CN107903615A - A kind of composite modified polyurethane material and preparation method thereof - Google Patents
A kind of composite modified polyurethane material and preparation method thereof Download PDFInfo
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- CN107903615A CN107903615A CN201711271454.2A CN201711271454A CN107903615A CN 107903615 A CN107903615 A CN 107903615A CN 201711271454 A CN201711271454 A CN 201711271454A CN 107903615 A CN107903615 A CN 107903615A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2201/00—Specific properties of additives
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- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of composite modified polyurethane material and preparation method thereof, including following parts by weight raw material to be prepared：50 60 parts of polyurethane, 5 15 parts of nano-aluminum hydroxide, 5 10 parts of modifying agent, 15 20 parts of neoprene, 0.3 0.8 parts of coupling agent, 25 parts of crosslinking agent, 5 10 parts of butyl titanate, 38 parts of zinc stearate；The present invention is for composite by the nano-aluminum hydroxide Jing Guo specific aim modification and polyurethane, and nano-aluminum hydroxide is set to be dispersed in polyurethane system, obtained modified polyurethane material resistance to elevated temperatures is excellent, is conducive to application of the polyurethane in more areas.
Description
Technical field
The present invention relates to modified material field, and in particular to a kind of composite modified polyurethane material and preparation method thereof.
Background technology
Polyurethane is the polymeric material containing carbamate groups in macromolecular main chain, has higher mechanical strength
And oxidation stability, higher flexibility and resilience, excellent oil resistivity, solvent resistance, water resistance and fire resistance, multiple
It is widely used in field.Polyurethane material is mainly used for aviation, railway, building, physical culture etc., available for wooden family
Tool and metallic surface Lacquer finish；For basin, pipeline, freezer, beer, fermentation tank, preservation drum adiabatic heat-insulation cold insulation, house is built
Build adiabatic waterproof, it can also be used to prefabricated polyurethane plate；It is fine available for manufacture plastic products, abrasive synthetic rubber product, synthesis
Dimension, hard and flex foam product, adhesive and coating etc.；For all kinds of woodenware, chemical industry equipment, telecommunication apparatus and instrument
And the top finishing of various forms of transport.
With the continuous improvement that people require material resistance to elevated temperatures, the polyurethane without heat resist modification has been difficult to full
Sufficient demand, thus, heat resist modification is carried out to polyurethane and is necessitated.Now to the heat resist modification processing method kind of polyurethane
Class is various, and modified effect is also fine, especially with the appearance and application of nano material, the heat-resisting quantity increase effect of polyurethane
Significantly, polyurethane is enable largely to be used in more areas, but there is also deficiency.Although nano material has high temperature resistant enhancing effect
It is good, the advantages of additive amount is small, but there is also difficulties in dispersion, it is of high cost the defects of.During heat resist modification is carried out, nanometer material
The scattered inequality of material can influence its high-temperature resistant result, and obtained modified material heat-resisting quantity is relatively low, production to modified material and should
With adversely affecting.
The content of the invention
The defects of it is an object of the invention to overcome existing modified polyurethane material heat-resisting quantity poor, there is provided a kind of compound
Modified polyurethane material and preparation method thereof；The present invention by the nano-aluminum hydroxide Jing Guo specific aim modification and polyurethane into
Row is compound, and nano-aluminum hydroxide is dispersed in polyurethane system, obtained modified polyurethane material resistance to elevated temperatures
It is excellent, be conducive to application of the polyurethane in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of composite modified polyurethane material, including following weight
Part raw material are prepared：50-60 parts of polyurethane, 5-15 parts of nano-aluminum hydroxide, 5-10 parts of modifying agent, 15-20 parts
Neoprene, 0.3-0.8 parts of coupling agent, 2-5 parts of crosslinking agent, 5-10 parts of butyl titanate, 3-8 parts of stearic acid
Zinc.
A kind of above-mentioned composite modified polyurethane material, can increase resin material high temperature resistant according to nano-aluminum hydroxide and crosslinking
The basic principle of property, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve a nanometer hydroxide
Compatibility between aluminium and polyurethane, and make nano-aluminum hydroxide disperse evenly, to make nano-aluminum hydroxide pair in polyurethane
The heat-resisting quantity humidification of polyurethane is more preferable, and modified modified polyurethane material is also made by controlling the degree of polymerization of polyurethane
Material reaches optimum balance relation between heat-resisting quantity and processability, so that the modified polyurethane material made is with excellent
Heat-resisting quantity under conditions of, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned composite modified polyurethane material, wherein, the nano-aluminum hydroxide particle diameter is 10-80nm；Nanometer
Aluminium hydroxide particle diameter is smaller, and dispersiveness is poorer, and nano-aluminum hydroxide particle diameter is bigger, and the high temperature resistant humidification of polyurethane is got over
Difference；Preferably, the nano-aluminum hydroxide particle diameter is 30-50nm；Most preferably, the nano-aluminum hydroxide particle diameter is
40nm。
A kind of above-mentioned composite modified polyurethane material, wherein, the modifying agent is phenyl phosphorus diamides and dimethyl mercapto
The mixture of base succinate composition；The modifying agent can improve nano-aluminum hydroxide and polyurethane compatibility and
Polar group is formed on nano-aluminum hydroxide surface, beneficial to scattered；Preferably, phenyl phosphorus diamides and two in the modifying agent
The ratio between amount of material of methyl mercapto succinate is 1 ︰ 1.
A kind of above-mentioned composite modified polyurethane material, wherein, the degree of polymerization of neoprene is bigger, then is crosslinked the poly- ammonia of post-modification
The heat-resisting quantity of ester material is poorer, and processability is better, and the polymer of neoprene is smaller, then is crosslinked post-modification polyurethane material
Heat-resisting quantity is better, and processability is poorer, therefore, selects the rational neoprene degree of polymerization, is balance heat-resisting quantity and processability
Important means.The degree of polymerization of the neoprene is 200-400；Preferably, the degree of polymerization of the neoprene is
250-350；Optimal, the degree of polymerization of the neoprene is 300；By preferred, obtained modified polyurethane material both had
There is excellent heat-resisting quantity, it may have preferable processability, is adapted to the application in more areas.
Wherein, it is 800-1500 that the polyurethane polyureas is right；Preferably, the degree of polymerization of the polyurethane is 1000-
1300；Most preferably, the degree of polymerization of the polyurethane is 1200；By preferred, obtained modified polyurethane material both had
Excellent heat-resisting quantity, it may have preferable processability.
A kind of above-mentioned composite modified polyurethane material, wherein, the coupling agent is three isopropyl ester coupling agent of aluminic acid；Aluminic acid
Three isopropyl esters can increase the compatibility between nano-aluminum hydroxide and polyurethane and modifying agent, improve modified polyurethane material
Performance.
Wherein, the crosslinking agent is tetraisocyanate, which can be by the polymer former material of two kinds of different polymerization degrees
The appropriate crosslinking of material, improves the heat-resisting quantity of modified polyurethane material.
A kind of above-mentioned composite modified polyurethane material, wherein, its raw material further include dispersant, plasticizer, antistatic additive,
One or more auxiliary agents in coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of modified polyurethane material, increase it
Feature etc. acts on, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of composite modified polyurethane material
Preparation method, comprises the following steps：
（1）Nano-aluminum hydroxide is handled with coupling agent；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-aluminum hydroxide after cladding and polyurethane processing for composite in the electric field after mixing, mixed
Material；
（4）By mixture and neoprene, crosslinking agent, zinc stearate, butyl titanate after mixing in processing for composite,
Obtain composite modified polyurethane material.
A kind of preparation method of composite modified polyurethane material, first carries out at coupling nano-aluminum hydroxide with coupling agent
Reason, increase nano-aluminum hydroxide and modifying agent, the compatibility of polyurethane；Place is modified to nano-aluminum hydroxide with modifying agent again
Reason, and form polar group on its surface；Finally make the polarity in nano-aluminum hydroxide surface and polyurethane chain using external electric field
Group polarizes, powered, by repelling each other between electric charge or attracting principle, while making nano-aluminum hydroxide dispersed, also can
It is bonded with the polar group in polyurethane chain, so that the high temperature resistant enhancing effect of nano-aluminum hydroxide obtains maximum body
It is existing, so as to get modified polyurethane heat-resisting quantity significantly improve；The preparation method is simple and reliable, is suitable for composite modified poly- ammonia
Extensive, the industrialized production of ester material.
A kind of preparation method of above-mentioned composite modified polyurethane material, wherein, it is preferred that step 1 carries out coupling processing mistake
Cheng Zhongke is aided in using ultrasonic wave；Shaken by the high speed of ultrasonic wave, make nano-aluminum hydroxide dispersiveness more preferable, and to coupling at
Reason has facilitation.
A kind of preparation method of above-mentioned composite modified polyurethane material, wherein, the electric field energy described in step 3 produces group
Raw polarization, makes group powered, so as to promote the scattered and bonded effect of nano-aluminum hydroxide, improves modified polyurethane
Heat-resisting quantity.
Preferably, the electric field strength is 1.5-2.5kv/m；Electric field strength is too small, and polarization effect is weak, to nanometer hydrogen-oxygen
The dispersion effect for changing aluminium is poor；Electric field strength is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces orientation and moves
It is dynamic, arrangement and the bonded performance for having an impact, may be decreased modified polyurethane material to strand；Most preferably, it is described
Electric field strength is 1.8-2.0kv/m.
Wherein, it is preferred that the electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stablized, and the scattered and bonded promotion to nano-aluminum hydroxide is made
Use best results.
Compared with prior art, beneficial effects of the present invention：
1st, modified polyurethane material of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes a nanometer hydrogen-oxygen
The compatibility changed between aluminium and polyurethane is more preferable, and the dispersiveness in polyurethane is more preferable, and nano-aluminum hydroxide is to the resistance to of polyurethane
High temperatures humidification is more preferable.
2nd, modified polyurethane material of the present invention makes modified change by controlling the degree of polymerization of polyurethane and neoprene
Property polyurethane material reaches optimum balance relation between heat-resisting quantity and processability, so as to get modified polyurethane material having
Under conditions of having an excellent heat-resisting quantity, it may have excellent processability.
3rd, the preparation method of modified polyurethane material of the present invention, using the polarization of external electric field, can promote nanometer hydrogen-oxygen
It is scattered and bonded in polyurethane system to change aluminium, the high temperature resistant enhancing effect of nano-aluminum hydroxide is more preferable, and obtained modification gathers
The heat-resisting quantity higher of urethane material.
4th, the preparation method of modified polyurethane material of the present invention is simple, reliable, is adapted to the big of composite modified polyurethane material
Scale, industrialized production.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）10 parts of nano-aluminum hydroxide is handled with 0.6 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 3.5 parts of phenyl phosphorus diamides and 3.5 parts of dimethyl sulfydryl
Succinate carries out cladding processing；
（3）By polyurethane that the nano-aluminum hydroxide after cladding and 55 parts of the degree of polymerization are 1200 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, mixture is obtained；
（4）The neoprene, 4 parts of tetraisocyanates, 8 parts of titanium that the mixture that step 3 is obtained and 18 parts of the degree of polymerization are 300
Sour four butyl esters, 5 parts of zinc stearate are extruded after mixing, obtain composite modified polyurethane material.
Embodiment 2
（1）5 parts of nano-aluminum hydroxide is handled with 0.3 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 2.5 parts of phenyl phosphorus diamides and 2.5 parts of dimethyl sulfydryl
Succinate carries out cladding processing；
（3）By polyurethane that the nano-aluminum hydroxide after cladding and 50 parts of the degree of polymerization are 1500 after mixing in electric-field strength
Spend in the electric field for 2.5kv/m and extruded, obtain mixture；
（4）The neoprene, 2 parts of tetraisocyanates, 5 parts of titanium that the mixture that step 3 is obtained and 20 parts of the degree of polymerization are 200
Sour four butyl esters, 3 parts of zinc stearate are extruded after mixing, obtain composite modified polyurethane material.
Embodiment 3
（1）15 parts of nano-aluminum hydroxide is handled with 0.8 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 5 parts of phenyl phosphorus diamides and 4 parts of dimethyl mercaptosuccinic
Acid esters carries out cladding processing；
（3）By polyurethane that the nano-aluminum hydroxide after cladding and 60 parts of the degree of polymerization are 800 after mixing in electric-field strength
Spend to be extruded in the constant parallel electric field of the direction of an electric field of 1.5kv/m, obtain mixture；
（4）Neoprene that the mixture that step 3 is obtained and 15 parts of the degree of polymerization are 400,5 parts of tetraisocyanates, 10 parts
Butyl titanate, 8 parts of zinc stearate are extruded after mixing, obtain composite modified polyurethane material.
Comparative example 1
（1）10 parts of nano-aluminum hydroxide is handled with 0.6 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment and 7 parts of dispersant, the polyurethane that 55 parts of the degree of polymerization is 1200
Extruded after mixing in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m, obtain mixture；
（3）The neoprene, 4 parts of tetraisocyanates, 8 parts of titanium that the mixture that step 2 is obtained and 18 parts of the degree of polymerization are 300
Sour four butyl esters, 5 parts of zinc stearate are extruded after mixing, obtain modified polyurethane material.
Comparative example 2
（1）10 parts of nano-aluminum hydroxide is handled with 0.6 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 3.5 parts of phenyl phosphorus diamides and 3.5 parts of dimethyl sulfydryl
Succinate carries out cladding processing；
（3）It is 300 by polyurethane that the nano-aluminum hydroxide after cladding and 55 parts of the degree of polymerization are 1200,18 parts of the degree of polymerization
Neoprene, 4 parts of tetraisocyanates, 8 parts of butyl titanate, 5 parts of zinc stearate are extruded after mixing, are changed
Property polyurethane material.
Comparative example 3
（1）10 parts of nano-aluminum hydroxide is handled with 0.6 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 3.5 parts of polystyrene and 3.5 parts of dimethyl mercaptosuccinic
Acid esters carries out cladding processing；
（3）By polyurethane that the nano-aluminum hydroxide after cladding and 55 parts of the degree of polymerization are 1200 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, mixture is obtained；
（4）The neoprene, 4 parts of tetraisocyanates, 8 parts of titanium that the mixture that step 3 is obtained and 18 parts of the degree of polymerization are 300
Sour four butyl esters, 5 parts of zinc stearate are extruded after mixing, obtain modified polyurethane material.
Comparative example 4
（1）10 parts of nano-aluminum hydroxide is handled with 0.6 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 3.5 parts of phenyl phosphorus diamides and 3.5 parts of dimethyl sulfydryl
Succinate carries out cladding processing；
（3）By neoprene that the nano-aluminum hydroxide after cladding and 18 parts of the degree of polymerization are 300,4 parts of tetraisocyanates, 8 parts
Butyl titanate, 5 parts of zinc stearate, 55 parts of the degree of polymerization be 1200 polyurethane be in electric field strength after mixing
Extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, obtain modified polyurethane material.
Comparative example 5
（1）10 parts of nano-aluminum hydroxide is handled with 0.6 part of three isopropyl ester of aluminic acid；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 3.5 parts of phenyl phosphorus diamides and 3.5 parts of dimethyl sulfydryl
Succinate carries out cladding processing；
（3）By polyurethane that the nano-aluminum hydroxide after cladding and 55 parts of the degree of polymerization are 700 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, mixture is obtained；
（4）Neoprene that the mixture that step 3 is obtained and 18 parts of the degree of polymerization are 180,4 parts of butyl titanate, 5 parts
Zinc stearate, 8 parts of tetraisocyanates are extruded after mixing, obtain modified polyurethane material.
By the modified polyurethane material in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data are such as
Under：
| Performance | Long-time service temperature（℃） | Processability |
| Embodiment 1 | 102 | ++++ |
| Embodiment 2 | 101 | ++++ |
| Embodiment 3 | 102 | ++++ |
| Comparative example 1 | 89 | ++++ |
| Comparative example 2 | 92 | ++++ |
| Comparative example 3 | 93 | ++++ |
| Comparative example 4 | 95 | ++++ |
| Comparative example 5 | 101 | ++ |
| Polyurethane | 80 | +++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the composite modified polyurethane material of the invention being prepared in embodiment 1-3,
Nano-aluminum hydroxide is uniformly dispersed, and good with the compatibility of polyurethane, modified polyurethane material heat-resisting quantity is good, and processability is good；And
In comparative example 1, modifying agent is not used processing is modified to nano-aluminum hydroxide, although adding dispersant, nanometer hydrogen-oxygen
Change aluminium dispersion effect is poor, and the poor compatibility with polyurethane, the heat-resisting quantity of modified polyurethane material significantly reduces；In comparative example 2
Not processing for composite in the electric field, nano-aluminum hydroxide dispersion effect is poor, and the heat-resisting quantity of modified polyurethane material significantly drops
It is low；Modifying agent is not the application defined in comparative example 3, and nano-aluminum hydroxide dispersion effect is poor, modified polyurethane material
Heat-resisting quantity significantly reduces；Cross-linking reaction equally carries out in the electric field in comparative example 4, and electric field produces unfavorable shadow to cross-linking reaction
Ring, so as to get modified polyurethane material heat-resisting quantity reduce；The polyurethane and the neoprene degree of polymerization used in comparative example 5
Too small, although heat-resisting quantity increased after compound, its processability significantly reduces, and is unfavorable for answering for modified polyurethane material
With.
Claims (10)
1. a kind of composite modified polyurethane material, it is characterised in that be prepared including following parts by weight raw material：50-60 parts
Polyurethane, 5-15 parts of nano-aluminum hydroxide, 5-10 parts of modifying agent, 15-20 parts of neoprene, 0.3-0.8 parts of idol
Join agent, 2-5 parts of crosslinking agent, 5-10 parts of butyl titanate, 3-8 parts of zinc stearate；The modifying agent is two acyl of phenyl phosphorus
The mixture of amine and dimethyl mercaptosuccinic acid esters composition；The coupling agent is three isopropyl ester coupling agent of aluminic acid, the crosslinking agent
For tetraisocyanate；The degree of polymerization of the neoprene is 200-400；The right polyurethane polyureas is 800-1500.
2. modified polyurethane material according to claim 1, it is characterised in that in the modifying agent phenyl phosphorus diamides with
The ratio between amount of material of dimethyl mercaptosuccinic acid esters is 1 ︰ 1.
3. modified polyurethane material according to claim 1, it is characterised in that the degree of polymerization of the neoprene is 250-
350。
4. modified polyurethane material according to claim 3, it is characterised in that the degree of polymerization of the neoprene is 300.
5. modified polyurethane material according to claim 1, it is characterised in that the right polyurethane polyureas is 1000-
1300。
6. modified polyurethane material according to claim 5, it is characterised in that the right polyurethane polyureas is 1200.
7. a kind of preparation method of the modified polyurethane material as described in claim any one of 1-6, it is characterised in that including following
Step：
（1）Nano-aluminum hydroxide is handled with coupling agent；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-aluminum hydroxide after cladding and polyurethane processing for composite in the electric field after mixing, mixed
Material；（4）By mixture and neoprene, crosslinking agent, zinc stearate, butyl titanate after mixing in processing for composite,
Obtain composite modified polyurethane material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric field strength is 1.5-2.5kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric field strength is 1.8-2.0kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field is put down for direction of an electric field is constant
Row electric field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711271454.2A CN107903615A (en) | 2017-12-05 | 2017-12-05 | A kind of composite modified polyurethane material and preparation method thereof |
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| CN201711271454.2A CN107903615A (en) | 2017-12-05 | 2017-12-05 | A kind of composite modified polyurethane material and preparation method thereof |
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| CN107903615A true CN107903615A (en) | 2018-04-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500051A (en) * | 2020-05-27 | 2020-08-07 | 宁波格林美孚新材料科技有限公司 | TPU micropore foaming particles, preparation method and tire |
-
2017
- 2017-12-05 CN CN201711271454.2A patent/CN107903615A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500051A (en) * | 2020-05-27 | 2020-08-07 | 宁波格林美孚新材料科技有限公司 | TPU micropore foaming particles, preparation method and tire |
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