CN107793585B - Liquid crystal flame-retardant foam material and preparation method thereof - Google Patents
Liquid crystal flame-retardant foam material and preparation method thereof Download PDFInfo
- Publication number
- CN107793585B CN107793585B CN201711035250.9A CN201711035250A CN107793585B CN 107793585 B CN107793585 B CN 107793585B CN 201711035250 A CN201711035250 A CN 201711035250A CN 107793585 B CN107793585 B CN 107793585B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- flame
- retardant
- acid
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a liquid crystal flame-retardant foam material and a preparation method thereof, wherein an aromatic diphenol monomer, an aromatic diacid monomer and an aromatic monomer containing terminal hydroxyl and terminal carboxyl are used as raw materials, and the raw materials are reacted for 30-60 min at 120-140 ℃ under the protection of nitrogen in the presence of an active terminal group, a catalyst and an acetic acid compound; then heating to 280-325 ℃ at the speed of 0.5-1.5 ℃/min, and reacting for 1-3 h to obtain a solid; and heating the solid in vacuum to obtain the liquid crystal flame-retardant foaming material. The invention uses the residual by-product acetic acid in the polycondensation reaction process of the liquid crystal polymer as the foaming agent, and the residual by-product acetic acid is decomposed to release CO at high temperature2The method has the advantages that a microporous structure is formed, and simultaneously, the matrix is subjected to a curing reaction to form a cross-linked network structure, so that a novel method for preparing the liquid crystal flame-retardant foam material is developed, particularly, the flame-retardant effect is achieved without adding a flame retardant, and the UL-94V 0 flame-retardant grade is achieved; in addition, the preparation method has the characteristics of environmental protection, simplicity, convenience and wide applicability.
Description
Technical Field
The invention relates to a liquid crystal flame-retardant foam material and a preparation method thereof, belonging to the field of high-performance polymers.
Background
The polymer foaming material such as a polystyrene foam insulation board, a polyurethane foam product and the like is widely applied to the fields of buildings, high-speed rails, aviation and the like due to excellent mechanical, acoustic, electrical, insulation and other properties. However, the heat resistance and flame retardance of the polymer foam material are poor, the fire loss caused by the flammability of the polymer foam material is huge every year, the contradiction between the market demand and the application safety is increasingly prominent, and the demand for improving the flame retardance of the polymer foam material is increased sharply.
Flame retardancy is obtained by adding various flame retardants in the preparation process of polymer foam materials, wherein the most commonly used flame retardants are organic compounds containing halogen or phosphorus nitrogen. For example, WO91/19758 discloses a method for improving the flame retardancy of polystyrene foams using hexabromocyclododecane; patent US6578911 discloses a method for improving the flame retardancy of polyurethane foam products by using a halogenated phosphate ester compound and a phosphate ester flame retardant; patent CN99814260.3 discloses a method for flame retarding polystyrene foam with expanded graphite and a phosphorus compound. However, the existing methods for improving the flame retardance of the polymer foaming material have the following problems: (1) the additive organic flame retardant is easy to decompose, can seriously corrode equipment and cause the attenuation of flame retardant property; (2) the addition of higher amounts of flame retardants tends to deteriorate the structural and surface quality of the foam, reducing the strength of the foam or its insulating properties; (3) the long-term use of organic flame retardants containing halogen, phosphorus, nitrogen, etc. has serious environmental pollution.
In addition, the foaming agent is an essential raw material for preparing the existing foam material, and the foaming agent (such as azodicarbonamide and the like) used in the preparation process of the foam material is mostly a compound harmful to human bodies. Therefore, how to prepare the foaming material with both easy foaming and high flame retardant performance without adding a flame retardant is a topic with great application value in the field of high-performance polymers at present.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a liquid crystal flame-retardant foaming material which does not need to be added with a flame retardant and has easy foaming and excellent flame-retardant performance and a preparation method thereof.
The technical scheme adopted for achieving the purpose of the invention is as follows:
a preparation method of a liquid crystal flame-retardant foaming material comprises the following steps:
(1) taking an aromatic diphenol monomer, an aromatic diacid monomer and an aromatic monomer containing a terminal hydroxyl group and a terminal carboxyl group as raw materials, and reacting for 30-60 min at 120-140 ℃ under the protection of nitrogen in the presence of an active terminal group, a catalyst and an acetic acid compound; then heating to 280-325 ℃ at the speed of 0.5-1.5 ℃/min, and reacting for 1-3 h to obtain a solid;
(2) and (3) treating the solid at the vacuum degree of 10-90 kilopascals for 20-60 min at the temperature of 320-380 ℃ to obtain the liquid crystal flame-retardant foaming material.
The invention also discloses a preparation method of the liquid crystal flame-retardant foaming material precursor, which comprises the following steps:
taking an aromatic diphenol monomer, an aromatic diacid monomer and an aromatic monomer containing a terminal hydroxyl group and a terminal carboxyl group as raw materials, and reacting for 30-60 min at 120-140 ℃ under the protection of nitrogen in the presence of an active terminal group, a catalyst and an acetic acid compound; then heating to 280-325 ℃ at the speed of 0.5-1.5 ℃/min, and reacting for 1-3 h to obtain a precursor of the liquid crystal flame-retardant foaming material; the method limits the heating rate to 0.5-1.5 ℃/min, is favorable for complete polycondensation reaction, and obtains the liquid crystal flame-retardant foaming material precursor meeting the target molecular weight, so that the precursor can be decomposed at high temperature to release CO2Forming a microporous structure, and simultaneously carrying out a curing reaction on the matrix to form a cross-linked network structure, thereby preparing the liquid crystal flame-retardant foam material without adding a flame retardant.
In the technical scheme, the aromatic diphenol monomer is one or more of 1, 4-hydroquinone, 1, 3-resorcinol, 4 ' -biphenol, 1 ' -biphenyl-3, 4 ' -diphenol, 1 ' -biphenyl-3, 3' -diphenol, 1, 6-naphthalenediol, 1, 7-naphthalenediol, 2, 6-naphthalenediol and 2, 7-naphthalenediol; the aromatic diacid monomer is one or more of 1, 4-terephthalic acid, 1, 3-isophthalic acid, 4 ' -biphenyl dicarboxylic acid, 1 ' -biphenyl-3, 4 ' -dicarboxylic acid, 1 ' -biphenyl-3, 3' -dicarboxylic acid, 1, 6-naphthalene dicarboxylic acid, 1, 7-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid and 2, 7-naphthalene dicarboxylic acid; the aromatic monomer containing the terminal hydroxyl and the terminal carboxyl is one or more of 3-hydroxybenzoic acid, 4 '-hydroxybiphenyl-3-carboxylic acid, 7-hydroxy-2-naphthoic acid and N- (3' -hydroxyphenyl) trimellitimide; .
In the technical scheme, the active end group is one or more of 3-aminophenylacetylene, N- (4-carboxyphenyl) -4-phenylethynyl phthalic acid imide, N- (4-acetic acid phenol ester group) -4-phenylethynyl phthalic acid imide, N- (3-carboxyphenyl) -4-phenylethynyl phthalic acid imide and N- (3-acetic acid phenol ester group) -4-phenylethynyl phthalic acid imide; the catalyst is one of potassium acetate, sodium acetate, zinc acetate, dibutyltin oxide, stannous octoate and dibutyltin laurate; the acetic acid compound is acetic anhydride.
In the technical scheme, the molar ratio of the aromatic diphenol monomer to the aromatic diacid monomer to the aromatic monomer containing terminal hydroxyl and terminal carboxyl, the molar ratio of the active terminal group to the catalyst to the acetic acid compound is 1: 1 to (0.5-2) to (0.03-0.45) to (0.5-5 thousandths to 5 thousandths) to (1.5-4); the invention limits the molar ratio range of the reaction starting materials, which is beneficial to obtaining the liquid crystal flame-retardant foaming material precursor which meets the target molecular weight, thereby being beneficial to the solidification reaction of the matrix to form a cross-linked network structure and preparing the liquid crystal flame-retardant foaming material without adding a flame retardant.
In the technical scheme, in the step (2), the solid is ground into powder and then treated for 20-60 min at 320-380 ℃ under the vacuum degree of 10-90 kilopascals, so as to obtain the liquid crystal flame-retardant foam material; the limited vacuum degree of 10-90 kPa is favorable for obtaining the liquid crystal flame-retardant foam material with uniform pore size distribution and controllable porosity; the limited temperature and time are respectively 320-380 ℃ and 20-60 min, which is beneficial to obtaining the liquid crystal flame-retardant foaming material which is fully foamed and solidified2The microporous structure is formed, and simultaneously, the matrix is subjected to curing reaction to form a cross-linked network structure, so that a novel method for preparing the liquid crystal flame-retardant foam material is developed.
The invention discloses a liquid crystal flame-retardant foam material prepared by the preparation method of the liquid crystal flame-retardant foam material.
The invention discloses a liquid crystal flame-retardant foaming material precursor prepared by the preparation method of the liquid crystal flame-retardant foaming material precursor and application of the liquid crystal flame-retardant foaming material precursor in preparation of a flame-retardant foaming material.
The invention can be represented by way of example as follows:
(1) adding 1mol of aromatic diphenol monomer (X), 1mol of aromatic diacid monomer (Y), 0.5-2 mol of meta-AB type aromatic monomer (Z) containing terminal hydroxyl A and terminal carboxyl B, active terminal group, 0.5-2 mmol of catalyst and 1.5-4 mol of acetic anhydride into a reactor; performing acetylation reaction at the temperature of 120-140 ℃ for 30-60 min under the protection of nitrogen;
(2) heating to 280-325 ℃ at the speed of 0.5-1.5 ℃/min, and carrying out ester exchange reaction for 1-3 h; cooling to room temperature after the reaction is finished, and grinding the product into fine powder;
(3) and (3) placing the fine powder obtained in the step (2) in a vacuum oven with the vacuum degree of 10-90 kilopascals (100-900 mbar) and the temperature of 320-380 ℃ for foaming and curing for 20-60 min to obtain the liquid crystal flame-retardant foaming material.
The invention uses the residual by-product acetic acid in the polycondensation reaction process of the liquid crystal polymer as the foaming agent, and the residual by-product acetic acid is decomposed to release CO at high temperature2The microporous structure is formed, and simultaneously, the matrix is subjected to curing reaction to form a cross-linked network structure, so that a novel method for preparing the liquid crystal flame-retardant foam material is developed. According to the invention, the flame retardant is not required to be added to achieve the flame retardant effect, but the excellent heat-resistant characteristic of the wholly aromatic main chain of the liquid crystal polymer is relied on, the self microporous structure of the foam material and the pore wall polymer are continuously foamed to release CO in the combustion process2Both have the effects of oxygen blocking and heat conduction. The invention discloses an application of the liquid crystal flame-retardant foam material in preparation of a flame-retardant foam material.
Compared with the prior art, the invention has the beneficial effects that:
1. different from the prior art that the foaming agent is added, the invention firstly utilizes the byproduct acetic acid generated in the polycondensation reaction process of the liquid crystal polymer as the foaming agent, and the byproduct acetic acid can be decomposed at high temperature to release CO2Forming a microporous structure; meanwhile, the matrix is subjected to curing reaction to form a cross-linked network structure, so that the foamed polymer is successfully obtained, and a novel method for preparing the liquid crystal flame-retardant foamed material is developed.
2. Different from the traditional method for preparing the flame-retardant foam material by adding the flame retardant, the invention is intrinsic flame-retardant, and the flame-retardant mechanism is different from the prior art; the invention selects wholly aromatic monomer as the initiator of the one-pot polymerization reaction, depends on the excellent heat-resisting property of the wholly aromatic main chain of the liquid crystal polymer, and the microcellular structure of the foam material and the polymer of the pore wall are continuously foamed to release CO in the combustion process2The flame retardant foaming material has the effects of blocking oxygen and heat conduction, so that the liquid crystal flame retardant foaming material with excellent flame retardant property is obtained, and the flame retardant grade of UL-94V 0 is achieved.
3. Because no flame retardant is added, the one-pot polycondensation reaction method is simple and controllable, and the preparation process of curing and foaming is energy-saving and efficient, the preparation method has the characteristics of environmental protection, simplicity, convenience and wide applicability.
Drawings
FIG. 1 is a composite viscosity-time curve of samples of liquid crystal polyester imide provided in example 2 of the present invention and liquid crystal polyester powder provided in example 3, heated from 200 ℃ to 370 ℃ at a heating rate of 3 ℃/min and held at the same temperature for 60 min;
FIG. 2 is a digital photo of a liquid crystal polyester imide provided in example 2 and a liquid crystal polyester flame retardant foam material provided in example 3;
FIG. 3 is a Scanning Electron Microscope (SEM) picture before combustion of the liquid crystal polyester flame-retardant foamed material provided by example 3 of the invention;
FIG. 4 is a three-dimensional X-ray tomography (CT) reconstructed picture before combustion of the liquid crystal polyester flame-retardant foamed material provided by the embodiment 3 of the invention;
FIG. 5 is the equivalent diameter of the microcells before combustion of the liquid crystal polyester flame-retardant foamed material provided in example 3 of the present invention;
FIG. 6 is a micropore volume before combustion of a liquid crystal polyester flame retardant foam provided in example 3 of the present invention;
FIG. 7 is a Thermogravimetric (TG) -temperature curve of the liquid crystal polyester flame retardant foaming material provided by the embodiment 3 of the invention;
FIG. 8 is a Scanning Electron Microscope (SEM) photograph of the liquid crystal polyester flame-retardant foamed material provided in example 3 of the invention after combustion;
FIG. 9 is a three-dimensional X-ray tomography (CT) reconstructed picture of the liquid crystal polyester flame-retardant foamed material provided in example 3 of the present invention after combustion;
FIG. 10 is the equivalent diameter of the burnt microcells of the flame-retardant foaming material of liquid crystal polyester provided in example 3 of the invention;
FIG. 11 shows the cell volume after burning of the liquid crystal polyester flame retardant foam provided in example 3 of the present invention.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and examples.
EXAMPLE 1 preparation of liquid Crystal polyester flame retardant foam
A250 mL three necked round bottom flask was charged with 16.02g of 1, 6-naphthalenediol, 21.62g of 2, 7-naphthalenedicarboxylic acid, 21.42g of 4' -hydroxybiphenyl-3-carboxylic acid, 3.84g N- (4-carboxyphenyl) -4-phenylethynylphthalimide, 4.02g N- (4-acetoxyphenol ester) -4-phenylethynylphthalimide, 50mL of acetic anhydride and 2mg of dibutyltin oxide. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing nitrogen flow, and carrying out acetylation reaction at the temperature of 130 ℃ for 45 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.0 deg.C/min, the reaction temperature increasing from 130 deg.C to 280 deg.C. After the reaction was completed, an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and then ground into a fine powder, which was a liquid crystalline polyester powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 320 ℃ and the vacuum degree of 80 kilopascals, foaming and curing for 60min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
EXAMPLE 2 preparation of liquid Crystal polyester imide flame retardant foam
A500 mL three necked round bottom flask was charged with 93.10g of 1, 3-resorcinol, 83.08g of 1, 3-isophthalic acid, 39.16g N- (3' -hydroxyphenyl) trimellitimide, 41.01g N- (3-carboxyphenyl) -4-phenylethynylphthalimide, 42.59g N- (3-acetoxyphenol ester) -4-phenylethynylphthalimide, 300mL of acetic anhydride, and 25mg of sodium acetate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and performing acetylation reaction at 120 ℃ for 60 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 0.5 deg.C/min, the reaction temperature increasing from 120 deg.C to 325 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. The composite viscosity-time curve of the powder sample is shown in figure 1, wherein the temperature of the powder sample is increased from 200 ℃ to 370 ℃ at the heating rate of 3 ℃/min and is kept constant for 60 min.
And (3) placing the obtained liquid crystal polyester imide powder in a vacuum oven with the temperature of 370 ℃ and the vacuum degree of 80 kilopascals, foaming and curing for 60min to obtain the liquid crystal polyester imide flame-retardant foam material, wherein the flame-retardant grade of the liquid crystal polyester imide foam material reaches UL-94V 0, and the digital photo of the substance is shown in figure 2.
EXAMPLE 3 preparation of liquid Crystal polyester flame retardant foam
A500 mL three necked round bottom flask was charged with 37.24g of 1, 4-hydroquinone, 33.23g of 1, 4-terephthalic acid, 69.06g of 3-hydroxybenzoic acid, 18.82g of 7-hydroxy-2-naphthoic acid, 27.34g of 27.34g N- (4-carboxyphenyl) -4-phenylethynylphthalimide, 28.39g N- (4-acetoxyphenolate) -4-phenylethynylphthalimide, 150mL of acetic anhydride, and 10mg of potassium acetate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction for 30min at the temperature of 140 ℃. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.0 deg.C/min, the reaction temperature increasing from 140 deg.C to 310 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. The composite viscosity-time curve of the powder sample is shown in figure 1, wherein the temperature of the powder sample is increased from 200 ℃ to 370 ℃ at the heating rate of 3 ℃/min and is kept constant for 60 min.
Placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 370 ℃ and the vacuum degree of 70 kilopascals, foaming and curing for 50min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the density, the porosity, the vertical combustion (UL-94) test result, the performance grading and the reference comparison refer to tables 1, 2, 3 and 4, the physical digital picture, the Scanning Electron Microscope (SEM) picture before combustion, the three-dimensional X-ray tomography (CT) reconstruction picture, the micropore equivalent diameter and the micropore volume refer to the attached figures 2, 3,4, 5 and 6 respectively, and the thermal weight loss (TG) -temperature curve, the Scanning Electron Microscope (SEM) picture after combustion, the three-dimensional X-ray tomography (CT) reconstruction picture, the micropore equivalent diameter and the micropore volume refer to the attached figures 7, 8, 9, 10 and 11 respectively.
EXAMPLE 4 preparation of liquid Crystal polyester flame retardant foam
A1000 mL three necked round bottom flask was charged with 80.09g of 2, 7-naphthalenediol, 93.11g of 4,4 '-biphenyldiphenol, 108.10g of 1, 6-naphthalenedicarboxylic acid, 121.12g of 4, 4' -biphenyldicarboxylic acid, 69.06g of 3-hydroxybenzoic acid, 7.38- (3-carboxyphenyl) -4-phenylethynylphthalimide, 7.67- (4-acetoxyphenol ester) -4-phenylethynylphthalimide, 300mL of acetic anhydride and 45mg of zinc acetate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction for 30min at the temperature of 140 ℃. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.5 deg.C/min, the reaction temperature increasing from 140 deg.C to 315 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 380 ℃ and the vacuum degree of 90 kilopascals, foaming and curing for 30min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
EXAMPLE 5 preparation of liquid Crystal polyester imide flame retardant foam
A1000 mL three necked round bottom flask was charged with 111.73g of 1,1 ' -biphenyl-3, 3' -diol, 129.71g of 1, 7-naphthalenedicarboxylic acid, 211.20g N- (3 ' -hydroxyphenyl) trimellitimide, 69.06g of 3-hydroxybenzoic acid, 14.77g N- (3-carboxyphenyl) -4-phenylethynylphthalimide, 15.33g N- (3-acetoxyphenol ester) -4-phenylethynylphthalimide, 300mL of acetic anhydride and 35mg of sodium acetate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and performing acetylation reaction at the temperature of 130 ℃ for 45 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.0 deg.C/min, the reaction temperature increasing from 130 deg.C to 280 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 370 ℃ and the vacuum degree of 60 kilopascals, foaming and curing for 20min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
EXAMPLE 6 preparation of liquid Crystal polyester flame retardant foam
A1000 mL three necked round bottom flask was charged with 160.17g of 2, 7-naphthalenediol, 108.10g of 1, 7-naphthalenedicarboxylic acid, 121.12g of 1,1 '-biphenyl-3, 4' -dicarboxylic acid, 69.06g of 3-hydroxybenzoic acid, 282.27g of 7-hydroxy-2-naphthoic acid, 18.46g N- (4-carboxyphenyl) -4-phenylethynylphthalimide, 19.17g N- (3-acetoxyphenolate) -4-phenylethynylphthalimide, 380mL of acetic anhydride, 5mg of sodium acetate, and 75mg of stannous octoate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and performing acetylation reaction at the temperature of 125 ℃ for 45 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.2 deg.C/min, the reaction temperature increasing from 125 deg.C to 300 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 330 ℃ and the vacuum degree of 10 kilopascals, foaming and curing for 50min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
Example 7 preparation of liquid crystalline polyester flame retardant foam
A1000 mL three necked round bottom flask was charged with 80.09g of 1, 7-naphthalenediol, 121.12g of 1,1 '-biphenyl-3, 4' -dicarboxylic acid, 69.06g of 3-hydroxybenzoic acid, 7.38g N- (3-carboxyphenyl) -4-phenylethynylphthalimide, 7.67g N- (4-acetoxyphenol ester) -4-phenylethynylphthalimide, 320mL of acetic anhydride, and 42mg of zinc acetate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction for 35min at the temperature of 125 ℃. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.1 deg.C/min, the reaction temperature increasing from 125 deg.C to 315 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 340 ℃ and the vacuum degree of 40 kilopascals, foaming and curing for 40min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
EXAMPLE 8 preparation of liquid Crystal polyester flame retardant foam
A500 mL three necked round bottom flask was charged with 48.05g of 2, 6-naphthalenediol, 64.86 g of 2, 6-naphthalenedicarboxylic acid, 282.27g of 7-hydroxy-2-naphthoic acid, 36.92g N- (4-carboxyphenyl) -4-phenylethynylphthalimide, 38.33g N- (3-acetoxyphenolate) -4-phenylethynylphthalimide, 180mL of acetic anhydride, and 20mg of stannous octoate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction at the temperature of 135 ℃ for 35 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.4 deg.C/min, the reaction temperature increasing from 135 deg.C to 320 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 320 ℃ and the vacuum degree of 10 kilopascals, foaming and curing for 60min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
EXAMPLE 9 preparation of liquid Crystal polyester flame retardant foam
A500 mL three necked round bottom flask was charged with 55.86g of 1,1 ' -biphenyl-3, 4 ' -diol, 72.67g of 1,1 ' -biphenyl-3, 3' -dicarboxylic acid, 214.22g of 4 ' -hydroxybiphenyl-3-carboxylic acid, 11.72g of 3-aminophenylacetylene, 100mL of acetic anhydride, 5mg of sodium acetate, and 25mg of dibutyltin laurate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction at the temperature of 135 ℃ for 30 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 0.9 deg.C/min, the reaction temperature increasing from 135 deg.C to 295 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 340 ℃ and the vacuum degree of 50 kilopascals, foaming and curing for 50min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
EXAMPLE 10 preparation of liquid Crystal polyester flame retardant foam
A1000 mL three necked round bottom flask was charged with 93.11g of 1,1 ' -biphenyl-3, 3' -diol, 80.09g of 2, 6-naphthalenediol, 242.23g of 4,4 ' -biphenyldicarboxylic acid, 138.12g of 7-hydroxy-2-naphthoic acid, 69.06g of 3-hydroxybenzoic acid, 12.92g of 12.92g N- (4-carboxyphenyl) -4-phenylethynylphthalimide, 13.42g N- (3-acetoxyphenolate) -4-phenylethynylphthalimide, 240mL of acetic anhydride, and 30mg of stannous octoate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and performing acetylation reaction at 130 ℃ for 55 min. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.3 deg.C/min, the reaction temperature increasing from 130 deg.C to 300 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder. Placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 330 ℃ and the vacuum degree of 15 kilopascals, foaming and curing for 55min to obtain the liquid crystal polyester flame-retardant foaming material, wherein the flame-retardant grade of UL-94V 0 is achieved.
Referring to FIG. 1, there are shown composite viscosity-time curves of a liquid crystal polyester imide provided in example 2 of the present invention and a liquid crystal polyester powder sample provided in example 3, which were heated from 200 ℃ to 370 ℃ at a heating rate of 3 ℃/min and then held at the same temperature for 60 min. It can be seen that the viscosity of the liquid crystal polymer tends to decrease and then increase with the increase of temperature, and the liquid crystal polyester imide provided in example 2 has a minimum melt viscosity of 1000Pa · s when the temperature is increased to 320 ℃, because imide groups in the main chain structure of the liquid crystal polyester imide have strong pi-pi interaction; on the other hand, the liquid crystal polyester provided by the example 3 has the lowest melt viscosity of 10 pas when the temperature is raised to 300 ℃, which shows that the two have wider processing windows. With further temperature rise, the chain extension and crosslinking curing reaction of the active end group begins to occur, the viscosity of the liquid crystal polyester imide provided by the example 2 and the viscosity of the liquid crystal polyester provided by the example 3 both rapidly increase, and finally the viscosity approaches the maximum value at the constant temperature of 370 ℃ for 60min, which indicates that the curing reaction is completely performed.
Referring to the attached figure 2, it is a digital photo of the liquid crystal polyester imide provided by the embodiment 2 and the liquid crystal polyester flame retardant foaming material provided by the embodiment 3. It can be seen that the liquid crystal polyester imide provided in example 2 and the liquid crystal polyester flame retardant foam material prepared in example 3 can be foamed into foam materials, and the interior of the foam materials has uniformly distributed cellular structures, which is enough to prove that the invention overcomes the defect that the existing foam materials need a foaming agent, and obtains unexpected technical effects.
Referring to FIG. 3, it is a Scanning Electron Microscope (SEM) picture before combustion of the liquid crystal polyester flame retardant foaming material provided by the embodiment 3 of the invention. It can be seen that the pore diameter of the microcellular structure of the liquid crystal polyester flame-retardant foam material prepared in example 3 is hundreds of microns, and the typical liquid crystal orientation fibrous morphology of the pore wall is observed under further magnification.
Referring to FIG. 4, it is a three-dimensional X-ray tomography (CT) reconstructed picture before combustion of the liquid crystal polyester flame-retardant foamed material provided in example 3 of the present invention. The pore size of the foam material is defined by different colors by using CT analysis software, and it can be seen that the pore size of the liquid crystal polyester flame-retardant foam material prepared in example 3 is hundreds of microns, which is consistent with the result observed from SEM pictures.
Referring to fig. 5, it is the equivalent diameter of the micropores before combustion of the flame-retardant foaming material of liquid crystal polyester provided in embodiment 3 of the invention, and the result is quantified by using three-dimensional X-ray tomography (CT) software with respect to fig. 4. It can be seen that the pore diameter of the liquid crystal polyester flame-retardant foaming material prepared in example 3 is mainly distributed at 200-2000 μm.
See table 1 for the density and porosity of the liquid crystalline polyester flame retardant foam provided in example 3 of the present invention. It can be seen from the table that the liquid crystal polyester flame retardant foamed material prepared in example 3 has low density and high porosity.
Table 1 density and porosity of liquid crystalline polyester flame retardant foam provided in example 3
Referring to FIG. 6, it is the result of statistics of the volume of the micro-pores before combustion of the liquid crystal polyester flame retardant foamed material provided in example 3 of the present invention using three-dimensional X-ray tomography (CT) software with respect to FIG. 5. It can be seen that the volume of the micro pores before burning of the liquid crystal polyester flame retardant foam material prepared in example 3 is mainly distributed at 107‒109μm3。
Referring to FIG. 7, it is a Thermogravimetric (TG) -temperature curve of the liquid crystal polyester flame retardant foaming material provided by the embodiment 3 of the invention. As can be seen, the liquid crystal polyester flame retardant foam obtained in example 3 has excellent heat resistance, initial thermal decomposition temperature (T)di 5wt%) The carbon residue rate is higher than 43% at 455 ℃ and 800 ℃. This is due to the highly heat-resistant wholly aromatic main chain structure of the liquid crystal polyester and the presence of a crosslinked network structure.
See tables 2 and 3 for vertical burning (UL-94) test results and performance ratings, respectively, for the liquid crystalline polyester flame retardant foam provided in example 3 of the present invention. The data in the table show that the flame retardant foaming material of the liquid crystal polyester prepared in the example 3 achieves the flame retardant rating of UL-94V 0.
Table 2 vertical burning test results (UL-94) of the liquid crystal polyester imide flame retardant foam material provided in example 3
Table 3 vertical burning (UL-94) performance classification of liquid crystal polyester imide flame retardant foam provided in example 3
See Table 4, which compares the limit oxygen index and UL-94 rating reported in the present invention with the liquid crystal polyester flame retardant foam material provided in example 3. It can be seen from the table that the liquid crystal polyester flame-retardant foam material prepared in example 3 has a higher limit oxygen index (36.4%), and is even better than other foam materials added with high-content flame retardants.
Table 4 comparative table of limit oxygen index and UL-94 rating of liquid crystal polyester flame retardant foamed material provided in example 3 and reported in the prior art
Referring to FIG. 8, it is a Scanning Electron Microscope (SEM) photograph after combustion of the liquid crystal polyester flame retardant foamed material provided in example 3 of the present invention. As can be seen from comparison with FIG. 3, the number of the micro-pores of the liquid crystal polyester flame-retardant foam material prepared in example 3 after burning is significantly increased, the pore diameter is reduced, and the fibrous morphology is changed into a smooth carbon residue protective layer.
Refer to FIG. 9, which is a reconstructed photograph of a post-combustion three-dimensional X-ray tomography (CT) scan of the liquid crystal polyester flame-retardant foam material provided in example 3 of the present invention. As can be seen from the comparison of FIG. 4, the number of the micro-pores of the liquid crystal polyester flame-retardant foam material prepared in example 3 after burning is significantly increased compared with that before burning, and the pore diameter is significantly reduced, which indicates that the residual acetic acid in the pore wall in the burning process continues to release CO2And promote the formation of a large number of new microporous structures with smaller pore sizes.
Referring to FIG. 10, it shows the equivalent diameter of the burnt microcells of the flame-retardant foaming material of liquid crystal polyester provided in example 3 of the present invention. As can be seen from comparison with FIG. 5, the number of the micro-pores of the liquid crystal polyester flame retardant foam material prepared in example 3 after burning is significantly increased, and the diameter of the micro-pores is mainly determinedDistributed at 20-300 μm, which indicates that residual acetic acid in the hole wall is continuously decomposed to release CO in the combustion process2More microporous structures with smaller pore diameters are formed in the system.
Referring to FIG. 11, it shows the volume of the micro pores after burning of the flame retardant foaming material of liquid crystal polyester provided in example 3 of the present invention. As can be seen from comparison with FIG. 6, the volume of the micro-pores after burning of the liquid crystal polyester flame-retardant foamed material prepared in example 3 is significantly increased compared to that before burning, and the pore diameter is significantly reduced, mainly distributed at 104‒108μm3. Shows that the residual acetic acid in the hole wall is further decomposed to release CO in the combustion process2And promote the formation of a large number of new microporous structures with smaller pore sizes.
Comparative example 1 preparation of liquid crystal polyester flame retardant foam Material
A500 mL three necked round bottom flask was charged with 37.24g of 1, 4-hydroquinone, 33.23g of 1, 4-terephthalic acid, 69.06g of 3-hydroxybenzoic acid, 18.82g of 7-hydroxy-2-naphthoic acid, 27.34g of 27.34g N- (4-carboxyphenyl) -4-phenylethynylphthalimide, 28.39g N- (4-acetoxyphenolate) -4-phenylethynylphthalimide, 150mL of acetic anhydride, and 10mg of potassium acetate. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction for 30min at the temperature of 140 ℃. The reaction mixture was heated in a fluidized sand bath at a ramp rate of 1.0 deg.C/min, the reaction temperature increasing from 140 deg.C to 310 deg.C. At the end of the reaction an opaque melt was obtained, cooled to room temperature, and the product was removed from the flask and ground to a fine powder.
And (3) placing the obtained liquid crystal polyester powder in a vacuum oven with the temperature of 370 ℃ and the vacuum degree of 970 kilopascals, foaming and curing for 50min, wherein the vacuum degree is too low and exceeds the vacuum degree range defined in the technical scheme, so that the liquid crystal flame-retardant foaming material cannot be successfully prepared.
In summary, the invention creatively utilizes the byproduct acetic acid remained in the polycondensation reaction process of the liquid crystal polymer as the foaming agent, and the byproduct acetic acid is decomposed to release CO at high temperature2Forming a micropore structure, simultaneously carrying out a curing reaction on the matrix to form a cross-linked network structure, successfully preparing the uniform gapThe foaming material opens up a new method for preparing the liquid crystal flame-retardant foaming material; the liquid crystal flame-retardant foam material provided by the invention has excellent flame-retardant performance. On one hand, the foam material has a microporous structure and a liquid crystal fibrous compact structure formed on the pore wall, which are beneficial to blocking the transfer of oxygen and heat in the initial combustion period, by virtue of the excellent heat-resistant characteristic of the wholly aromatic main chain of the liquid crystal polymer; on the other hand, the residual acetic acid in the hole wall continuously releases CO in the combustion process2And a large number of new microporous structures with smaller pore diameters are formed, so that the oxygen and heat conduction effects are achieved, and the combustion inhibition is facilitated.
Claims (2)
1. The preparation method of the liquid crystal flame-retardant foaming material is characterized by comprising the following steps of:
(1) taking an aromatic diphenol monomer, an aromatic diacid monomer and an aromatic monomer containing a terminal hydroxyl group and a terminal carboxyl group as raw materials, and reacting for 30-60 min at 120-140 ℃ under the protection of nitrogen in the presence of an active terminal group, a catalyst and an acetic acid compound; then heating to 280-325 ℃ at the speed of 0.5-1.5 ℃/min, and reacting for 1-3 h to obtain a solid;
(2) treating the solid at the vacuum degree of 10-90 kPa for 20-60 min at the temperature of 320-380 ℃ to obtain a liquid crystal flame-retardant foam material;
the aromatic diphenol monomer is one or more of 1, 4-hydroquinone, 1, 3-resorcinol, 4 ' -biphenol, 1 ' -biphenyl-3, 4 ' -diphenol, 1 ' -biphenyl-3, 3' -diphenol, 1, 6-naphthalenediol, 1, 7-naphthalenediol, 2, 6-naphthalenediol and 2, 7-naphthalenediol; the aromatic diacid monomer is one or more of 1, 4-terephthalic acid, 1, 3-isophthalic acid, 4 ' -biphenyl dicarboxylic acid, 1 ' -biphenyl-3, 4 ' -dicarboxylic acid, 1 ' -biphenyl-3, 3' -dicarboxylic acid, 1, 6-naphthalene dicarboxylic acid, 1, 7-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid and 2, 7-naphthalene dicarboxylic acid; the aromatic monomer containing the terminal hydroxyl and the terminal carboxyl is one or more of 3-hydroxybenzoic acid, 4' -hydroxybiphenyl-3-carboxylic acid and 7-hydroxy-2-naphthoic acid;
the active end group is one or more of 3-aminophenylacetylene, N- (4-carboxyphenyl) -4-phenylethynyl phthalic acid imide, N- (4-acetic acid phenol ester group) -4-phenylethynyl phthalic acid imide, N- (3-carboxyphenyl) -4-phenylethynyl phthalic acid imide and N- (3-acetic acid phenol ester group) -4-phenylethynyl phthalic acid imide; the catalyst is one of potassium acetate, sodium acetate, zinc acetate, dibutyltin oxide, stannous octoate and dibutyltin laurate; the acetic acid compound is acetic anhydride;
the molar ratio of the aromatic diphenol monomer to the aromatic diacid monomer to the aromatic monomer containing a terminal hydroxyl group and a terminal carboxyl group to the active terminal group to the acetic acid compound is 1: 0.5-2: 0.03-0.45: 0.5-5 ‰ 1.5-4.
2. The method for preparing the liquid crystal flame-retardant foam material according to claim 1, which is characterized in that: in the step (2), the solid is ground into powder and then treated for 20-60 min at 320-380 ℃ under the vacuum degree of 10-90 kPa, so as to obtain the liquid crystal flame-retardant foam material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011004117.9A CN112094423B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and application thereof |
| CN201711035250.9A CN107793585B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711035250.9A CN107793585B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and preparation method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011004117.9A Division CN112094423B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107793585A CN107793585A (en) | 2018-03-13 |
| CN107793585B true CN107793585B (en) | 2020-10-27 |
Family
ID=61548305
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011004117.9A Active CN112094423B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and application thereof |
| CN201711035250.9A Active CN107793585B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011004117.9A Active CN112094423B (en) | 2017-10-30 | 2017-10-30 | Liquid crystal flame-retardant foam material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN112094423B (en) |
Families Citing this family (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 |
| 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 |
| CN115490629A (en) * | 2019-08-28 | 2022-12-20 | 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 |
| CN112144140B (en) * | 2020-09-28 | 2023-01-13 | 浙江恒逸石化研究院有限公司 | Preparation method of thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester fiber |
| 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 |
| 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 |
| 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 |
| 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 |
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 |
| CN106810676B (en) * | 2017-01-12 | 2019-05-17 | 苏州大学 | A kind of aromatic polyester and preparation method thereof |
| CN106810695B (en) * | 2017-01-12 | 2019-09-06 | 苏州大学 | A kind of aromatic polyesterimides and preparation method thereof |
-
2017
- 2017-10-30 CN CN202011004117.9A patent/CN112094423B/en active Active
- 2017-10-30 CN CN201711035250.9A patent/CN107793585B/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 |
|---|
| All-Aromatic (AB)n-Multiblock Copolymers via Simple One-Step Melt Condensation Chemistry;Guan Qingbao et al.;《Macromolecules》;20161102;第49卷;第8549-8562页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112094423B (en) | 2022-06-07 |
| CN112094423A (en) | 2020-12-18 |
| CN107793585A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107793585B (en) | Liquid crystal flame-retardant foam material and preparation method thereof | |
| JP3687496B2 (en) | Foamed polyimide and process for producing the same | |
| CN104974527B (en) | A kind of preparation method and applications of the polymer-modified foamed composite of organic siliconresin | |
| CN113683812B (en) | Flame-retardant and heat-insulating polyimide nanofiber aerogel and preparation method thereof | |
| JP2000515584A (en) | Aromatic polyimide foam | |
| CN102964597B (en) | Polyimide foam and preparation method thereof | |
| CN104559201A (en) | Method for preparing polyimide-organic silicon composite foam material | |
| CN107286343A (en) | A kind of Halogen composite flame-proof Polyimide foams and preparation method thereof | |
| CN102850569B (en) | Preparation method of polyimide foam | |
| WO2010150955A1 (en) | Method for preparing polyisocyanurate foam by using liquid nucleating agent and polyisocyanurate foam prepared by the same | |
| US6746759B2 (en) | Cellular plastic material based on phenolic resin | |
| CN115109298B (en) | Flame-retardant polystyrene composite material and preparation method thereof | |
| WO2019100408A1 (en) | Liquid crystal flame-retardant foam material and preparation method therefor | |
| CN109867942A (en) | A kind of preparation method and products thereof of fire-retardant fretting map polyphenylene oxide composite material | |
| CN112592454B (en) | Amino silicone oil modified polyimide foam material and preparation method thereof | |
| CN110452487B (en) | Graphene-based flame retardant for polymethacrylimide foam and preparation method of flame-retardant foam | |
| CN102757554A (en) | Halogen-containing aromatic polycarbonate polyol as well as preparation method and application thereof | |
| CN110982196A (en) | Foam fireproof material suitable for charging station | |
| JP2004515897A (en) | High density polyimide foam insulator | |
| JP5436024B2 (en) | Styrenic resin foam | |
| CN115197570B (en) | Soft polyimide foam material with improved cell structure and preparation method thereof | |
| KR102534859B1 (en) | Semi-non-combustible phenolic foam | |
| CN114804078B (en) | Poly-dicyclopentadienyl carbon nano tube/graphene nano sheet aerogel flame-retardant electromagnetic shielding composite material and preparation method thereof | |
| EP1222228B1 (en) | Cellular plastic material based on phenolic resin | |
| CN114874542B (en) | Halogen-free flame-retardant polypropylene material, preparation method thereof, electric control box and air conditioner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |