CN107793585A - A kind of liquid crystal flame-retardant foam material and preparation method thereof - Google Patents
A kind of liquid crystal flame-retardant foam material and preparation method thereof Download PDFInfo
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- CN107793585A CN107793585A CN201711035250.9A CN201711035250A CN107793585A CN 107793585 A CN107793585 A CN 107793585A CN 201711035250 A CN201711035250 A CN 201711035250A CN 107793585 A CN107793585 A CN 107793585A
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a kind of liquid crystal flame-retardant foam material and preparation method thereof; using aromatic series diphenol monomer, aromatic diacid monomer, the aromatic monomer containing terminal hydroxy group and end carboxyl as raw material; in the presence of active end group, catalyst, acetic acid compound; under nitrogen protection, 30~60min is reacted in 120~140 DEG C；Then 280~325 DEG C are warming up to 0.5~1.5 DEG C/min speed, react 1~3h, obtain solids；Solids heating in vacuum is obtained into liquid crystal flame-retardant foam material.It is foaming agent that the present invention, which utilizes accessory substance acetic acid remaining in liquid crystal polymer polycondensation process, and release CO is solved in the high temperature time-division2Microcellular structure is formed, while matrix occurs curing reaction and forms cross-linked network structure, opens the new method for preparing liquid crystal flame-retardant foam material, the especially present invention need not add fire retardant to reach flame retardant effect, reach the V0 flame retardant ratings of UL 94；The preparation method of the present invention has the characteristics of environmental protection, easy, applicability is wide in addition.
Description
Technical field
The present invention relates to a kind of liquid crystal flame-retardant foam material and preparation method thereof, belong to high-performance polymer field.
Background technology
Polymeric foamable material such as polystyrene foam warming plate, polyurethane foam product etc. are with its excellent mechanics, sound
The performances such as, electricity, insulation, it is widely used in the fields such as building, high ferro and aviation.But polymeric foamable material heat-resisting and
Fire resistance is poor, and fire damage is very huge caused by its is flammable every year, and the market demand contradiction safe with application is increasingly
It is prominent, the demand for improving polymeric foamable material anti-flammability is sharply increased.
Anti-flammability is obtained by adding various fire retardants in polymeric foamable material preparation process, wherein most generally adopting
Fire retardant is with containing the organic compound such as halogen or phosphorus nitrogen.For example, patent WO91/19758, which discloses one kind, uses hexabromo
The method that cyclododecane improves polystyrene foam anti-flammability；Patent US6578911 discloses one kind and uses halophosphoric acid esters
The method that compound and phosphate ester flame retardants improve polyurethane foam product anti-flammability；Patent CN99814260.3 disclose with
The method of expanded graphite and phosphorus compound flame retardant polystyrene foam.But the existing method for improving polymeric foamable material anti-flammability
Following problem be present：（1）Addition type organic fire-retardant easily decomposes, and meeting severe corrosion equipment simultaneously causes fire resistance
Decay；（2）Addition high level fire retardant often deteriorates the architecture quality and surface quality of foam, reduce foam intensity or its
Insulating properties；（3）Long-term use of environmental pollution containing the organic fire-retardant such as halogen or phosphorus nitrogen is serious.
In addition, foaming agent is that existing foamed material prepares essential raw material, and in foamed material preparation process
Used foaming agent（Such as azodicarbonamide）Mostly harmful compound.Therefore, how fire retardant is not being added
On the premise of, it is that current one, high-performance polymer field has weight to prepare and have the easily expanded material of foaming and high flame resistance concurrently
The problem of big application value.
The content of the invention
In order to overcome the shortcomings of the prior art, it is an object of the invention to provide one kind need not add fire retardant, simultaneous
Tool easily liquid crystal flame-retardant foam material of foaming and excellent fire-retardancy and preparation method thereof.
Technical scheme is used by realizing the object of the invention:
A kind of preparation method of liquid crystal flame-retardant foam material, comprises the following steps：
（1）Using aromatic series diphenol monomer, aromatic diacid monomer, the aromatic monomer containing terminal hydroxy group and end carboxyl as raw material,
In the presence of active end group, catalyst, acetic acid compound, under nitrogen protection, 30~60min is reacted in 120~140 DEG C；So
280~325 DEG C are warming up to 0.5~1.5 DEG C/min speed afterwards, 1~3h is reacted, obtains solids；
（2）By solids under 10~90 kPas of vacuum, 20~60min is handled in 320~380 DEG C, obtains the fire-retardant hair of liquid crystal
Foam material.
The invention also discloses a kind of preparation method of liquid crystal flame-retardant foam material presoma, comprise the following steps：
Using aromatic series diphenol monomer, aromatic diacid monomer, the aromatic monomer containing terminal hydroxy group and end carboxyl as raw material, in work
Property end group, catalyst, in the presence of acetic acid compound, under nitrogen protection, react 30~60min in 120~140 DEG C；Then with
0.5~1.5 DEG C/min speed is warming up to 280~325 DEG C, reacts 1~3h, obtains liquid crystal flame-retardant foam material presoma；This
Invention limits heating rate contributes to polycondensation reaction to carry out completely, obtaining the liquid for meeting target molecular weight as 0.5~1.5 DEG C/min
Brilliant flame-retardant foam material presoma, so as to solve release CO in the high temperature time-division2Microcellular structure is formed, while matrix solidifies
Reaction forms cross-linked network structure, prepares the liquid crystal flame-retardant foam material that need not add fire retardant.
In above-mentioned technical proposal, the aromatic series diphenol monomer is Isosorbide-5-Nitrae-hydroquinones, 1,3- resorcinols, 4,4 '-connection
Benzenediol, 1,1 '-biphenyl -3,4 '-diphenol, 1,1 '-biphenyl -3,3 '-diphenol, 1,6- naphthalenediols, 1,7- naphthalenediols, 2,6- naphthalenes two
One or more in phenol, 2,7- naphthalenediols；The aromatic diacid monomer is 1,4- terephthalic acid (TPA)s, 1,3- isophthalic diformazans
Acid, 4,4 '-biphenyl dicarboxylic acid, 1,1 '-biphenyl -3,4 '-dicarboxylic acids, 1,1 '-biphenyl -3,3 '-dicarboxylic acids, 1,6- naphthalenedicarboxylic acids,
One or more in 1,7- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids；The virtue containing terminal hydroxy group and end carboxyl
Fragrant race's monomer is 3- hydroxybenzoic acids, 4 '-Hydroxybiphenyl -3- carboxylic acids, 7- hydroxy-2-naphthoic acids, N-（3'- hydroxyphenyls）Inclined benzene
One or more in three acid imides；.
In above-mentioned technical proposal, the active end group is 3- amino phenylacetylene, N-（4- carboxyl phenyls）- 4- phenylacetylene bases are adjacent
Phthalic acid acid imide, N-（4- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, N-（3- carboxyl phenyls）-
4- phenylacetylene bases phthalic acid imides, N-（3- acetoxyphenyl bases）In -4- phenylacetylene base phthalic acid imides
It is one or more of；The catalyst is potassium acetate, sodium acetate, zinc acetate, Dibutyltin oxide, stannous octoate, the fourth of laurate two
One kind in base tin；The acetic acid compound is acetic anhydride.
In above-mentioned technical proposal, the aromatic series diphenol monomer, aromatic diacid monomer, containing terminal hydroxy group and end carboxyl
Aromatic monomer, active end group, catalyst, the mol ratio of acetic acid compound are 1: 1:（0.5~2）∶（0.03~0.45）∶
（0.5 ‰~5 ‰）∶（1.5~4）；The present invention restriction start material molar ratio range, which helps to obtain, meets target molecule
The liquid crystal flame-retardant foam material presoma of amount, curing reaction formation cross-linked network structure occurs so as to be advantageous to matrix, prepares not
Need the liquid crystal flame-retardant foam material of addition fire retardant.
In above-mentioned technical proposal, step（2）In, solids is ground to after powder under 10~90 kPas of vacuum,
20~60min is handled in 320~380 DEG C, obtains liquid crystal flame-retardant foam material；The present invention limits vacuum to be had as 10~90 kPas
Help obtain even aperture distribution, the liquid crystal flame-retardant foam material of controlled porosity；Limiting temperature and time is respectively 320~
The 380 DEG C and 20~60min liquid crystal flame-retardant foam materials for helping fully to be foamed and solidified, the utilization of the invention
Remaining accessory substance acetic acid is foaming agent in liquid crystal polymer polycondensation process, and release CO is solved in the high temperature time-division2Form micropore
Structure, while matrix occurs curing reaction and forms cross-linked network structure, opens the new method for preparing liquid crystal flame-retardant foam material.
The invention discloses the liquid crystal flame-retardant foam material prepared according to the preparation method of above-mentioned liquid crystal flame-retardant foam material.
The invention discloses the fire-retardant hair of liquid crystal prepared according to the preparation method of above-mentioned liquid crystal flame-retardant foam material presoma
The application of foam material presoma and above-mentioned liquid crystal flame-retardant foam material presoma in flame-retardant foam material is prepared.
The present invention, which can illustrate, represents as follows：
（1）By 1mol aromatic series diphenol monomers（X）, 1mol aromatic diacid monomers（Y）, 0.5~2mol contain terminal hydroxy group A and end
Carboxyl B meta AB type aromatic monomers（Z）, active end group, 0.5~2mmol catalyst and 1.5~4mol acetic anhydride add it is anti-
Answer in device；Under nitrogen protection, 30~60min of acetylization reaction at 120~140 DEG C of temperature；
（2）Speed according to 0.5~1.5 DEG C/min is warming up to 280~325 DEG C, carries out 1~3h of ester exchange reaction；Reaction terminates
After be cooled to room temperature, product is ground to fine powder；
（3）By step（2）Obtained fine powder is placed in vacuum as 10~90 kPas（100-900mbar）And temperature is 320
Foamed in~380 DEG C of vacuum drying oven and solidify 20~60min, that is, obtain a kind of liquid crystal flame-retardant foam material.
It is foaming agent that the present invention, which utilizes accessory substance acetic acid remaining in liquid crystal polymer polycondensation process, in the high temperature time-division
Solution release CO2Microcellular structure is formed, while matrix occurs curing reaction and forms cross-linked network structure, open that to prepare liquid crystal fire-retardant
The new method of expanded material.The present invention need not add fire retardant to reach flame retardant effect, but rely on the complete of liquid crystal polymer
The excellent heat-resistant quality of aromatic main chain, the microcellular structure and hole wall polymer of foamed material itself continue in combustion
Foaming release CO2Play the effect of blocking oxygen and heat transfer.The invention discloses above-mentioned liquid crystal flame-retardant foam material to make
Application in standby flame-retardant foam material.
Compared with prior art, the beneficial effect that obtains of the present invention is：
1st, different from prior art addition foaming agent, the present invention utilizes caused pair in liquid crystal polymer polycondensation process first
Acetic acid product is foaming agent, and it can solve release CO in the high temperature time-division2Form microcellular structure；At the same time, solidification occurs for matrix anti-
Cross-linked network structure should be formed, so as to successfully obtaining foamable polymer, opens and a kind of prepares the new of liquid crystal flame-retardant foam material
Method.
2nd, different from preparing the conventional method of flame-retardant foam material by addition fire retardant, the present invention is fire-retardant for Intrinsical,
And fire retardant mechanism is unlike the prior art；The present invention, as one kettle way polymerisation starting material, is relied on from all aromatic monomer
The excellent heat-resistant quality of all aromatic main chain of liquid crystal polymer, the microcellular structure and hole wall polymer of foamed material itself exist
Combustion process relaying supervention bubble release CO2The effect of blocking oxygen and heat transfer is played, possesses excellent resistance so as to obtain one kind
The liquid crystal flame-retardant foam material of performance is fired, has reached UL-94 V0 flame retardant ratings.
3rd, due to that need not add fire retardant, one pot of polycondensation reaction method is simply controllable, the preparation technology section to be foamed in solidification
Can efficiently, therefore the preparation method of the present invention has the characteristics of environmental protection, easy, applicability is wide.
Brief description of the drawings
The liquid-crystalline polyster powder sample that Fig. 1 is the liquid crystal polyester imide that the embodiment of the present invention 2 provides and embodiment 3 provides
With 3 DEG C/min of heating rate by 200 DEG C of complex viscosity-time graphs for being warming up to 370 DEG C and constant temperature 60min；
The liquid crystal polyester flame-retardant foam material that Fig. 2 is the liquid crystal polyester imide that the embodiment of the present invention 2 provides and embodiment 3 provides
Digital photograph in kind；
Fig. 3 be the embodiment of the present invention 3 provide liquid crystal polyester flame-retardant foam material burning before ESEM（SEM）Photo；
Fig. 4 be the embodiment of the present invention 3 provide liquid crystal polyester flame-retardant foam material burning before three-dimensional X-ray tomoscan
（CT）Reconstruct photo；
Fig. 5 is the micropore equivalent diameter before the burning for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides；
Fig. 6 is the micro pore volume before the burning for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides；
Fig. 7 is the thermal weight loss for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides（TG）- temperature curve；
Fig. 8 be the embodiment of the present invention 3 provide liquid crystal polyester flame-retardant foam material burning after ESEM（SEM）Photo；
Fig. 9 be the embodiment of the present invention 3 provide liquid crystal polyester flame-retardant foam material burning after three-dimensional X-ray tomoscan
（CT）Reconstruct photo；
Figure 10 is the micropore equivalent diameter after the burning for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides；
Figure 11 is the micro pore volume after the burning for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides.
Embodiment
With reference to the accompanying drawings and examples, technical solution of the present invention will be further described.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 1
16.02g 1,6- naphthalenediols, 21.62g 2,7- naphthalenedicarboxylic acids, 21.42g are added in a 250mL three neck round bottom flask
4 '-Hydroxybiphenyl -3- carboxylic acids, 3.84g N-（4- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides, 4.02g N-
（4- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, 50mL acetic anhydride and 2mg Dibutyltin oxides.Flask
It is equipped with seal glass dasher, a nitrogen inlet tube and an insulation still head.Nitrogen stream is passed through, in 130 DEG C of temperature
Lower acetylization reaction 45min.Reactant mixture is heated with 1.0 DEG C/min of heating rate in drift sand bath, reaction temperature is by 130
DEG C rise to 280 DEG C.Reaction terminates to obtain opaque melt, is cooled to room temperature, by product by being removed in flask, then grinds
It is liquid-crystalline polyster powder for fine powder.It is 80 kPas that obtained liquid-crystalline polyster powder is placed in into 320 DEG C of temperature and vacuum
Solidify 60min in foaming in vacuum drying oven, that is, obtain a kind of liquid crystal polyester flame-retardant foam material, it is fire-retardant to have reached UL-94 V0
Grade.
The preparation of the liquid crystal polyester imide flame-retardant foam material of embodiment 2
Added in a 500mL three neck round bottom flask 93.10g 1,3- resorcinols, 83.08g 1,3- M-phthalic acids,
39.16g N-（3'- hydroxyphenyls）The inclined acid imide of benzene three, 41.01g N-（3- carboxyl phenyls）- 4- phenylacetylene base phthalic acid acyls
Imines, 42.59g N-（3- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, 300mL acetic anhydride and 25mg vinegar
Sour sodium.Flask is equipped with seal glass dasher, a nitrogen inlet tube and an insulation still head.It is passed through moderate nitrogen
Stream, the acetylization reaction 60min at 120 DEG C of temperature.Reactant mixture is added with 0.5 DEG C/min of heating rate in drift sand bath
Heat, reaction temperature rise to 325 DEG C by 120 DEG C.Reaction terminates to obtain opaque melt, room temperature is cooled to, by product by burning
Removed in bottle, be then ground to fine powder.Its powder sample is warming up to 370 DEG C and perseverance with 3 DEG C/min of heating rate by 200 DEG C
Warm 60min complex viscosity-time graph is referring to accompanying drawing 1.
Obtained liquid crystal polyester imide powder is placed in 370 DEG C of temperature and vacuum as side in 80 kPas of vacuum drying oven
Foam side solidification 60min, that is, obtains a kind of liquid crystal polyester imide flame-retardant foam material, reached UL-94 V0 flame retardant ratings,
Its digital photograph in kind is referring to accompanying drawing 2.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 3
Added in a 500mL three neck round bottom flask 37.24g 1,4- hydroquinones, 33.23g 1,4- terephthalic acid (TPA)s,
69.06g 3- hydroxybenzoic acids, 18.82g 7- hydroxy-2-naphthoic acids, 27.34g N-（4- carboxyl phenyls）- 4- phenylacetylene bases are adjacent
Phthalic acid acid imide, 28.39g N-（4- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, 150mL acetic acid
Acid anhydride and 10mg potassium acetates.Flask is equipped with seal glass dasher, a nitrogen inlet tube and an insulation still head.It is passed through
Moderate nitrogen stream, the acetylization reaction 30min at 140 DEG C of temperature.It will be reacted with 1.0 DEG C/min of heating rate in drift sand bath
Mixture heats, and reaction temperature rises to 310 DEG C by 140 DEG C.Reaction terminates to obtain opaque melt, is cooled to room temperature, will
Product is then ground to fine powder by being removed in flask.Its powder sample is warming up to 3 DEG C/min of heating rate by 200 DEG C
370 DEG C and constant temperature 60min of complex viscosity-time graph is referring to accompanying drawing 1.
By in obtained liquid-crystalline polyster powder is placed in 370 DEG C of temperature and vacuum is 70 kPas vacuum drying oven in foaming
Solidify 50min, that is, obtain a kind of liquid crystal polyester flame-retardant foam material, its density, porosity, vertical combustion（UL-94）Test knot
Fruit, grading performance and with reference pair ratio referring to table 1,2,3 and 4, ESEM before digital photograph in kind, burning（SEM）Photo,
Three-dimensional X-ray tomoscan（CT）Photo, micropore equivalent diameter and volume is reconstructed to lose referring to accompanying drawing 2,3,4,5 and 6, heat respectively
Weight（TG）ESEM after-temperature curve, burning（SEM）Photo, three-dimensional X-ray tomoscan（CT）Reconstruct photo, micropore etc.
Diameter and volume are imitated respectively referring to accompanying drawing 7,8,9,10 and 11.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 4
Added in a 1000mL three neck round bottom flask 80.09g 2,7- naphthalenediols, 93.11g 4,4 '-'-biphenyl diphenol,
108.10g 1,6- naphthalenedicarboxylic acids, 121.12g 4,4 '-biphenyl dicarboxylic acid, 69.06g 3- hydroxybenzoic acids, 7.38g N-（3-
Carboxyl phenyl）- 4- phenylacetylene bases phthalic acid imides, 7.67g N-（4- acetoxyphenyl bases）- 4- phenylacetylene base neighbour's benzene
Diformazan acid imide, 300mL acetic anhydride and 45mg zinc acetates.Flask is equipped with seal glass dasher, a nitrogen inlet
Pipe and an insulation still head.Moderate nitrogen stream is passed through, the acetylization reaction 30min at 140 DEG C of temperature.Drift sand bath in
1.5 DEG C/min of heating rate heats reactant mixture, and reaction temperature rises to 315 DEG C by 140 DEG C.Reaction end obtains impermeable
Bright melt, is cooled to room temperature, by product by being removed in flask, is then ground to fine powder.The liquid crystal polyester powder that will be obtained
Solidify 30min in foaming in the vacuum drying oven that end is placed in 380 DEG C of temperature and vacuum is 90 kPas, that is, obtain a kind of liquid crystal and gather
Ester flame-retardant foam material, UL-94 V0 flame retardant ratings are reached.
The preparation of the liquid crystal polyester imide flame-retardant foam material of embodiment 5
111.73g 1,1 '-biphenyl -3,3 '-diphenol, 129.71g 1,7- naphthalenes are added in a 1000mL three neck round bottom flask
Dioctyl phthalate, 211.20g N-（3'- hydroxyphenyls）The inclined acid imide of benzene three, 69.06g 3- hydroxybenzoic acids, 14.77g N-（3- carboxyls
Phenyl）- 4- phenylacetylene bases phthalic acid imides, 15.33g N-（3- acetoxyphenyl bases）- 4- phenylacetylene base O-phthalics
Acid imide, 300mL acetic anhydride and 35mg sodium acetates.Flask is equipped with seal glass dasher, a nitrogen inlet tube and
One insulation still head.Moderate nitrogen stream is passed through, the acetylization reaction 45min at 130 DEG C of temperature.With heating in drift sand bath
1.0 DEG C/min of speed heats reactant mixture, and reaction temperature rises to 280 DEG C by 130 DEG C.Reaction end obtains opaque
Melt, room temperature is cooled to, by product by being removed in flask, is then ground to fine powder.Obtained liquid-crystalline polyster powder is put
Solidify 20min while during 370 DEG C of temperature and vacuum is 60 kPas of vacuum drying ovens in foaming, that is, obtain a kind of liquid crystal polyester resistance
Expanded material is fired, has reached UL-94 V0 flame retardant ratings.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 6
Added in a 1000mL three neck round bottom flask 160.17g 2,7- naphthalenediols, 108.10g 1,7- naphthalenedicarboxylic acids,
121.12g 1,1 '-biphenyl -3,4 '-dicarboxylic acids, 69.06g 3- hydroxybenzoic acids, 282.27g 7- hydroxy-2-naphthoic acids,
18.46g N-（4- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides, 19.17g N-（3- acetoxyphenyl bases）-4-
Phenylacetylene base phthalic acid imides, 380mL acetic anhydride, 5mg sodium acetates and 75mg stannous octoates.Flask is equipped with seal glass
Dasher, a nitrogen inlet tube and an insulation still head.Moderate nitrogen stream is passed through, the acetyl at 125 DEG C of temperature
Change reaction 45min.Reactant mixture is heated with 1.2 DEG C/min of heating rate in drift sand bath, reaction temperature is by 125 DEG C of risings
To 300 DEG C.Reaction terminates to obtain opaque melt, is cooled to room temperature, by product by being removed in flask, is then ground to fine
Powder.Obtained liquid-crystalline polyster powder is placed in 330 DEG C of temperature and vacuum to consolidate in 10 kPas of vacuum drying oven in foaming
Change 50min, that is, obtain a kind of liquid crystal polyester flame-retardant foam material, reached UL-94 V0 flame retardant ratings.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 7
80.09g 1,7- naphthalenediols, 121.12g 1,1 '-biphenyl -3,4 '-two are added in a 1000mL three neck round bottom flask
Carboxylic acid, 69.06g 3- hydroxybenzoic acids, 7.38g N-（3- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides,
7.67g N-（4- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, 320mL acetic anhydride and 42mg zinc acetates.
Flask is equipped with seal glass dasher, a nitrogen inlet tube and an insulation still head.Moderate nitrogen stream is passed through,
Acetylization reaction 35min at 125 DEG C of temperature.Reactant mixture is heated with 1.1 DEG C/min of heating rate in drift sand bath, reacted
Temperature rises to 315 DEG C by 125 DEG C.Reaction terminates to obtain opaque melt, room temperature is cooled to, by product by being moved in flask
Go out, be then ground to fine powder.By the vacuum that obtained liquid-crystalline polyster powder is placed in 340 DEG C of temperature and vacuum is 40 kPas
Solidify 40min in foaming in baking oven, that is, obtain a kind of liquid crystal polyester flame-retardant foam material, it is fire-retardant etc. to have reached UL-94 V0
Level.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 8
Added in a 500mL three neck round bottom flask 48.05g 2,6- naphthalenediols, 64.86 g 2,6- naphthalenedicarboxylic acids,
282.27g 7- hydroxy-2-naphthoic acids, 36.92g N-（4- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides,
38.33g N-（3- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, 180mL acetic anhydride and 20mg octanoic acids are sub-
Tin.Flask is equipped with seal glass dasher, a nitrogen inlet tube and an insulation still head.It is passed through moderate nitrogen
Stream, the acetylization reaction 35min at 135 DEG C of temperature.Reactant mixture is added with 1.4 DEG C/min of heating rate in drift sand bath
Heat, reaction temperature rise to 320 DEG C by 135 DEG C.Reaction terminates to obtain opaque melt, room temperature is cooled to, by product by burning
Removed in bottle, be then ground to fine powder.It is 10 kPas that obtained liquid-crystalline polyster powder is placed in into 320 DEG C of temperature and vacuum
Vacuum drying oven in while foaming while solidify 60min, that is, obtain a kind of liquid crystal polyester flame-retardant foam material, reached UL-94 V0 hinder
Fire grade.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 9
In a 500mL three neck round bottom flask add 55.86g 1,1 '-biphenyl -3,4 '-diphenol, 72.67g 1,1 '-biphenyl -
3,3 '-dicarboxylic acids, 214.22g 4 '-Hydroxybiphenyl -3- carboxylic acids, 11.72g 3- amino phenylacetylene, 100mL acetic anhydride, 5mg
Sodium acetate and 25mg dibutyl tin laurates.Flask is equipped with seal glass dasher, a nitrogen inlet tube and a guarantor
Warm still head.Moderate nitrogen stream is passed through, the acetylization reaction 30min at 135 DEG C of temperature.With heating rate in drift sand bath
0.9 DEG C/min heats reactant mixture, and reaction temperature rises to 295 DEG C by 135 DEG C.Reaction terminates to obtain opaque melt
Body, room temperature is cooled to, by product by being removed in flask, is then ground to fine powder.Obtained liquid-crystalline polyster powder is placed in
Solidify 50min in foaming in 340 DEG C of temperature and the vacuum drying oven that vacuum is 50 kPas, that is, it is fire-retardant to obtain a kind of liquid crystal polyester
Expanded material, UL-94 V0 flame retardant ratings are reached.
The preparation of the liquid crystal polyester flame-retardant foam material of embodiment 10
93.11g 1,1 '-biphenyl -3,3 '-diphenol, 80.09g 2,6- naphthalenes two are added in a 1000mL three neck round bottom flask
Phenol, 242.23g 4,4 '-biphenyl dicarboxylic acid, 138.12g 7- hydroxy-2-naphthoic acids, 69.06g 3- hydroxybenzoic acids, 12.92g
N-（4- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides, 13.42g N-（3- acetoxyphenyl bases）- 4- phenylacetylenes
Base phthalic acid imides, 240mL acetic anhydride and 30mg stannous octoates.Flask is equipped with seal glass dasher, one
Nitrogen inlet tube and an insulation still head.Moderate nitrogen stream is passed through, the acetylization reaction 55min at 130 DEG C of temperature.Flowing
Reactant mixture is heated with 1.3 DEG C/min of heating rate in sand-bath, reaction temperature rises to 300 DEG C by 130 DEG C.Reaction terminates
Opaque melt is obtained, is cooled to room temperature, by product by being removed in flask, is then ground to fine powder.The liquid that will be obtained
Solidify 55min in foaming in the vacuum drying oven that brilliant polyester powder is placed in 330 DEG C of temperature and vacuum is 15 kPas, that is, obtain one
Kind liquid crystal polyester flame-retardant foam material, has reached UL-94 V0 flame retardant ratings.
Referring to accompanying drawing 1, it is that the liquid crystal polyester imide that the embodiment of the present invention 2 provides and the liquid crystal that embodiment 3 provides gather
Ester powder sample is with 3 DEG C/min of heating rate by 200 DEG C of complex viscosity-time graphs for being warming up to 370 DEG C and constant temperature 60min.
There it can be seen that there is the trend risen after falling before, the liquid that embodiment 2 provides with temperature rise in liquid crystal polymer viscosity
Brilliant polyesterimide is warming up to 320 DEG C and lowest melt viscosity 1000Pas occurs, and this is due to liquid crystal polyester imide main chain knot
There is imide group in structure stronger π-π to interact；And the liquid crystal polyester that embodiment 3 provides is warming up to 300 DEG C of appearance
Lowest melt viscosity 10Pas, illustrate that both of which has wider process window.As temperature is further up, active end group
Chain extension and cross-linking and curing reaction takes place, the liquid crystal polyester that the liquid crystal polyester imide and embodiment 3 that embodiment 2 provides provide
Viscosity increase rapidly, finally in 370 DEG C of constant temperature 60min viscosity close to maximum, it is complete to show that curing reaction is carried out.
Referring to accompanying drawing 2, the liquid crystal that it is the liquid crystal polyester imide that embodiment 2 provides in the present invention and embodiment 3 provides
The digital photograph in kind of polyester flame-retardant expanded material.There it can be seen that liquid crystal polyester imide and the implementation of the offer of embodiment 2
Liquid crystal polyester flame-retardant foam material made from example 3 is expandable to turn into foamed material, and inside all has equally distributed micropore
Structure, it is sufficient to the defects of proving to need foaming agent instant invention overcomes existing expanded material, achieve unexpected technology effect
Fruit.
Referring to accompanying drawing 3, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning before ESEM
（SEM）Photo.There it can be seen that the aperture of the microcellular structure of liquid crystal polyester flame-retardant foam material made from embodiment 3 is number
Hundred microns, further multiplication factor observes that hole wall is typical liquid crystal aligning fibrous morphology.
Referring to accompanying drawing 4, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning before three-dimensional X- penetrate
Line tomoscan（CT）Reconstruct photo.Expanded material pore size is defined in different colors using CT analysis softwares, from
In as can be seen that liquid crystal polyester flame-retardant foam material aperture made from embodiment 3 be hundreds of microns, from from SEM photograph
To result match.
Referring to accompanying drawing 5, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning before micropore it is equivalent
Diameter, using three-dimensional X-ray tomoscan（CT）The result that software is quantified to obtain for accompanying drawing 4.Embodiment as seen from the figure
The aperture of liquid crystal polyester flame-retardant foam material is mainly distributed on 200-2000 μm made from 3.
Referring to table 1, it is the density and porosity for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides.From
Liquid crystal polyester flame-retardant foam material made from visible embodiment 3 has low-density and high porosity in table.
The density and porosity for the liquid crystal polyester flame-retardant foam material that the embodiment 3 of table 1 provides
Referring to accompanying drawing 6, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning before micro pore volume, adopt
With three-dimensional X-ray tomoscan（CT）Software counts obtained result for accompanying drawing 5.Liquid crystal made from embodiment 3 as seen from the figure
Micro pore volume before the burning of polyester flame-retardant expanded material is mainly distributed on 107‒109μm3。
Referring to accompanying drawing 7, it is the thermal weight loss for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides（TG）- temperature
Write music line.Therefrom visible, liquid crystal polyester flame-retardant foam material has excellent heat resistance, initial pyrolyzation made from embodiment 3
Temperature（Tdi 5wt%）Carbon yield during higher than 455 DEG C, 800 DEG C is higher than 43%.This has benefited from all aromatic main chain knot of liquid crystal polyester
Structure has the presence of high heat resistance and cross-linked network structure.
Referring to table 2 and 3, they are the vertical combustion for the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides respectively
Burn（UL-94）Test result and grading performance.The liquid crystal polyester flame-retardant foam material as made from data in table understand embodiment 3
UL-94 V0 flame retardant ratings are reached.
The liquid crystal polyester imide flame-retardant foam material vertical combustion that the embodiment 3 of table 2 provides（UL-94）Test result
The liquid crystal polyester imide flame-retardant foam material vertical combustion that the embodiment 3 of table 3 provides（UL-94）Grading performance
Referring to table 4, it is the limited oxygen index of liquid crystal polyester flame-retardant foam material and existing report that the embodiment of the present invention 3 provides
Contrasted with UL-94 grades.There is liquid crystal polyester flame-retardant foam material made from embodiment 3 higher limit oxygen to refer to as seen from the table
Number（36.4%）, the expanded material of even better than other addition high levels of flame-retardant additives.
Liquid crystal polyester flame-retardant foam material and the limited oxygen index of existing report and UL-94 that the embodiment 3 of table 4 provides etc.
Level contrast table
Referring to accompanying drawing 8, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning after ESEM
（SEM）Photo.Understood compared with Fig. 3, it is bright in the micropore quantity after liquid crystal polyester flame-retardant foam material burning made from embodiment 3
Aobvious to increase, aperture reduces, and fibrous morphology is changed into smooth carbon residue protective layer.
Referring to accompanying drawing 9, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning after three-dimensional X- penetrate
Line tomoscan（CT）Reconstruct photo.Understood compared with Fig. 4, after liquid crystal polyester flame-retardant foam material burning made from embodiment 3
Micropore quantity relatively burn before showed increased, and aperture is substantially reduced, and illustrate acetic acid continuation remaining in combustion process middle hole wall
Discharge CO2, the microcellular structure for promoting a large amount of new apertures smaller formed.
Referring to accompanying drawing 10, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning after micropore etc.
Imitate diameter.Understood compared with Fig. 5, it is obvious in the micropore quantity after liquid crystal polyester flame-retardant foam material burning made from embodiment 3
Increase, aperture is mainly distributed on 20-300 μm, illustrates that acetic acid remaining in hole wall continues to decompose release CO in combustion2,
The smaller microcellular structure of more multiple aperture is formd in system.
Referring to accompanying drawing 11, it be the liquid crystal polyester flame-retardant foam material that the embodiment of the present invention 3 provides burning after porous body
Product.Understood compared with Fig. 6, the micro pore volume after liquid crystal polyester flame-retardant foam material burning made from embodiment 3 is bright before relatively burning
It is aobvious to increase, and aperture is substantially reduced, and is mainly distributed on 104‒108μm3.Illustrate that acetic acid remaining in combustion process middle hole wall enters one
Step decomposes release CO2, the microcellular structure for promoting a large amount of new apertures smaller formed.
The preparation of the liquid crystal polyester flame-retardant foam material of comparative example 1
Added in a 500mL three neck round bottom flask 37.24g 1,4- hydroquinones, 33.23g 1,4- terephthalic acid (TPA)s,
69.06g 3- hydroxybenzoic acids, 18.82g 7- hydroxy-2-naphthoic acids, 27.34g N-（4- carboxyl phenyls）- 4- phenylacetylene bases are adjacent
Phthalic acid acid imide, 28.39g N-（4- acetoxyphenyl bases）- 4- phenylacetylene bases phthalic acid imides, 150mL acetic acid
Acid anhydride and 10mg potassium acetates.Flask is equipped with seal glass dasher, a nitrogen inlet tube and an insulation still head.It is passed through
Moderate nitrogen stream, the acetylization reaction 30min at 140 DEG C of temperature.It will be reacted with 1.0 DEG C/min of heating rate in drift sand bath
Mixture heats, and reaction temperature rises to 310 DEG C by 140 DEG C.Reaction terminates to obtain opaque melt, is cooled to room temperature, will
Product is then ground to fine powder by being removed in flask.
Obtained liquid-crystalline polyster powder is placed in into 370 DEG C of temperature and vacuum to foam for side in 970 kPas of vacuum drying oven
Side solidifies 50min, and because vacuum is too low, the vacuum ranges that are limited in technical scheme lead to not successfully preparation solution
Brilliant flame-retardant foam material.
To sum up, the invention is foaming using accessory substance acetic acid remaining in liquid crystal polymer polycondensation process
Agent, release CO is solved in the high temperature time-division2Microcellular structure is formed, while matrix occurs curing reaction and forms cross-linked network structure, success
The uniform expanded material in space is prepared, opens the new method for preparing liquid crystal flame-retardant foam material；And liquid provided by the invention
Brilliant flame-retardant foam material shows excellent fire resistance.This aspect is excellent by all aromatic main chain of liquid crystal polymer
Heat-resistant quality, the liquid crystal fiber shape compact texture formed on the microcellular structure and hole wall of foamed material itself contribute to barrier to fire
The transmission of burning oxygen at initial stage and heat；On the other hand, acetic acid remaining in hole wall continues to discharge CO in combustion2, and shape
The microcellular structure smaller into a large amount of new apertures, the effect of blocking oxygen and heat transfer is played, is advantageous to suppress burning.
Claims (10)
1. a kind of preparation method of liquid crystal flame-retardant foam material, it is characterised in that comprise the following steps：
（1）Using aromatic series diphenol monomer, aromatic diacid monomer, the aromatic monomer containing terminal hydroxy group and end carboxyl as raw material,
In the presence of active end group, catalyst, acetic acid compound, under nitrogen protection, 30~60min is reacted in 120~140 DEG C；So
280~325 DEG C are warming up to 0.5~1.5 DEG C/min speed afterwards, 1~3h is reacted, obtains solids；
（2）By solids under 10~90 kPas of vacuum, 20~60min is handled in 320~380 DEG C, obtains the fire-retardant hair of liquid crystal
Foam material.
2. according to the preparation method of liquid crystal flame-retardant foam material described in claim 1, it is characterised in that：The aromatic series diphenol list
Body be 1,4- hydroquinones, 1,3- resorcinols, 4,4 '-'-biphenyl diphenol, 1,1 '-biphenyl -3,4 '-diphenol, 1,1 '-biphenyl -3,
One or more in 3 '-diphenol, 1,6- naphthalenediols, 1,7- naphthalenediols, 2,6- naphthalenediols, 2,7- naphthalenediols；The aromatic series
Diacid monomer is 1,4- terephthalic acid (TPA)s, 1,3- M-phthalic acids, 4,4 '-biphenyl dicarboxylic acid, 1,1 '-biphenyl -3,4 '-dicarboxyl
Acid, 1,1 '-biphenyl -3,3 '-dicarboxylic acids, 1,6- naphthalenedicarboxylic acids, 1,7- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids
In one or more；The aromatic monomer containing terminal hydroxy group and end carboxyl be 3- hydroxybenzoic acids, 4 '-Hydroxybiphenyl-
3- carboxylic acids, 7- hydroxy-2-naphthoic acids, N-（3'- hydroxyphenyls）One or more in the inclined acid imide of benzene three.
3. according to the preparation method of liquid crystal flame-retardant foam material described in claim 1, it is characterised in that：The active end group is 3-
Amino phenylacetylene, N-（4- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides, N-（4- acetoxyphenyl bases）- 4- benzene
Acetenyl phthalic acid imides, N-（3- carboxyl phenyls）- 4- phenylacetylene bases phthalic acid imides, N-（3- acetic acid benzene
Phenolic ester base）One or more in -4- phenylacetylene base phthalic acid imides；The catalyst is potassium acetate, sodium acetate, vinegar
One kind in sour zinc, Dibutyltin oxide, stannous octoate, dibutyl tin laurate；The acetic acid compound is acetic anhydride.
4. according to the preparation method of liquid crystal flame-retardant foam material described in claim 1, it is characterised in that：The aromatic series diphenol list
Body, aromatic diacid monomer, aromatic monomer containing terminal hydroxy group and end carboxyl, active end group, catalyst, acetic acid compound
Mol ratio is 1: 1:（0.5~2）∶（0.03~0.45）∶（0.5 ‰~5 ‰）∶（1.5~4）.
5. according to the preparation method of liquid crystal flame-retardant foam material described in claim 1, it is characterised in that：Step（2）In, by solid
Thing is ground to after powder under 10~90 kPas of vacuum, is handled 20~60min in 320~380 DEG C, is obtained the fire-retardant hair of liquid crystal
Foam material.
6. liquid crystal flame-retardant foam material prepared by the preparation method according to liquid crystal flame-retardant foam material described in claim 1.
7. a kind of preparation method of liquid crystal flame-retardant foam material presoma, it is characterised in that comprise the following steps, with aromatic series two
Phenol monomer, aromatic diacid monomer, the aromatic monomer containing terminal hydroxy group and end carboxyl are raw material, active end group, catalyst,
In the presence of acetic acid compound, under nitrogen protection, 30~60min is reacted in 120~140 DEG C；Then with 0.5~1.5 DEG C/min
Speed be warming up to 280~325 DEG C, react 1~3h, obtain liquid crystal flame-retardant foam material presoma.
8. liquid crystal flame-retardant foam material prepared by the preparation method according to liquid crystal flame-retardant foam material presoma described in claim 7
Presoma.
9. application of the liquid crystal flame-retardant foam material presoma in flame-retardant foam material is prepared described in claim 8.
10. application of the liquid crystal flame-retardant foam material in flame-retardant foam material is prepared described in claim 6.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019100408A1 (en) * | 2017-11-27 | 2019-05-31 | 苏州大学 | Liquid crystal flame-retardant foam material and preparation method therefor |
| WO2019188959A1 (en) * | 2018-03-27 | 2019-10-03 | 住友化学株式会社 | Aromatic liquid crystal polyester, aromatic liquid crystal polyester composition, and molded article |
| CN112144140A (en) * | 2020-09-28 | 2020-12-29 | 浙江恒澜科技有限公司 | Preparation method of thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester fiber |
| CN112250848A (en) * | 2020-09-28 | 2021-01-22 | 浙江恒澜科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester material and preparation method thereof |
| CN112574402A (en) * | 2020-12-17 | 2021-03-30 | 上海思涛新材料科技有限公司 | Thermotropic anti-droplet aromatic liquid crystal copolyester and preparation method thereof |
| CN112608461A (en) * | 2020-12-17 | 2021-04-06 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112646153A (en) * | 2020-12-17 | 2021-04-13 | 上海思涛新材料科技有限公司 | Flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112646141A (en) * | 2020-12-17 | 2021-04-13 | 上海思涛新材料科技有限公司 | Flame-retardant aromatic liquid crystal copolyester and preparation method thereof |
| CN113045737A (en) * | 2021-04-06 | 2021-06-29 | 深圳市华盈新材料有限公司 | High heat-resistant liquid crystal polymer |
| CN115322135A (en) * | 2019-08-28 | 2022-11-11 | 东华大学 | Aromatic thermosetting liquid crystal fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276868A (en) * | 2011-06-10 | 2011-12-14 | 同济大学 | Preparation method for aromatic copolyester porous material |
| CN103570927A (en) * | 2012-07-06 | 2014-02-12 | 金发科技股份有限公司 | Thermotropic liquid crystal polyester and preparation method thereof |
| CN106633059A (en) * | 2016-11-04 | 2017-05-10 | 沈阳航空航天大学 | Ethynyl terminated polyarylene ether nitrile imide resin and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012177103A (en) * | 2011-01-31 | 2012-09-13 | Sumitomo Chemical Co Ltd | Liquid crystal polyester and production method thereof |
| CN106810695B (en) * | 2017-01-12 | 2019-09-06 | 苏州大学 | A kind of aromatic polyesterimides and preparation method thereof |
| CN106810676B (en) * | 2017-01-12 | 2019-05-17 | 苏州大学 | A kind of aromatic polyester and preparation method thereof |
-
2017
- 2017-10-30 CN CN201711035250.9A patent/CN107793585B/en active Active
- 2017-10-30 CN CN202011004117.9A patent/CN112094423B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276868A (en) * | 2011-06-10 | 2011-12-14 | 同济大学 | Preparation method for aromatic copolyester porous material |
| CN103570927A (en) * | 2012-07-06 | 2014-02-12 | 金发科技股份有限公司 | Thermotropic liquid crystal polyester and preparation method thereof |
| CN106633059A (en) * | 2016-11-04 | 2017-05-10 | 沈阳航空航天大学 | Ethynyl terminated polyarylene ether nitrile imide resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| GUAN QINGBAO ET AL.: "All-Aromatic (AB)n-Multiblock Copolymers via Simple One-Step Melt Condensation Chemistry", 《MACROMOLECULES》 * |
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|---|---|---|---|---|
| WO2019100408A1 (en) * | 2017-11-27 | 2019-05-31 | 苏州大学 | Liquid crystal flame-retardant foam material and preparation method therefor |
| WO2019188959A1 (en) * | 2018-03-27 | 2019-10-03 | 住友化学株式会社 | Aromatic liquid crystal polyester, aromatic liquid crystal polyester composition, and molded article |
| JPWO2019188959A1 (en) * | 2018-03-27 | 2021-03-11 | 住友化学株式会社 | Aromatic liquid crystal polyester, aromatic liquid crystal polyester composition and molded article |
| JP7267257B2 (en) | 2018-03-27 | 2023-05-01 | 住友化学株式会社 | Aromatic liquid crystal polyester, aromatic liquid crystal polyester composition and molded article |
| CN115322135A (en) * | 2019-08-28 | 2022-11-11 | 东华大学 | Aromatic thermosetting liquid crystal fiber and preparation method thereof |
| CN112250848B (en) * | 2020-09-28 | 2022-08-12 | 浙江恒逸石化研究院有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester material and preparation method thereof |
| CN112144140A (en) * | 2020-09-28 | 2020-12-29 | 浙江恒澜科技有限公司 | Preparation method of thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester fiber |
| CN112250848A (en) * | 2020-09-28 | 2021-01-22 | 浙江恒澜科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester material and preparation method thereof |
| CN112608461A (en) * | 2020-12-17 | 2021-04-06 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112608461B (en) * | 2020-12-17 | 2021-08-17 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112646141A (en) * | 2020-12-17 | 2021-04-13 | 上海思涛新材料科技有限公司 | Flame-retardant aromatic liquid crystal copolyester and preparation method thereof |
| CN112646153A (en) * | 2020-12-17 | 2021-04-13 | 上海思涛新材料科技有限公司 | Flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112574402A (en) * | 2020-12-17 | 2021-03-30 | 上海思涛新材料科技有限公司 | Thermotropic anti-droplet aromatic liquid crystal copolyester and preparation method thereof |
| CN113045737A (en) * | 2021-04-06 | 2021-06-29 | 深圳市华盈新材料有限公司 | High heat-resistant liquid crystal polymer |
| CN113045737B (en) * | 2021-04-06 | 2022-11-18 | 河南华盈新材料有限公司 | High heat-resistant liquid crystal polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112094423B (en) | 2022-06-07 |
| CN107793585B (en) | 2020-10-27 |
| CN112094423A (en) | 2020-12-18 |
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