thermoplastic polyurethane,
Therefore can be uniformly distributed in polyurethane elastomer so that the micropore in finished product is evenly distributed, uniform force during use.
Described chain extender is little molecule glycol, and the molecular weight of little molecule glycol is 50-140, such as 60,70,80,90,
100,120 or 130 etc..
Preferably, described chain extender is preferably ethylene glycol (EG), 1,2-PD (PG), BDO (BDO), first
Any one in base propylene glycol, 1,3 butylene glycol, diglycol, 1,6-hexanediol or neopentyl glycol or the group of at least two
Closing, typical but non-limiting combination has ethylene glycol (EG) and 1,2-PD (PG), BDO (BDO) and methyl-prop two
Alcohol, 1,3 butylene glycol, diglycol, 1,6-hexanediol and neopentyl glycol, 1,3 butylene glycol, diglycol and 1,6-
Hexanediol etc..
Described age resister be mass ratio be (4-10): the 1076 and UV-531 of 1.
The preparation method of flame retarding type thermoplastic polyurethane elastomer of the present invention, described preparation method includes walking as follows
Rapid:
(1) by the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, inflatable micro-
Ball, catalyst, age resister, chain extender add in the reactor being furnished with mechanical agitation and thermometer, under agitation temperature are added
Heat to 100-120 DEG C, is dehydrated 1-3h at 0.85-0.1MPa, then cools the temperature to 70-90 DEG C, adds fusing and accurately counts
The methyl diphenylene diisocyanate of amount, mixes 1-3min under 3000-4000r/min stirs, pours into and be pre-coated with releasing agent
Flat plate mold in, ripening 20-30h in 80-110 DEG C of baking oven, obtain thin slice；
(2) gained thin slice is broken into the single-size that particle diameter is 1-2mm, is processed into 1-3mm's with vertical injection molding machine injection
Thin slice, ambient temperatare puts 3-8 days.
The present invention compared with prior art, has the advantages that
The present invention hinders by adding expended microsphere and nitrogen system bittern-free during synthetic thermoplastic polyurethane elastomer
Combustion agent, foams within being placed in the expansion temperature window of expended microsphere, the Polyurethane Thermoplastic Elastomer tool prepared
There are microcellular structure, and nitrogen system bittern-free fire retardant phase mutual with expended microsphere same-action so that prepared thermoplastic polyurethane
Elastomer has the anti-flammability of excellence.
The present invention, by polyester-diol is branched modification, is former with diisocyanate, chain extender and a small amount of auxiliary agent
Material uses simple one-step method, has synthesized Polyurethane Thermoplastic Elastomer.Synthesized TPU is at its soft chain segment, soft chain segment and hard
Segment microcell contains the chemical crosslinking of trace, imparts combination property good for TPU and relatively low tensile set characteristic.Greatly
Extend greatly its dimensional stability and ruggedness.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
The synthesis of flame retardant type TPU:
According to percent by weight,
Described catalyst be mass ratio be organotin and the organo-bismuth of 3:1.
Age resister be mass ratio be the 1076 and UV-531 of 7:1.
The degree of functionality of polyether polyol is 2.02；
The molecular weight of described polyether polyol is 1000.
Nitrogen system bittern-free fire retardant is tripolycyanamide.
Chain extender is ethylene glycol.
By the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, expended microsphere,
Catalyst, age resister and chain extender mixing, be dehydrated 2h at 110 DEG C, then cool the temperature to 80 DEG C, add the MDI-of metering
100, under 4000r/min rotating speed, mix 2min, pour in the flat plate mold being pre-coated with releasing agent, ripening in 90 DEG C of baking ovens
24h, gained thin slice is broken into the single-size that particle diameter is 1.5mm, is processed into the thin slice of 2mm, room temperature with vertical injection molding machine injection
Lower placement surveys its performance in 6 days, obtains the goods of shore hardness 87A when 25 DEG C.Product properties is shown in Table 1.
Embodiment 2
The synthesis of flame retardant type TPU:
According to percent by weight,
Described catalyst be mass ratio be organotin and the organo-bismuth of 5:1.
Age resister be mass ratio be the 1076 and UV-531 of 4:1.
The degree of functionality of polyether polyol is 2.10；
The molecular weight of described polyether polyol is 200.
Nitrogen system bittern-free fire retardant is tripolycyanamide and dicyandiamide.
Chain extender is ethylene glycol and 1,2-PD.
By the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, expended microsphere,
Catalyst, age resister and chain extender mixing, be dehydrated 2h at 110 DEG C, then cool the temperature to 80 DEG C, add the MDI-of metering
100, under 4000r/min rotating speed, mix 2min, pour in the flat plate mold being pre-coated with releasing agent, ripening in 90 DEG C of baking ovens
24h, gained thin slice is broken into the single-size that particle diameter is 1.5mm, is processed into the thin slice of 2mm, room temperature with vertical injection molding machine injection
Lower placement surveys its performance in 6 days, obtains the goods of shore hardness 84A when 25 DEG C.Product properties is shown in Table 1.
Embodiment 3
The synthesis of flame retardant type TPU:
According to percent by weight,
Described catalyst be mass ratio be organotin and the organo-bismuth of 4:1.
Age resister be mass ratio be the 1076 and UV-531 of 10:1.
The degree of functionality of polyether polyol is 2.2；
The molecular weight of described polyether polyol is 500-600.
Nitrogen system bittern-free fire retardant is tripolycyanamide, dicyandiamide and melamine cyanurate.
Chain extender is ethylene glycol, 1,2-PD and BDO.
By the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, expended microsphere,
Catalyst, age resister and chain extender mixing, be dehydrated 2h at 110 DEG C, then cool the temperature to 80 DEG C, add the MDI-of metering
100, under 4000r/min rotating speed, mix 2min, pour in the flat plate mold being pre-coated with releasing agent, ripening in 90 DEG C of baking ovens
24h, gained thin slice is broken into the single-size that particle diameter is 1.5mm, is processed into the thin slice of 2mm, room temperature with vertical injection molding machine injection
Lower placement surveys its performance in 6 days, obtains the goods of shore hardness 81A when 25 DEG C.Product properties is shown in Table 1.
Embodiment 4
The synthesis of flame retardant type TPU:
According to percent by weight,
Described catalyst be mass ratio be organotin and the organo-bismuth of 3:1.
Age resister be mass ratio be the 1076 and UV-531 of 4:1.
The degree of functionality of polyether polyol is 2.08；
The molecular weight of described polyether polyol is 400-500.
Nitrogen system bittern-free fire retardant is melamine cyanurate.
Chain extender is neopentyl glycol.
By the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, expended microsphere,
Catalyst, age resister and chain extender mixing, be dehydrated 2h at 110 DEG C, then cool the temperature to 80 DEG C, add the MDI-of metering
100, under 4000r/min rotating speed, mix 2min, pour in the flat plate mold being pre-coated with releasing agent, ripening in 90 DEG C of baking ovens
24h, gained thin slice is broken into the single-size that particle diameter is 1.5mm, is processed into the thin slice of 2mm, room temperature with vertical injection molding machine injection
Lower placement surveys its performance in 6 days, obtains the goods of shore hardness 84A when 25 DEG C.Product properties is shown in Table 1.
Embodiment 5
Described catalyst be mass ratio be organotin and the organo-bismuth of 3:1.
Age resister be mass ratio be the 1076 and UV-531 of 8:1.
The degree of functionality of polyether polyol is 2.25；
The molecular weight of described polyether polyol is 800-1000.
Nitrogen system bittern-free fire retardant is dicyandiamide.
Chain extender is methyl propanediol.
By the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, expended microsphere,
Catalyst, age resister and chain extender mixing, be dehydrated 2h at 110 DEG C, then cool the temperature to 80 DEG C, add the MDI-of metering
100, under 4000r/min rotating speed, mix 2min, pour in the flat plate mold being pre-coated with releasing agent, ripening in 90 DEG C of baking ovens
24h, gained thin slice is broken into the single-size that particle diameter is 1.5mm, is processed into the thin slice of 2mm, room temperature with vertical injection molding machine injection
Lower placement surveys its performance in 6 days, obtains the goods of shore hardness 84A when 25 DEG C.Product properties is shown in Table 1.
Comparative example 1
In addition to not containing melamine cyanurate in raw material, remaining is the same as in Example 4.
Comparative example 2
In addition to not containing expended microsphere in raw material, remaining is the same as in Example 4.
Comparative example 3
In addition to not containing polyether polyol in raw material, remaining is the same as in Example 4.
Comparative example 4
Except catalyst be mass ratio be organotin and the organo-bismuth of 2:1, remaining is the same as in Example 4.
Comparative example 5
Except catalyst be mass ratio be organotin and the organo-bismuth of 6:1, remaining is the same as in Example 4.
Fire resistance
Vertical combustion experiment according to UL (Underwriter ' s Laboratory) 94, measures the fire resistance of sample
(thickness: 3mm, width: 12.7mm, and length: 127mm；And thickness: 1mm, width: 12.7mm, and length: 127mm).?
In measurement, after flame combustion sample 10 seconds, record fall time (t1), the most again with flame combustion sample after 10 seconds, record
Fall time (t2).Here, when the summation of t1 and t2 was less than 30 seconds, fire-retardant rank is V1 or V2, when summation was less than 10 seconds
Time, fire-retardant rank is V0.Equally, when the absorbent tampons being placed on bottom is burnt due to burning drippage, flame retardant rating is V2, instead
It, when Cotton Gossypii is not burnt, flame retardant rating is V0 or V1.Equally, in UL94 vertical combustion is tested, also measure the secondary of drippage
Number.
Polyurethane elastomer product performance obtained by each embodiment of table 1 and comparative example
Applicant states, the foregoing is only the detailed description of the invention of the present invention, but protection scope of the present invention not office
Being limited to this, person of ordinary skill in the field is it will be clearly understood that any those skilled in the art of belonging to take off in the present invention
In the technical scope of dew, the change that can readily occur in or replacement, within the scope of all falling within protection scope of the present invention and disclosure.
Claims (9)
1. a flame retarding type thermoplastic polyurethane elastomer, it is characterised in that described flame retarding type thermoplastic polyurethane elastomer is pressed
Weight percentage is mainly prepared by following raw material:
Described catalyst be mass ratio be (3-5): the organotin of 1 and organo-bismuth.
Flame retarding type thermoplastic polyurethane elastomer the most according to claim 1, it is characterised in that described flame retarded thermoplastic
Polyurethane elastomer percentage composition by weight is mainly prepared by following raw material:
Flame retarding type thermoplastic polyurethane elastomer the most according to claim 1 and 2, it is characterised in that described flame retardant type heat
Plastic polyurethane elastomer percentage composition by weight is mainly prepared by following raw material:
4. according to the flame retarding type thermoplastic polyurethane elastomer one of claim 1-3 Suo Shu, it is characterised in that described polyethers
The degree of functionality of polyhydric alcohol is 2.02-2.10；
Preferably, the molecular weight of described polyether polyol is 200-1000.
5. according to the flame retarding type thermoplastic polyurethane elastomer one of claim 1-4 Suo Shu, it is characterised in that described nitrogen system
Halogen-free flame retardants is the combination of a kind of or at least two in tripolycyanamide, dicyandiamide or melamine cyanurate.
6. according to the flame retarding type thermoplastic polyurethane elastomer one of claim 1-5 Suo Shu, it is characterised in that described can be swollen
Swollen microsphere is the microcapsule of heat expandable, is made up of polymer shell and the foaming agent wrapped up by it；
Preferably, described polymer shell is acrylonitrile copolymer.
7. according to the flame retarding type thermoplastic polyurethane elastomer one of claim 1-6 Suo Shu, it is characterised in that described chain extension
Agent is little molecule glycol, and the molecular weight of little molecule dihydroxylic alcohols is 50-140；
Preferably, described chain extender be ethylene glycol, 1,2-PD, BDO, methyl propanediol, 1,3 butylene glycol,
One or more of diglycol, 1,6-hexanediol or neopentyl glycol.
8. according to the flame retarding type thermoplastic polyurethane elastomer one of claim 1-7 Suo Shu, it is characterised in that described is anti-ageing
Agent be mass ratio be (4-10): the 1076 and UV-531 of 1.
9. the preparation method of the flame retarding type thermoplastic polyurethane elastomer that one of claim 1-8 is described, it is characterised in that
Described preparation method comprises the steps:
(1) by the polyhexamethylene adipate glycol of formula ratio, polyether polyol, nitrogen system bittern-free fire retardant, expended microsphere, urge
Agent, age resister, chain extender add in the reactor being furnished with mechanical agitation and thermometer, under agitation temperature are heated to
100-120 DEG C, it is dehydrated 1-3h at 0.85-0.1MPa, then cools the temperature to 70-90 DEG C, add fusing and accurately measure
Methyl diphenylene diisocyanate, mixes 1-3min under 3000-4000r/min stirs, and pours into and is pre-coated with the flat of releasing agent
In board mold, ripening 20-30h in 80-110 DEG C of baking oven, obtain thin slice；
(2) gained thin slice is broken into the single-size that particle diameter is 1-2mm, is processed into the thin slice of 1-3mm with vertical injection molding machine injection,
Ambient temperatare puts 3-8 days.
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| CN114920981A (en) * | 2022-07-20 | 2022-08-19 | 山东一诺威聚氨酯股份有限公司 | Polyurethane tire filler foamed by using expanded microspheres and preparation method thereof |
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