CN115322530A - Halogen-free flame-retardant enhanced PBT and processing technology thereof - Google Patents
Halogen-free flame-retardant enhanced PBT and processing technology thereof Download PDFInfo
- Publication number
- CN115322530A CN115322530A CN202210953292.5A CN202210953292A CN115322530A CN 115322530 A CN115322530 A CN 115322530A CN 202210953292 A CN202210953292 A CN 202210953292A CN 115322530 A CN115322530 A CN 115322530A
- Authority
- CN
- China
- Prior art keywords
- parts
- halogen
- retardant
- hyperbranched
- flame
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4623—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing primary or secondary terminal aminogroups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a halogen-free flame-retardant enhanced PBT and a processing technology thereof; in order to enhance the flame retardant effect of the PBT material and prevent the flame retardant from generating polluted toxic gas in the flame retardant process, the halogen-free flame-retardant enhanced PBT prepared by the invention prepares the charring agent with a hyperbranched structure, and enhances the fluidity of the PBT material by utilizing the spheroidal structure and more branched groups, so that the construction performance of the PBT material is enhanced; in addition, the hyperbranched char-forming agent prepared by the invention has excellent flame retardant property, a large amount of nitrogen elements are contained in the molecule, a large amount of water vapor can be generated in the combustion process, and the nitrogen elements expand to form an expanded carbon layer, so that the heat exchange of the base material is reduced, and the purpose of flame retardance is achieved; the halogen-free flame-retardant reinforced PBT prepared by the invention has excellent flame retardant property and CTI value, can be effectively applied to the field of electronic products, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant reinforced PBT and a processing technology thereof.
Background
PBT (polybutylene terephthalate), a linear high molecular polymer, has excellent heat resistance, weather resistance and excellent mechanical strength, and is widely applied to many fields, however, due to the nature of the high molecular polymer, the flame-resistant and flame-retardant properties of the PBT are not excellent, so that the PBT is often required to be blended with other flame-retardant materials to achieve a good flame-retardant effect. The halogen flame retardant has good flame retardant performance, but when the halogen flame retardant is combusted, a large amount of smoke and hydrogen halide are generated, and the halogen flame retardant has great harm to both human bodies and the environment; therefore, a halogen-free flame retardant PBT material which is environment-friendly and has less harm to human bodies is urgently needed at present to meet the market demand.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant reinforced PBT and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a halogen-free flame-retardant reinforced PBT has the following characteristics: the halogen-free flame-retardant reinforced PBT comprises the following components in parts by weight: 50-80 parts of PBT resin, 30-50 parts of PC resin, 1-3 parts of antioxidant, 10-15 parts of flame retardant, 10-15 parts of hyperbranched char forming agent and 5-10 parts of compatible toughening agent;
wherein the hyperbranched charring agent is prepared by copolymerizing glycerol, 2-bis (hydroxymethyl) propionic acid, aminoacetic acid and 4,4' -diphenylmethane diisocyanate.
Further, the antioxidant is phosphite ester; the flame retardant is an antimony trioxide flame retardant; the compatible toughening agent is ACR resin.
Wherein the antimony trioxide flame retardant is an antimony trioxide product sold by Jinying Tai chemical Co., ltd, jinan; the compatible toughening agent is an ACR resin sold by Mitsubishi corporation, model S-2001.
A processing technology of halogen-free flame-retardant reinforced PBT comprises the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing glycerol, 2-bis (hydroxymethyl) propionic acid and p-toluenesulfonic acid, heating to 120-160 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction for 3-6h, and carrying out vacuum evaporation to remove redundant reactants to obtain a hydroxyl-terminated prepolymer;
s12, mixing the hydroxyl-terminated prepolymer with p-toluenesulfonic acid, dissolving in N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving aminoacetic acid in N, N-dimethylformamide, slowly dripping into the mixed solution of the hydroxyl-terminated prepolymer, heating to 120-160 ℃, performing reflux reaction for 8-12h, washing a reaction product by using deionized water after the reaction is finished, and performing vacuum drying to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving the amino-terminated hyperbranched prepolymer in N, N-dimethylformamide to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80-90 ℃ under the protection of nitrogen atmosphere; dissolving 4,4' -diphenylmethane diisocyanate in N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, stirring and mixing for 30-45min, adding 0.5-1 part of ethylenediamine, reacting for 8-12h, washing a reaction product by using deionized water, and performing vacuum evaporation and drying to obtain a hyperbranched char-forming agent;
s2, immersing the flame retardant in a silane coupling agent, performing ultrasonic dispersion treatment for 15-30min, centrifuging and drying to obtain a modified flame retardant;
and S3, blending the PBT resin, the PC resin, the antioxidant, the compatible toughening agent and the hyperbranched char forming agent with the flame retardant prepared in the step S2, performing melt extrusion, cooling and granulating to obtain the halogen-free flame-retardant reinforced PBT material.
Further, in step S11, the molar ratio of glycerol, 2-bis (hydroxymethyl) propionic acid and p-toluenesulfonic acid is (12-15): (25-50): (0.1-0.5).
Further, in step S12, the molar ratio of the hydroxyl-terminated prepolymer, p-toluenesulfonic acid and glycine is (12-15): (0.1-0.5): (25-50).
Further, in step S13, the molar ratio of the amino-terminated hyperbranched prepolymer, 4' -diphenylmethane diisocyanate, and ethylenediamine is (12-15): (20-30): (1-1.5).
Further, in step S2, the silane coupling agent is any one or more of KH-550, KH-560 and KH-570, and the ultrasonic treatment frequency is 25-30KHz.
Further, in step S3, the melt extrusion temperature is 230-250 ℃.
In order to enhance the flame retardant property of the PBT material and avoid the release of a large amount of toxic gas pollution in the flame retardant process of the conventional halogen flame retardant, the hyperbranched charring agent with the hyperbranched characteristic is prepared; the method comprises the steps of firstly using glycerol as a core, using 2, 2-bis (hydroxymethyl) propionic acid to perform esterification reaction with glycerol, grafting the mixture to a prepolymer generating terminal hydroxyl groups, then reacting the prepolymer generating terminal hydroxyl groups with aminoacetic acid, replacing and grafting the hydroxyl groups with amino groups, thereby forming an amino-terminated hyperbranched prepolymer, finally adding 4,4' -diphenylmethane diisocyanate, and generating a hyperbranched char-forming agent containing a large amount of nitrogen elements and carbon elements under the catalysis of ethylenediamine.
When the combustion reaction is carried out, the hyperbranched charring agent is heated and decomposed to generate a large amount of non-combustible gas and water vapor, so that the combustible gas on the surface of the product is diluted to be reduced to be below the combustion concentration, and the combustion reaction is prevented from being carried out; meanwhile, after being heated, the hyperbranched carbon forming agent can be heated to expand to form a continuous and compact expanded carbon layer, so that the transmission of oxygen and combustible gas is blocked, the contact between air and a substrate is reduced, the formed carbon layer can reflect most of combustion radiation, the temperature rise rate of the substrate is reduced, the thermal decomposition rate of the substrate in the combustion process is effectively reduced, and the supply amount of the combustible gas in the combustion process is reduced.
In addition, the hyperbranched charring agent prepared by the invention also has a sphere-like spatial shape, has a plurality of branched groups, has good compatibility with a PBT matrix, can effectively improve the melt fluidity of the PBT material, and can effectively improve the dispersion performance of the antimony trioxide flame retardant in the PBT matrix.
The PBT material has excellent physical properties, but relatively speaking, the CTI value of the PBT material is lower, so that the CTI value of the PBT material can be effectively improved by adding the PC resin, and meanwhile, in order to improve the compatibility of the PC resin and the PBT material, the ACR resin is also added as a compatible toughening agent to improve the performance of the PBT.
Compared with the prior art, the invention has the following beneficial effects: in order to enhance the flame retardant effect of the PBT material and prevent the flame retardant from generating polluted toxic gas in the flame retardant process, the halogen-free flame-retardant enhanced PBT prepared by the invention prepares the charring agent with a hyperbranched structure, and the flowability of the PBT material is enhanced by utilizing the spheroidal structure and more branched groups, so that the construction performance of the charring agent is enhanced; in addition, the hyperbranched char-forming agent prepared by the invention has excellent flame retardant property, a large amount of nitrogen elements are contained in the molecule, a large amount of water vapor can be generated in the combustion process, and the nitrogen elements expand to form an expanded carbon layer, so that the heat exchange of the base material is reduced, and the purpose of flame retardance is achieved; the halogen-free flame-retardant reinforced PBT prepared by the invention has excellent flame retardant property and CTI value, can be effectively applied to the field of electronic products, and has wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment and the comparative example of the invention, the PBT material used is 1100HQ type PBT resin sold by Nantong star synthetic materials, inc.; the PC resin used was a commercially available LEXAN CFR9712 type PC resin; the antimony trioxide flame retardant is an antimony trioxide product sold by Jinying Tai chemical Co., ltd, jinan; the compatible toughening agent is ACR resin sold by Mitsubishi corporation of Japan as model S-2001.
Example 1.
The processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing 12 parts of glycerol, 25 parts of 2, 2-bis (hydroxymethyl) propionic acid and 0.1 part of p-toluenesulfonic acid in parts by mole, heating in an oil bath under the protection of nitrogen atmosphere until the temperature of a reaction system is 120 ℃, stirring at a stirring speed of 100rpm, carrying out reflux reaction for 3 hours, and after the reaction is finished, carrying out vacuum evaporation for 4 hours at 80 ℃ to remove redundant reactants to obtain a hydroxyl-terminated prepolymer;
s12, mixing 12 parts of hydroxyl-terminated prepolymer with 0.1 part of p-toluenesulfonic acid in parts by mole, dissolving in 60 parts of N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving 25 parts of aminoacetic acid in 120 parts of N, N-dimethylformamide, slowly dropwise adding the aminoacetic acid into the hydroxyl-terminated prepolymer mixed solution for 2 hours, heating a reaction system to 120 ℃ after dropwise adding, stirring at 100rpm, refluxing for reaction for 8 hours, washing a reaction product for 3 times by using deionized water after the reaction is finished, and performing vacuum drying for 4 hours at 80 ℃ to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving 12 parts of amino-terminated hyperbranched prepolymer in 40 parts of N, N-dimethylformamide in parts by mole to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80 ℃ under the protection of nitrogen atmosphere; dissolving 20 parts of 4,4' -diphenylmethane diisocyanate in 60 parts of N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, wherein the dropwise adding time is 2 hours, stirring and mixing at the speed of 100rpm for 30 minutes, then adding 1 part of ethylenediamine, reacting for 8 hours, washing the reaction product for 3 times by using deionized water, and performing vacuum evaporation drying at 80 ℃ for 4 hours to obtain a hyperbranched char-forming agent;
s2, immersing the antimony trioxide flame retardant into a KH-550 type silane coupling agent, performing 25KHz ultrasonic dispersion treatment for 15min, centrifuging and drying to obtain a modified flame retardant;
s3, pouring 50 parts of PBT resin, 30 parts of PC resin, 1 part of phosphite antioxidant, 5 parts of S-2001 ACR resin, 10 parts of hyperbranched char forming agent and 10 parts of the flame retardant prepared in the step S2 into a double-screw extruder for mixing, melting and extruding at the die head temperature of 230 ℃, cooling, granulating, and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
Example 2.
Compared with the example 1, the addition amount of the 2, 2-bis (hydroxymethyl) propionic acid in the step S11 is increased;
the processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing 12 parts of glycerol, 36 parts of 2, 2-bis (hydroxymethyl) propionic acid and 0.1 part of p-toluenesulfonic acid in parts by mole, heating in an oil bath under the protection of nitrogen atmosphere until the temperature of a reaction system is 120 ℃, stirring at a stirring speed of 100rpm, carrying out reflux reaction for 3 hours, after the reaction is finished, carrying out vacuum evaporation for 4 hours at 80 ℃, and removing redundant reactants to obtain a hydroxyl-terminated prepolymer;
s12, mixing 12 parts of hydroxyl-terminated prepolymer with 0.1 part of p-toluenesulfonic acid in parts by mole, dissolving in 60 parts of N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving 25 parts of aminoacetic acid in 120 parts of N, N-dimethylformamide, slowly dropwise adding the aminoacetic acid into the hydroxyl-terminated prepolymer mixed solution for 2 hours, heating a reaction system to 120 ℃ after dropwise adding, stirring at 100rpm, refluxing for reaction for 8 hours, washing a reaction product for 3 times by using deionized water after the reaction is finished, and performing vacuum drying for 4 hours at 80 ℃ to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving 12 parts of amino-terminated hyperbranched prepolymer in 40 parts of N, N-dimethylformamide in parts by mole to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80 ℃ under the protection of nitrogen atmosphere; dissolving 20 parts of 4,4' -diphenylmethane diisocyanate in 60 parts of N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, wherein the dropwise adding time is 2 hours, stirring and mixing at the speed of 100rpm for 30 minutes, then adding 1 part of ethylenediamine, reacting for 8 hours, washing the reaction product for 3 times by using deionized water, and performing vacuum evaporation drying at 80 ℃ for 4 hours to obtain a hyperbranched char-forming agent;
s2, immersing the antimony trioxide flame retardant in a KH-550 type silane coupling agent, performing ultrasonic dispersion treatment on the antimony trioxide flame retardant for 15min by using 25KHz, centrifuging and drying to obtain a modified flame retardant;
s3, pouring 50 parts of PBT resin, 30 parts of PC resin, 1 part of phosphite antioxidant, 5 parts of S-2001 ACR resin, 10 parts of hyperbranched char forming agent and 10 parts of the flame retardant prepared in the step S2 into a double-screw extruder for mixing, melting and extruding at the die head temperature of 230 ℃, cooling, granulating and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
Example 3.
This example increased the amount of glycine added in step S12 compared to example 2;
the processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing 12 parts of glycerol, 36 parts of 2, 2-bis (hydroxymethyl) propionic acid and 0.1 part of p-toluenesulfonic acid in parts by mole, heating in an oil bath under the protection of nitrogen atmosphere until the temperature of a reaction system is 120 ℃, stirring at a stirring speed of 100rpm, performing reflux reaction for 3 hours, and after the reaction is finished, performing vacuum evaporation for 4 hours at 80 ℃, removing redundant reactants, thereby obtaining a hydroxyl-terminated prepolymer;
s12, mixing 12 parts of hydroxyl-terminated prepolymer with 0.1 part of p-toluenesulfonic acid in parts by mole, dissolving in 60 parts of N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving 36 parts of aminoacetic acid in 120 parts of N, N-dimethylformamide, slowly dropwise adding the aminoacetic acid into the hydroxyl-terminated prepolymer mixed solution for 2 hours, heating a reaction system to 120 ℃ after dropwise adding, stirring at 100rpm, refluxing for reaction for 8 hours, washing a reaction product for 3 times by using deionized water after the reaction is finished, and performing vacuum drying for 4 hours at 80 ℃ to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving 12 parts of amino-terminated hyperbranched prepolymer in 40 parts of N, N-dimethylformamide in parts by mole to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80 ℃ under the protection of nitrogen atmosphere; dissolving 20 parts of 4,4' -diphenylmethane diisocyanate in 60 parts of N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, wherein the dropwise adding time is 2 hours, stirring and mixing at the speed of 100rpm for 30 minutes, then adding 1 part of ethylenediamine, reacting for 8 hours, washing the reaction product for 3 times by using deionized water, and performing vacuum evaporation drying at 80 ℃ for 4 hours to obtain a hyperbranched char-forming agent;
s2, immersing the antimony trioxide flame retardant into a KH-550 type silane coupling agent, performing 25KHz ultrasonic dispersion treatment for 15min, centrifuging and drying to obtain a modified flame retardant;
s3, pouring 50 parts of PBT resin, 30 parts of PC resin, 1 part of phosphite antioxidant, 5 parts of S-2001 ACR resin, 10 parts of hyperbranched char forming agent and 10 parts of the flame retardant prepared in the step S2 into a double-screw extruder for mixing, melting and extruding at the die head temperature of 230 ℃, cooling, granulating and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
Example 4.
Compared with the embodiment 3, the embodiment increases the adding amount of the hyperbranched char-forming agent in the step S3;
the processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing 12 parts of glycerol, 36 parts of 2, 2-bis (hydroxymethyl) propionic acid and 0.1 part of p-toluenesulfonic acid in parts by mole, heating in an oil bath under the protection of nitrogen atmosphere until the temperature of a reaction system is 120 ℃, stirring at a stirring speed of 100rpm, performing reflux reaction for 3 hours, and after the reaction is finished, performing vacuum evaporation for 4 hours at 80 ℃, removing redundant reactants, thereby obtaining a hydroxyl-terminated prepolymer;
s12, mixing 12 parts of hydroxyl-terminated prepolymer with 0.1 part of p-toluenesulfonic acid in parts by mole, dissolving in 60 parts of N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving 36 parts of aminoacetic acid in 120 parts of N, N-dimethylformamide, slowly dropwise adding the aminoacetic acid into the hydroxyl-terminated prepolymer mixed solution for 2 hours, heating a reaction system to 120 ℃ after dropwise adding, stirring at 100rpm, refluxing for reaction for 8 hours, washing a reaction product for 3 times by using deionized water after the reaction is finished, and performing vacuum drying at 80 ℃ for 4 hours to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving 12 parts of amino-terminated hyperbranched prepolymer in 40 parts of N, N-dimethylformamide in parts by mole to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80 ℃ under the protection of nitrogen atmosphere; dissolving 20 parts of 4,4' -diphenylmethane diisocyanate in 60 parts of N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, wherein the dropwise adding time is 2 hours, stirring and mixing at the speed of 100rpm for 30 minutes, then adding 1 part of ethylenediamine, reacting for 8 hours, washing the reaction product for 3 times by using deionized water, and performing vacuum evaporation drying at 80 ℃ for 4 hours to obtain a hyperbranched char-forming agent;
s2, immersing the antimony trioxide flame retardant in a KH-550 type silane coupling agent, performing ultrasonic dispersion treatment on the antimony trioxide flame retardant for 15min by using 25KHz, centrifuging and drying to obtain a modified flame retardant;
s3, pouring 50 parts of PBT resin, 30 parts of PC resin, 1 part of phosphite antioxidant, 5 parts of S-2001 ACR resin, 15 parts of hyperbranched char forming agent and 10 parts of the flame retardant prepared in the step S2 into a double-screw extruder for mixing, melting and extruding at the die head temperature of 230 ℃, cooling, granulating and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
Example 5.
The processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing 15 parts of glycerol, 50 parts of 2, 2-bis (hydroxymethyl) propionic acid and 0.5 part of p-toluenesulfonic acid in parts by mole, heating in an oil bath under the protection of nitrogen atmosphere, heating to 160 ℃ of a reaction system, stirring at a stirring speed of 100rpm, performing reflux reaction for 6 hours, and after the reaction is finished, performing vacuum evaporation for 4 hours at 80 ℃, removing redundant reactants, thereby obtaining a hydroxyl-terminated prepolymer;
s12, mixing 15 parts of hydroxyl-terminated prepolymer with 0.5 part of p-toluenesulfonic acid in parts by mole, dissolving in 60 parts of N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving 50 parts of aminoacetic acid in 120 parts of N, N-dimethylformamide, slowly dropwise adding into the hydroxyl-terminated prepolymer mixed solution for 2 hours, after dropwise adding, heating a reaction system to 160 ℃, stirring at 100rpm, refluxing for reaction for 12 hours, washing a reaction product for 3 times by using deionized water after the reaction is finished, and performing vacuum drying at 80 ℃ for 4 hours to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving 15 parts of amino-terminated hyperbranched prepolymer in 40 parts of N, N-dimethylformamide in parts by mole to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 90 ℃ under the protection of nitrogen atmosphere; dissolving 30 parts of 4,4' -diphenylmethane diisocyanate in 60 parts of N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, wherein the dropwise adding time is 2 hours, stirring and mixing at the speed of 100rpm for 30min, adding 1.5 parts of ethylenediamine, reacting for 12 hours, washing a reaction product for 3 times by using deionized water, and performing vacuum evaporation drying at 80 ℃ for 4 hours to obtain a hyperbranched char-forming agent;
s2, immersing the antimony trioxide flame retardant in a KH-550 type silane coupling agent, performing 35KHz ultrasonic dispersion treatment for 30min, centrifuging and drying to obtain a modified flame retardant;
s3, pouring 80 parts of PBT resin, 50 parts of PC resin, 3 parts of phosphite antioxidant, 10 parts of S-2001 ACR resin, 15 parts of hyperbranched char forming agent and 15 parts of the flame retardant prepared in the step S2 into a double-screw extruder for mixing, melting and extruding at the die head temperature of 230 ℃, cooling, granulating and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
Comparative example 1.
Compared with example 3, the present comparative example did not prepare a synthetic hyperbranched char-forming agent;
the processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, immersing an antimony trioxide flame retardant into a KH-550 type silane coupling agent, performing 25KHz ultrasonic dispersion treatment for 15min, centrifuging and drying to obtain a modified flame retardant;
s1, pouring 50 parts of PBT resin, 30 parts of PC resin, 1 part of phosphite antioxidant, 5 parts of S-2001 ACR resin and 10 parts of the flame retardant prepared in the step S1 into a double-screw extruder for blending, melting and extruding at the die head temperature of 230 ℃, cooling, granulating, and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
Example 2.
Compared with the embodiment 3, the comparative example reduces the addition amount of the hyperbranched char-forming agent in the step S3;
the processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing 12 parts of glycerol, 36 parts of 2, 2-bis (hydroxymethyl) propionic acid and 0.1 part of p-toluenesulfonic acid in parts by mole, heating in an oil bath under the protection of nitrogen atmosphere until the temperature of a reaction system is 120 ℃, stirring at a stirring speed of 100rpm, carrying out reflux reaction for 3 hours, after the reaction is finished, carrying out vacuum evaporation for 4 hours at 80 ℃, and removing redundant reactants to obtain a hydroxyl-terminated prepolymer;
s12, mixing 12 parts of hydroxyl-terminated prepolymer with 0.1 part of p-toluenesulfonic acid in parts by mole, dissolving in 60 parts of N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving 36 parts of aminoacetic acid in 120 parts of N, N-dimethylformamide, slowly dropwise adding the aminoacetic acid into the hydroxyl-terminated prepolymer mixed solution for 2 hours, heating a reaction system to 120 ℃ after dropwise adding, stirring at 100rpm, refluxing for reaction for 8 hours, washing a reaction product for 3 times by using deionized water after the reaction is finished, and performing vacuum drying at 80 ℃ for 4 hours to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving 12 parts of amino-terminated hyperbranched prepolymer in 40 parts of N, N-dimethylformamide in parts by mole to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80 ℃ under the protection of nitrogen atmosphere; dissolving 20 parts of 4,4' -diphenylmethane diisocyanate in 60 parts of N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, wherein the dropwise adding time is 2 hours, stirring and mixing at the speed of 100rpm for 30 minutes, then adding 1 part of ethylenediamine, reacting for 8 hours, washing the reaction product for 3 times by using deionized water, and performing vacuum evaporation drying at 80 ℃ for 4 hours to obtain a hyperbranched char-forming agent;
s2, immersing the antimony trioxide flame retardant in a KH-550 type silane coupling agent, performing ultrasonic dispersion treatment on the antimony trioxide flame retardant for 15min by using 25KHz, centrifuging and drying to obtain a modified flame retardant;
s3, pouring 50 parts of PBT resin, 30 parts of PC resin, 1 part of phosphite antioxidant, 5 parts of S-2001 ACR resin, 5 parts of hyperbranched char forming agent and 10 parts of the flame retardant prepared in the step S2 into a double-screw extruder for mixing, melting and extruding at the die head temperature of 230 ℃, cooling, granulating and vacuum drying at 40 ℃ for 2 hours to obtain the halogen-free flame-retardant reinforced PBT material.
The halogen-free flame-retardant enhanced PBT material prepared in the embodiments 1-5 and the comparative examples 1-2 is prepared into a standard injection molding material sample by melt injection molding, the flame retardant property of the injection molding material is detected according to UL94, the bending strength of the injection molding material is detected according to GB/T9341-2000, the tensile strength and the elongation at break of the injection molding material are detected according to GB/T10401992, the melt flow rate of the injection molding material is detected according to GB/T3682-2000, and a KS-53D (flame retardant plastics) electric leakage trace tester is used for detecting a CTI (comparative tracking index) value; the results of the measurements are shown in the following table:
Claims (8)
1. a halogen-free flame-retardant reinforced PBT is characterized in that: the halogen-free flame-retardant reinforced PBT comprises the following components in parts by weight: 50-80 parts of PBT resin, 30-50 parts of PC resin, 1-3 parts of antioxidant, 10-15 parts of flame retardant, 10-15 parts of hyperbranched char forming agent and 5-10 parts of compatible toughening agent;
wherein the hyperbranched charring agent is prepared by copolymerizing glycerol, 2-bis (hydroxymethyl) propionic acid, aminoacetic acid and 4,4' -diphenylmethane diisocyanate.
2. The halogen-free flame-retardant reinforced PBT according to claim 1, characterized in that: the antioxidant is phosphite ester; the flame retardant is an antimony trioxide flame retardant; the compatible toughening agent is ACR resin.
3. The processing technology of the halogen-free flame-retardant reinforced PBT is characterized by comprising the following steps:
s1, synthesizing a hyperbranched char-forming agent:
s11, mixing glycerol, 2-bis (hydroxymethyl) propionic acid and p-toluenesulfonic acid, heating to 120-160 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction for 3-6h, and carrying out vacuum evaporation to remove redundant reactants to obtain a hydroxyl-terminated prepolymer;
s12, mixing the hydroxyl-terminated prepolymer with p-toluenesulfonic acid, dissolving in N, N-dimethylformamide to obtain a hydroxyl-terminated prepolymer mixed solution, and protecting in a nitrogen atmosphere; dissolving aminoacetic acid in N, N-dimethylformamide, slowly dropwise adding into the hydroxyl-terminated prepolymer mixed solution, heating to 120-160 ℃, carrying out reflux reaction for 8-12h, washing a reaction product by using deionized water after the reaction is finished, and carrying out vacuum drying to obtain an amino-terminated hyperbranched prepolymer;
s13, dissolving the amino-terminated hyperbranched prepolymer in N, N-dimethylformamide to obtain an amino-terminated hyperbranched prepolymer mixed solution, and heating to 80-90 ℃ under the protection of nitrogen atmosphere; dissolving 4,4' -diphenylmethane diisocyanate in N, N-dimethylformamide, slowly dropwise adding into the amino-terminated hyperbranched prepolymer mixed solution, stirring and mixing for 30-45min, adding 0.5-1 part of ethylenediamine, reacting for 8-12h, washing a reaction product by using deionized water, and performing vacuum evaporation and drying to obtain a hyperbranched char-forming agent;
s2, immersing the flame retardant in a silane coupling agent, performing ultrasonic dispersion treatment for 15-30min, centrifuging and drying to obtain a modified flame retardant;
and S3, blending the PBT resin, the PC resin, the antioxidant, the compatible toughening agent and the hyperbranched char forming agent with the flame retardant prepared in the step S2, performing melt extrusion, cooling and granulating to obtain the halogen-free flame-retardant reinforced PBT material.
4. The processing technology of the halogen-free flame-retardant reinforced PBT according to claim 3, characterized in that: in step S11, the molar ratio of the glycerol, the 2, 2-bis (hydroxymethyl) propionic acid and the p-toluenesulfonic acid is (12-15) in parts by mole: (25-50): (0.1-0.5).
5. The processing technology of the halogen-free flame-retardant reinforced PBT according to claim 3, characterized in that: in step S12, the molar ratio of the hydroxyl-terminated prepolymer, the p-toluenesulfonic acid and the glycine is (12-15): (0.1-0.5): (25-50).
6. The processing technology of the halogen-free flame-retardant reinforced PBT according to claim 3, characterized in that: in step S13, the molar ratio of the amino-terminated hyperbranched prepolymer, the 4,4' -diphenylmethane diisocyanate and the ethylenediamine is (12-15): (20-30): (1-1.5).
7. The processing technology of the halogen-free flame-retardant reinforced PBT according to claim 3, characterized in that: in the step S2, the silane coupling agent is any one or more of KH-550, KH-560 and KH-570, and the ultrasonic treatment frequency is 25-30KHz.
8. The processing technology of the halogen-free flame-retardant reinforced PBT according to claim 3, characterized in that: in step S3, the melt extrusion temperature is 230-250 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210953292.5A CN115322530B (en) | 2022-08-10 | 2022-08-10 | Halogen-free flame-retardant enhanced PBT (polybutylene terephthalate) and processing technology thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210953292.5A CN115322530B (en) | 2022-08-10 | 2022-08-10 | Halogen-free flame-retardant enhanced PBT (polybutylene terephthalate) and processing technology thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115322530A true CN115322530A (en) | 2022-11-11 |
CN115322530B CN115322530B (en) | 2023-07-11 |
Family
ID=83921730
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210953292.5A Active CN115322530B (en) | 2022-08-10 | 2022-08-10 | Halogen-free flame-retardant enhanced PBT (polybutylene terephthalate) and processing technology thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115322530B (en) |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3008810A1 (en) * | 1980-03-07 | 1981-09-24 | Basf Ag, 6700 Ludwigshafen | Self-crosslinking cationic binder prepn. - by reacting ammonia or di:amine and epoxide adduct with blocked poly:isocyanate and opt. poly:amine |
WO1998005696A1 (en) * | 1996-08-01 | 1998-02-12 | Wolff Walsrode Ag | Aqueous dispersions, their preparation and use as paint binders |
JP2006160789A (en) * | 2004-12-02 | 2006-06-22 | Toyobo Co Ltd | Phosphorus-containing hyper-branched polymer and flame retardant resin composition |
US20070272903A1 (en) * | 2003-12-19 | 2007-11-29 | Burk Johst H | Arylalkylsilyls Used as a Flame Retardant Additives |
CN102942664A (en) * | 2012-11-28 | 2013-02-27 | 安徽大学 | Preparation method of hydroxyl-terminated hyperbranched polyurethane |
CN102964559A (en) * | 2012-12-19 | 2013-03-13 | 江南大学 | Preparation and application methods of high-branched polyester polyol for UV (Ultraviolet) curing waterborne polyurethane coating |
CN103881076A (en) * | 2014-03-07 | 2014-06-25 | 济南大学 | Halogen-free hyper-branched intumescent flame retardant and preparation method thereof |
CN104177791A (en) * | 2014-08-14 | 2014-12-03 | 北京工商大学 | Halogen-free expanded flame-retardant PBT and preparation method thereof |
CN104193944A (en) * | 2014-08-21 | 2014-12-10 | 苏州瑞红电子化学品有限公司 | Controllable-acid-value photosensitive alkali-soluble polyurethane acrylate resin and photoresist composition thereof |
CN104861851A (en) * | 2015-05-05 | 2015-08-26 | 段宝荣 | Method for preparing flame retardant aqueous polyurethane coating and adhesive |
CN105504519A (en) * | 2016-01-25 | 2016-04-20 | 上海捷棉新材料科技有限公司 | Halogen-free environment-friendly flame-retardant polyolefin master batch for replacing bromine-containing flame retardant and preparation method of master batch |
US20160159965A1 (en) * | 2013-07-30 | 2016-06-09 | Mitsui Chemicals, Inc. | Polyurethane dispersion and polyurethane laminate |
CN107099132A (en) * | 2017-04-07 | 2017-08-29 | 北京理工大学 | A kind of hyperbranched blending modified chain extension extinguishing waterborn polyurethane of soft segment |
CN107740278A (en) * | 2017-11-01 | 2018-02-27 | 北京中纺化工股份有限公司 | A kind of comb polyurethane flame-retardant water-repellent finishing agent and preparation method and application |
CN109867922A (en) * | 2018-12-28 | 2019-06-11 | 聚石化学(苏州)有限公司 | A kind of and excellent halogen free flame-retardant reinforced PBT composite material and preparation method thereof of adhering with epoxy resin |
CN112724365A (en) * | 2020-11-30 | 2021-04-30 | 温州大学 | Flame-retardant hyperbranched polymer leather retanning agent |
CN112831268A (en) * | 2019-11-25 | 2021-05-25 | 万华化学集团股份有限公司 | Photo-curing water-based paint resin and preparation method thereof |
CN113717368A (en) * | 2021-08-05 | 2021-11-30 | 金色摇篮新材料股份公司 | Double-type photoinitiation group-containing modified 2 nd-generation hyperbranched self-initiated UV resin |
WO2022068621A1 (en) * | 2020-09-30 | 2022-04-07 | 黎明职业大学 | Halogen-free flame-retardant reinforced pet composite material and preparation method therefor |
-
2022
- 2022-08-10 CN CN202210953292.5A patent/CN115322530B/en active Active
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3008810A1 (en) * | 1980-03-07 | 1981-09-24 | Basf Ag, 6700 Ludwigshafen | Self-crosslinking cationic binder prepn. - by reacting ammonia or di:amine and epoxide adduct with blocked poly:isocyanate and opt. poly:amine |
WO1998005696A1 (en) * | 1996-08-01 | 1998-02-12 | Wolff Walsrode Ag | Aqueous dispersions, their preparation and use as paint binders |
US20070272903A1 (en) * | 2003-12-19 | 2007-11-29 | Burk Johst H | Arylalkylsilyls Used as a Flame Retardant Additives |
JP2006160789A (en) * | 2004-12-02 | 2006-06-22 | Toyobo Co Ltd | Phosphorus-containing hyper-branched polymer and flame retardant resin composition |
CN102942664A (en) * | 2012-11-28 | 2013-02-27 | 安徽大学 | Preparation method of hydroxyl-terminated hyperbranched polyurethane |
CN102964559A (en) * | 2012-12-19 | 2013-03-13 | 江南大学 | Preparation and application methods of high-branched polyester polyol for UV (Ultraviolet) curing waterborne polyurethane coating |
US20160159965A1 (en) * | 2013-07-30 | 2016-06-09 | Mitsui Chemicals, Inc. | Polyurethane dispersion and polyurethane laminate |
CN103881076A (en) * | 2014-03-07 | 2014-06-25 | 济南大学 | Halogen-free hyper-branched intumescent flame retardant and preparation method thereof |
CN104177791A (en) * | 2014-08-14 | 2014-12-03 | 北京工商大学 | Halogen-free expanded flame-retardant PBT and preparation method thereof |
CN104193944A (en) * | 2014-08-21 | 2014-12-10 | 苏州瑞红电子化学品有限公司 | Controllable-acid-value photosensitive alkali-soluble polyurethane acrylate resin and photoresist composition thereof |
CN104861851A (en) * | 2015-05-05 | 2015-08-26 | 段宝荣 | Method for preparing flame retardant aqueous polyurethane coating and adhesive |
CN105504519A (en) * | 2016-01-25 | 2016-04-20 | 上海捷棉新材料科技有限公司 | Halogen-free environment-friendly flame-retardant polyolefin master batch for replacing bromine-containing flame retardant and preparation method of master batch |
CN107099132A (en) * | 2017-04-07 | 2017-08-29 | 北京理工大学 | A kind of hyperbranched blending modified chain extension extinguishing waterborn polyurethane of soft segment |
CN107740278A (en) * | 2017-11-01 | 2018-02-27 | 北京中纺化工股份有限公司 | A kind of comb polyurethane flame-retardant water-repellent finishing agent and preparation method and application |
CN109867922A (en) * | 2018-12-28 | 2019-06-11 | 聚石化学(苏州)有限公司 | A kind of and excellent halogen free flame-retardant reinforced PBT composite material and preparation method thereof of adhering with epoxy resin |
CN112831268A (en) * | 2019-11-25 | 2021-05-25 | 万华化学集团股份有限公司 | Photo-curing water-based paint resin and preparation method thereof |
WO2022068621A1 (en) * | 2020-09-30 | 2022-04-07 | 黎明职业大学 | Halogen-free flame-retardant reinforced pet composite material and preparation method therefor |
CN112724365A (en) * | 2020-11-30 | 2021-04-30 | 温州大学 | Flame-retardant hyperbranched polymer leather retanning agent |
CN113717368A (en) * | 2021-08-05 | 2021-11-30 | 金色摇篮新材料股份公司 | Double-type photoinitiation group-containing modified 2 nd-generation hyperbranched self-initiated UV resin |
Non-Patent Citations (6)
Title |
---|
刘裕红;: "无卤阻燃PC/ABS合金的改性研究", 化工管理, no. 35, pages 168 - 170 * |
周丰;武春雨;: "聚氨酯复合材料的研究进展", 合成树脂及塑料, no. 03, pages 100 - 105 * |
张友强;王旭华;王宝生;姚立凯;张学锋;王鑫淼;: "无卤阻燃增强增韧PBT研制", 工程塑料应用, no. 08, pages 55 - 59 * |
张鹏飞;杨保平;: "超支化聚氨酯钢结构防火涂料的研制", 上海涂料, no. 02, pages 8 - 12 * |
许博;陈雅君;辛菲;钱立军;: "二乙基次膦酸铝与三嗪成炭剂协同阻燃PBT的研究", 功能材料, no. 09, pages 84 - 89 * |
韩文松: "紫外光固化超支化聚酯丙烯酸酯_二氧化硅杂化材料的制备_韩文松", 《高分子材料科学与工程》, vol. 30, no. 12, pages 160 - 162 * |
Also Published As
Publication number | Publication date |
---|---|
CN115322530B (en) | 2023-07-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112266619B (en) | Polycarbonate composition resistant to wet heat aging and preparation method thereof | |
CN114539743A (en) | Degradable barrier composition and preparation method and application thereof | |
CN112538252B (en) | Transparent hydrolysis-resistant weather-resistant halogen-free flame-retardant polycarbonate composite material | |
CN115368716B (en) | Preparation method of efficient flame-retardant plastic | |
CN102558808B (en) | Environment-friendly flame-retardant scratch-resistant polycarbonate resin and preparation method thereof | |
CN112552663A (en) | High-fluidity flame-retardant polylactic acid composite material | |
CN107236273A (en) | A kind of PC/ABS plastic alloys of halogen-free flameproof and preparation method thereof | |
CN114349968B (en) | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof | |
CN112111138A (en) | Flame-retardant polycarbonate composition and preparation method thereof | |
CN113136097B (en) | Halogen-free flame-retardant antistatic natural-color PC/ABS alloy and preparation method thereof | |
CN113773628A (en) | Flame-retardant PC composition and preparation method thereof | |
CN115322530B (en) | Halogen-free flame-retardant enhanced PBT (polybutylene terephthalate) and processing technology thereof | |
CN109575324B (en) | Chemically modified transparent flame-retardant PET master batch and manufacturing method and application thereof | |
CN112979951B (en) | Flame retardant, flame-retardant transparent polycarbonate resin and preparation method thereof | |
KR20090066599A (en) | Flame retardant thermoplastic polyester resin composition | |
CN114479407B (en) | Thin-wall flame-retardant polycarbonate material and preparation method thereof | |
CN114590006A (en) | High-temperature-resistant anti-decoloration PETG skin-feel film and preparation method thereof | |
CN114213827A (en) | Solvent-resistant halogen-free flame-retardant PC/PETG alloy and preparation method thereof | |
CN111004476B (en) | Engineering plastic composition and preparation method thereof | |
CN112851862A (en) | Environment-friendly flame-retardant plastic and preparation method thereof | |
CN111057349A (en) | Environment-friendly flame-retardant plastic, preparation method and application | |
CN116903962B (en) | Composite flame-retardant master batch and application thereof | |
CN116332983B (en) | Modified cyclic siloxane flame retardant, transparent flame retardant polycarbonate composition and preparation method thereof | |
CN114316584B (en) | Brominated flame-retardant high-heat-resistance bio-based polyamide composition and preparation method thereof | |
CN115368723A (en) | Formula and preparation method of high-impact-resistance low-temperature-resistance flame-retardant PC/PBT alloy material |
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 |