CN109385071A - A kind of flame retardant property reaches the TPU material and preparation method thereof of vertical combustion V0 grade - Google Patents
A kind of flame retardant property reaches the TPU material and preparation method thereof of vertical combustion V0 grade 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
- C08L75/08—Polyurethanes from polyethers
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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
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- C08K2003/387—Borates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention provides the TPU materials and preparation method thereof that a kind of flame retardant property reaches vertical combustion V0 grade, in parts by weight, the TPU material is by 100 parts of thermoplastic polyurethanes, 35~65 parts of phosphorus nitrogen flame-retardant systems, 2~10 parts of carbon forming agents and 3~15 parts of flame retardants are kneaded to obtain, the present invention is by being applied to thermoplastic polyurethane for phosphorus nitrogen flame-retardant system, change simultaneously the proportion relation between wherein each component, a kind of excellent fireproof performance can be obtained, vertical combustion grade reaches V0 grades, oxygen index (OI) reaches 39% and the TPU material that does not change substantially of mechanical property, it can satisfy demand of the use occasion for its flame retardant property of most TPU materials.
Description
Technical field
The invention belongs to the TPU materials that fire proofing field more particularly to a kind of flame retardant property reach vertical combustion V0 grade
Material and preparation method thereof.
Background technique
Polyurethane, especially thermoplastic polyurethane (TPU) material have been widely used in many fields tool, however, it has
One very fatal weakness, that is, inflammable and it is not easy self-extinguishment, containing a large amount of flammable hydrocarbon segments in the molecular structure of TPU material,
Its density is small, and large specific surface area, thermal coefficient is low, and not fire retardant treated TPU material is common combustibles, and limit oxygen refers to
Number generally below 19, can generate a large amount of toxic smog when meeting fire burning, bring difficulty to fire extinguishing, especially it is in combustion process
In it also occur that expansion orifice, percent opening is higher, and combustible component is more, once kindling, due to air stream with higher when burning
The general character and oxygen disconnected in a steady stream supply, are difficult self-extinguishment, seriously limit it and be widely used.
With the fast development of global economy and the enhancing of mankind's environmental consciousness, each field to the quality of TPU material and
The requirement of performance is higher and higher, especially in terms of its flame retardant property, in order to reduce fire incidence and occur fire when
The death rate, low cigarette, Halogen, fire-retardant, the environmentally friendly mainstream development direction for becoming TPU materials industry.Traditional flame-retardant modified side
Method is the components such as a large amount of chlorinated paraffin and inorganic filler to be added in TPU material to reach flame retardant effect, however, a large amount of above-mentioned
The addition of fire proofing, physical mechanical property and processing performance to TPU material make it at normal temperature there are large effect
Softness, weather-resistant property, oil resistance, resistance to low temperature etc. are not fine.Reaction-type flame-retarding is added into TPU material
Agent is to improve the more convenient and cost-effective method of one kind of its flame retardant property, mainly pass through inorganic fire retardants for example antimony, aluminium,
The compound and organic fire-retardant of boron, phosphorus etc. such as phosphorus-halogen organic ester, halogenated phosphate, halogenated aliphatic hydrocarbon, organic phosphorus compound etc.
Occur combination reaction during burning between fire retarding synergist, such as carbon forming agent and flame retardant, generate thermal conductivity compared with
The carburization zone of difference, the influence with starvation and high temperature to internal material avoid the further occurrence of combustion process.
Currently, the fire retardant and fire retarding synergist that can be used for TPU material are usually with the change of the elements such as organic phosphorous, chlorine, bromine
Close based on object, for example, disclosed in CN104650441A it is a kind of can ceramic flame-retardant high-molecular composite material, including 30~40
The thermoplastic polyurethane elastomer of parts by weight, 25~45 parts by weight at porcelain filling, the halogen-free flame retardants of 20~30 parts by weight, 1
The synergistic flame retardant of~5 parts by weight, the plasticizer of 1~3 parts by weight, the antioxidant of 0.5~2 parts by weight and 0.02~0.15 weight
The crosslinking agent of part, the performance indicator of testing vertical flammability can reach V0 grades, and limit oxygen index can reach 28%；
A kind of halogen-free flameproof Polyether-type thermoplastic polyurethane elastomer is disclosed in CN104693782A, material component includes 100 parts
Polyether-type thermoplastic polyurethane elastomer resin, 30~50 parts by weight phosphorus nitrogen flame-retardant system, 1~5 parts by weight fire-retardant increasing
Imitate agent, the antioxidant of 0.5~2 parts by weight, the surface modifier of 0.5~2 parts by weight, 0.5~2 parts by weight coupling agent and 0.5
The lubricant of~4 parts by weight, obtained approximately fire-retardant TPU material also have preferable flame retardant effect, and UL-94 test can reach
To V0 rank, limit oxygen index can reach 33% or more；However, fire-retardant when above-mentioned organic fire-resisting system is for TPU material
Effect still needs to be further increased, after it is blended with polyurethane material, to the mechanical property such as toughness and mould of polyurethane material
Amount etc., reduction degree is larger, and the compatibility after being blended with polyurethane material is also poor, is dispersed in it by processing poly-
More difficult in urethane material, price is relatively expensive, also limits its application.
Therefore, on the basis of existing technology, it is good to need to develop a kind of novel flame retardant property by those skilled in the art
Good flame-retardant system, making it, cost is relatively low, is suitable for Thermoplastic polyurethane elastomer material, processing technology is easy, in polyurethane
The TPU material for being uniformly dispersed in elastomer, not will lead to the decline of TPU material mechanical performance, while making has excellent
Flame retardant property, flame retardant property reaches vertical combustion V0 grade, and limit oxygen index can reach 33% or more.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of novel good resistance of flame retardant property
Combustion system, making it, cost is relatively low, is suitable for Thermoplastic polyurethane elastomer material, processing technology is easy, in polyurethane elastomer
In be uniformly dispersed, the TPU material that not will lead to the decline of TPU material mechanical performance, while making has excellent fire-retardant
Performance, flame retardant property reach vertical combustion V0 grade, and limit oxygen index can reach 33% or more.
For this purpose, one of the objects of the present invention is to provide a kind of flame retardant properties to reach vertical combustion V0 grade
TPU material, in parts by weight, the TPU material are kneaded to obtain by following component:
Wherein, the parts by weight of phosphorus nitrogen flame-retardant system can for 37 parts, 39 parts, 41 parts, 43 parts, 45 parts, 47 parts, 49 parts,
51 parts, 53 parts, 55 parts, 57 parts, 59 parts, 61 parts or 63 parts etc., the parts by weight of carbon forming agent can be 3 parts, 4 parts, 5 parts, 6 parts, 7
Part, 8 parts or 9 parts etc., the parts by weight of flame retardant can be 5 parts, 7 parts, 9 parts, 11 parts, 13 parts or 14 parts etc..
The phosphorus nitrogen flame-retardant system presses 0.5~1.5:1 (for example, by melamine cyanurate and aluminum diethylphosphinate
0.6:1,0.7:1,0.8:1,0.9:1,1:1,1.1:1,1.2:1,1.3:1 or 1.4:1 etc.) weight ratio be blended to obtain, upper
It states under conditions of mixture ratios, obtained phosphorus nitrogen flame-retardant system has optimal flame retardant effect, the association between carbon forming agent and flame retardant
Also it is optimal with effect.
Preferably, in parts by weight, the TPU material is blended to obtain by following component:
Preferably, the carbon forming agent is lignin, and lignin is the slave waste wood containing more phenyl, alkyl chain and phenolic hydroxyl group
It is middle to purify obtained compound, compared with easy firing when being used alone, but when it is cooperateed with fire retardant and flame retardant in use, altogether
When being mixed in polyurethane system, phenolic hydroxyl group therein can slough water at high temperature, and simultaneously ring, crosslinking etc. occur between other phenyl ring
Reaction, obtains heat-insulated carbonized structure, at charcoal excellent effect, moreover, lignin itself is because of phenyl and hydroxy functional group there are many containing,
The effect that toughener can be played is blended in polyurethane, and the TPU material that can guarantee still maintains at high temperature
The mechanical properties such as higher toughness.
Preferably, the number-average molecular weight of the lignin be 1000~10000, for example, 1500,2000,2500,3000,
3500,4000,4500,5000,5500,6000,6500,7000,7500,8000,8500,9000 or 9500 etc..
Preferably, the number-average molecular weight of the lignin be 3000~8000, under above-mentioned molecular weight, lignin with it is fire-retardant
Synergy between agent and flame retardant is optimal.
Preferably, the flame retardant is any one in hydrotalcite, organo montmorillonite, zinc borate or rare earth oxide
Or at least two mixture.
Preferably, the flame retardant be zinc borate and organo montmorillonite weight ratio be 0.4~2:1 (for example, 0.5:1,
0.6:1,0.7:1,0.8:1,0.9:1,1:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1 or
1.9:1 etc.) mixture.
Preferably, the thermoplastic polyurethane is polyether polyurethane.
The second object of the present invention is to provide a kind of preparation method of TPU material, and the preparation method includes such as
Lower step:
The thermoplastic polyurethane of formula ratio, phosphorus nitrogen flame-retardant system, carbon forming agent and flame retardant are uniformly mixed, mixing is placed in
It is kneaded in machine to get the TPU material is arrived.
Preferably, described be uniformly mixed carries out in a high speed mixer.
Preferably, the temperature of the mixing is 160~190 DEG C, for example, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C
Or 188 DEG C etc..
Preferably, the time of the mixing be 0.5~1h, for example, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h,
0.85h, 0.9h or 0.95h etc..
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
The present invention changes simultaneously matching between wherein each component by the way that phosphorus nitrogen flame-retardant system is applied to thermoplastic polyurethane
Than relationship, a kind of excellent fireproof performance can be obtained, vertical combustion grade reaches V0 grades, and oxygen index (OI) reaches 39% and mechanical property
Substantially the TPU material not changed can satisfy need of the use occasion for its flame retardant property of most TPU materials
It asks.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
It is prepared via a method which TPU material 1:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 5000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 1.
Embodiment 2
It is prepared via a method which TPU material 2:
By 10kg polyether thermoplastic polyurethane, 3kg melamine cyanurate, 2kg aluminum diethylphosphinate, 0.8kg
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that number-average molecular weight is 5000 are mixed using high-speed mixer
Uniformly, it is placed in mixer and is kneaded, the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material 2.
Embodiment 3
It is prepared via a method which TPU material 3:
By 10kg polyether thermoplastic polyurethane, 2kg melamine cyanurate, 4kg aluminum diethylphosphinate, 0.8kg
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that number-average molecular weight is 5000 are mixed using high-speed mixer
Uniformly, it is placed in mixer and is kneaded, the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material 3.
Embodiment 4
It is prepared via a method which TPU material 4:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 1kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 5000 use high-speed mixer
It is uniformly mixed, is placed in mixer and is kneaded, the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
4。
Embodiment 5
It is prepared via a method which TPU material 5:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
The carbon forming agent lignin, 0.09kg zinc borate and 0.21kg organo montmorillonite that 0.8kg number-average molecular weight is 5000 are mixed using high speed
Conjunction machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU
Material 5.
Embodiment 6
It is prepared via a method which TPU material 6:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.2kg number-average molecular weight is 5000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 160 DEG C, and the time of mixing is 30min, obtains the TPU material
Material 6.
Embodiment 7
It is prepared via a method which TPU material 7:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 1kg number-average molecular weight is 5000 use high-speed mixer
It is uniformly mixed, is placed in mixer and is kneaded, the temperature of mixing is 190 DEG C, and the time of mixing is 60min, obtains the TPU material
7。
Embodiment 8
It is prepared via a method which TPU material 8:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 8000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 8.
Embodiment 9
It is prepared via a method which TPU material 9:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 3000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 9.
Embodiment 10
It is prepared via a method which TPU material 10:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 12000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 10.
Embodiment 11
It is prepared via a method which TPU material 11:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 1.2kg number-average molecular weight is 5000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 11.
Embodiment 12
It is prepared via a method which TPU material 12:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
0.8kg carbon forming agent piperazine pyrophosphate, 0.5kg zinc borate and 0.5kg organo montmorillonite are uniformly mixed using high-speed mixer, are placed in
It is kneaded in mixer, the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material 12.
Reference examples 1
It is prepared via a method which TPU material 13:
By 10kg polyether thermoplastic polyurethane, 3.5kg melamine cyanurate, 3.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 5000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 13.
Reference examples 2
It is prepared via a method which TPU material 14:
By 10kg polyether thermoplastic polyurethane, 1.5kg melamine cyanurate, 1.5kg aluminum diethylphosphinate,
Carbon forming agent lignin, 0.5kg zinc borate and the 0.5kg organo montmorillonite that 0.8kg number-average molecular weight is 5000 use mixed at high speed
Machine is uniformly mixed, and is placed in mixer and is kneaded, and the temperature of mixing is 180 DEG C, and the time of mixing is 40min, obtains the TPU material
Material 14.
Reference examples 3
It is prepared via a method which TPU material 15:
By 10kg polyether thermoplastic polyurethane, 2.5kg melamine cyanurate, 2.5kg aluminum diethylphosphinate,
0.5kg zinc borate and 0.5kg organo montmorillonite are uniformly mixed using high-speed mixer, are placed in mixer and are kneaded, the temperature of mixing
Degree is 180 DEG C, and the time of mixing is 40min, obtains the TPU material 15.
It is carried out according to performance of the following test method to TPU material 1~15 obtained in the various embodiments described above and reference examples
Test, test result are listed in table 1:
(1) Mechanics Performance Testing
According to method described in Nippon Standard JIS K7311-1995 " test method of thermoplastic polyurethane elastomer "
Test the elongation at break of obtained TPU material 1~15.
(2) flame retardant property is tested
The TPU tested according to method described in GB/T 10707-2008 " the measurement standard of rubber combustion performance "
The vertical combustion grade and oxygen index (OI) of material 1~15, to characterize its flame retardant property, wherein vertical combustion grade be V0 grades when and
Flame retardant property is more excellent when oxygen index (OI) is higher.
The performance comparison table of table 1TPU material 1~15
| TPU material | Vertical combustion grade (grade) | Oxygen index (OI) (%) | Elongation at break (%) |
| 1 | V0 | 39 | 591 |
| 2 | V0 | 38 | 566 |
| 3 | V0 | 37 | 581 |
| 4 | V0 | 37 | 585 |
| 5 | V0 | 37 | 580 |
| 6 | V0 | 35 | 567 |
| 7 | V0 | 38 | 575 |
| 8 | V0 | 37 | 584 |
| 9 | V0 | 37 | 570 |
| 10 | V0 | 37 | 562 |
| 11 | V0 | 36 | 571 |
| 12 | V0 | 37 | 520 |
| 13 | V0 | 32 | 532 |
| 14 | V1 | 33 | 565 |
| 15 | V1 | 30 | 514 |
From table 1 embodiment 1 and embodiment 12 and reference examples 3 to TPU material performance comparison it is found that in the present invention
Influence of the carbon forming agent for flame retardant property is fairly obvious, and when lignin material is as carbon forming agent, relative to other carbon forming agents with
It is more preferable at charcoal effect after fire retardant compounding, while the toughness for the TPU material that can also be obviously improved, make its extension at break
Rate improves 15% or so, and the performance comparison of the TPU material obtained from embodiment 1 and embodiment 6~11 is it is found that work as lignin component
Content is 2~10 parts, and for number-average molecular weight at 3000~10000 or so, obtained TPU material not only has excellent anti-flammability
Can, mechanical property will not be remarkably decreased.
From the performance comparison between the TPU material that Examples 1 to 5 in table 1 and reference examples 1~2 obtain it is found that working as component
When middle phosphorus nitrogen flame-retardant system content is excessive, very few or its component proportion changes, the anti-flammability for the TPU material that can accordingly reduce
Energy and mechanical property, but decline unobvious.
In conclusion the present invention changes simultaneously wherein each group by the way that phosphorus nitrogen flame-retardant system is applied to thermoplastic polyurethane
/ proportion relation, a kind of excellent fireproof performance can be obtained, vertical combustion grade reaches V0 grades, and oxygen index (OI) reaches 39%
And the TPU material that mechanical property does not change substantially, the use occasion that can satisfy most TPU materials are fire-retardant for its
The demand of performance.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. the TPU material that a kind of flame retardant property reaches vertical combustion V0 grade, which is characterized in that in parts by weight, described
TPU material is kneaded to obtain by following component:
The phosphorus nitrogen flame-retardant system is total to by melamine cyanurate and aluminum diethylphosphinate by the weight ratio of 0.5~1.5:1
It is mixed to obtain.
2. TPU material according to claim 1, which is characterized in that in parts by weight, the TPU material is by as follows
Component is blended to obtain:
3. TPU material according to claim 1 or 2, which is characterized in that the carbon forming agent is lignin.
4. TPU material according to claim 3, which is characterized in that the number-average molecular weight of the lignin be 1000~
10000。
5. TPU material according to claim 3, which is characterized in that the number-average molecular weight of the lignin be 3000~
8000。
6. TPU material described according to claim 1~one of 5, which is characterized in that the flame retardant is hydrotalcite, organic
In montmorillonite, zinc borate or rare earth oxide any one or at least two mixture.
7. TPU material described according to claim 1~one of 6, which is characterized in that the flame retardant is zinc borate and organic
Montmorillonite weight ratio is the mixture of 0.4~2:1.
8. TPU material described according to claim 1~one of 7, which is characterized in that the thermoplastic polyurethane is poly- for polyether-type
Urethane.
9. a kind of preparation method of the TPU material as described in one of claim 1~8, which is characterized in that the preparation method packet
Include following steps:
The thermoplastic polyurethane of formula ratio, phosphorus nitrogen flame-retardant system, carbon forming agent and flame retardant are uniformly mixed, are placed in mixer
It is kneaded to get the TPU material is arrived.
10. preparation method according to claim 9, which is characterized in that described be uniformly mixed carries out in a high speed mixer；
Preferably, the temperature of the mixing is 160~190 DEG C；
Preferably, the time of the mixing is 0.5~1h.
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| CN112812366A (en) * | 2020-12-30 | 2021-05-18 | 浙江新化化工股份有限公司 | Flame-retardant composition and application thereof, PBT composite material and preparation method thereof |
| CN113265141A (en) * | 2020-03-08 | 2021-08-17 | 广东奇德新材料股份有限公司 | Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application |
| CN113416406A (en) * | 2021-07-27 | 2021-09-21 | 中广核高新核材科技（苏州）有限公司 | TPU fuel inhibitor and preparation method thereof |
| CN114437425A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Thermoplastic vulcanized rubber composition, thermoplastic vulcanized rubber, and preparation method and application thereof |
| WO2022136413A1 (en) * | 2020-12-21 | 2022-06-30 | Basf Se | Flame-retarded thermoplastic polyurethane |
| CN116478527A (en) * | 2023-06-25 | 2023-07-25 | 潍坊潍星联合橡塑有限公司 | Flame-retardant polyurethane cable outer sheath material |
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| WO2022136413A1 (en) * | 2020-12-21 | 2022-06-30 | Basf Se | Flame-retarded thermoplastic polyurethane |
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| CN116478527A (en) * | 2023-06-25 | 2023-07-25 | 潍坊潍星联合橡塑有限公司 | Flame-retardant polyurethane cable outer sheath material |
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