阅读说明：本技术 一种防滴落高分子磺酸盐阻燃剂及其制备方法 (anti-dripping macromolecular sulfonate flame retardant and preparation method thereof ) 是由 王启瑶 于 2019-09-23 设计创作，主要内容包括：本发明涉及高分子技术领域,具体涉及一种防滴落高分子磺酸盐阻燃剂及其制备方法,包括如下步骤：1)按照重量份,将乳化剂、不饱和磺酸盐、不饱和单体以及部分去离子水混合,加热搅拌至均匀,得到混合物A保温,备用；2)将引发剂加入混合物A中,并加热、搅拌进行自由基反应,得到高分子磺酸盐共聚物乳液,备用；3)将另一部分去离子水和聚四氟乙烯乳液加入高分子磺酸盐共聚物乳液中,并升温、搅拌,得到混合物B,备用；4)将凝聚剂加入混合物B中,搅拌均匀后加热、反应,将得到的沉淀产物洗涤、烘干、粉碎,得到防滴落高分子磺酸盐阻燃剂。本发明的防滴落高分子磺酸盐阻燃剂既具有持久阻燃性又具有抗滴落特性。(The invention relates to the technical field of macromolecules, in particular to an anti-dripping macromolecular sulfonate flame retardant and a preparation method thereof, and the preparation method comprises the following steps: 1) mixing an emulsifier, unsaturated sulfonate, an unsaturated monomer and part of deionized water according to parts by weight, heating and stirring until the mixture is uniform to obtain a mixture A, and keeping the temperature for later use; 2) adding an initiator into the mixture A, heating and stirring to perform free radical reaction to obtain a high-molecular sulfonate copolymer emulsion for later use; 3) adding the other part of deionized water and the polytetrafluoroethylene emulsion into the high-molecular sulfonate copolymer emulsion, heating and stirring to obtain a mixture B for later use; 4) and adding a coagulant into the mixture B, uniformly stirring, heating, reacting, washing, drying and crushing the obtained precipitate to obtain the anti-dripping macromolecular sulfonate flame retardant. The anti-dripping macromolecular sulfonate flame retardant has lasting flame retardance and anti-dripping characteristic.)

1. A preparation method of an anti-dripping macromolecular sulfonate flame retardant is characterized by comprising the following steps: the method comprises the following steps:

1) Mixing an emulsifier, unsaturated sulfonate, an unsaturated monomer and part of deionized water according to parts by weight, heating and stirring the mixture uniformly to obtain a mixture A, and keeping the temperature for later use;

2) Adding an initiator into the mixture A obtained in the step 1), heating and stirring to perform free radical reaction to obtain high-molecular sulfonate copolymer emulsion for later use;

3) Adding the polytetrafluoroethylene emulsion and the other part of deionized water into the high-molecular sulfonate copolymer emulsion obtained in the step 2), heating and stirring to obtain a mixture B for later use; the mass ratio of the deionized water added in the step 1) to the deionized water added in the step 3) is 3-6: 6-10;

4) And adding a coagulant into the mixture B, stirring uniformly, heating, demulsifying, washing, drying and crushing the obtained precipitate to obtain the anti-dripping macromolecular sulfonate flame retardant.

2. the method for preparing an anti-dripping polymeric sulfonate flame retardant according to claim 1, wherein the anti-dripping polymeric sulfonate flame retardant comprises the following steps: the heating in the step 1) is carried out to the temperature of 40-80 ℃, and the stirring speed is 180-220 r/min.

3. the method for preparing an anti-dripping polymeric sulfonate flame retardant according to claim 1, wherein the anti-dripping polymeric sulfonate flame retardant comprises the following steps: in the step 2), the temperature is heated to 40-80 ℃, and the reaction time is 2-4 h.

4. The method for preparing an anti-dripping polymeric sulfonate flame retardant according to claim 1, wherein the anti-dripping polymeric sulfonate flame retardant comprises the following steps: in the step 3), the temperature is increased to 70-90 ℃, and the stirring is carried out for 2-4 h.

5. The method for preparing an anti-dripping polymeric sulfonate flame retardant according to claim 1, wherein the anti-dripping polymeric sulfonate flame retardant comprises the following steps: in the step 4), the mixture is heated to 60-80 ℃, the demulsification time is 3-7h, and the drying temperature during drying is 100-.

6. An anti-dripping polymeric sulfonate flame retardant prepared by the preparation method of any one of claims 1 to 5, wherein: the feed comprises the following raw materials in parts by weight:

7. the anti-dripping polymeric sulfonate flame retardant of claim 6, wherein: each part of the unsaturated sulfonate is at least one of sodium styrene sulfonate, sodium allyl sulfonate, sodium vinyl sulfonate, sodium methallyl sulfonate, 3-allyloxy-2-hydroxy-1-sodium propane sulfonate and 2-acrylamide-2-sodium methyl propane sulfonate.

8. The anti-dripping polymeric sulfonate flame retardant of claim 6, wherein: each part of the unsaturated monomer is a vinyl monomer, a styrene monomer, an acrylate monomer and an acrylonitrile monomer; the vinyl monomer is at least one of 5-vinyl-2-norbornene, vinyl imidazole, vinyl methyl ether, vinyl ethyl ether, vinyl acetate, vinyl butyrate, vinyl furan, N-vinyl carbazole, vinyl pyrrolidine and diallyl phthalate; the styrene monomer is at least one of styrene, alpha-methylstyrene, alpha-ethylstyrene, p-methylstyrene and o-tert-butylstyrene; the acrylic ester monomer is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, n-pentyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate; the acrylonitrile monomer is acrylonitrile and/or methacrylonitrile.

9. The anti-dripping polymeric sulfonate flame retardant of claim 6, wherein: each part of the initiator is at least two of ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide-sodium bisulfite redox system.

10. the anti-dripping polymeric sulfonate flame retardant of claim 6, wherein: each part of the coagulant is at least one of inorganic acid, organic acid and inorganic salt; each part of the emulsifier is a mixture consisting of anionic surfactant, cationic surfactant and nonionic surfactant according to the weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0.

Technical Field

the invention relates to the technical field of macromolecules, in particular to an anti-dripping macromolecular sulfonate flame retardant and a preparation method thereof.

Background

The thermoplastic material has the advantages of light weight, convenience in manufacturing and industrial production and the like, has the figure in the aspects of daily production and life, and brings huge power to the development of human beings, but because the thermoplastic material is easy to burn, is easy to soften and deform when heated, and even drops, a flame retardant is required to be added in the production process to enable the thermoplastic material to have a wider application range, and at present, the flame retardant modification research and application of plastic products prove that the flame retardant can be added to delay the combustion and reduce the combustion strength. However, in the burning process of the plastic product, besides the plastic product burns, the plastic product also can generate drops to ignite other combustible substances, so that the fire spread is caused, and the consequences are more serious than that of the plastic product burning per se. Therefore, the addition of flame retardants alone is not sufficient in the flame retarding of polymers, and additives are often also needed to prevent dripping of the polymer during the burning process. The introduction of sulfonate can endow polycarbonate with catalytic flame-retardant effect, organic sulfonate such as diphenyl sulfone potassium sulfonate (KSS) which is industrially applied has good catalytic flame-retardant effect on polycarbonate materials, but the organic sulfonate is a small molecular flame retardant, is easy to separate out due to lack of physical entanglement with a polycarbonate material substrate, and has large application limitation.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide an anti-dripping high-molecular sulfonate flame retardant, which is prepared by preparing a high-molecular sulfonate copolymer and poly (tetrafluoroethylene) through an emulsion polymerization method to be subjected to co-coagulation coating to prepare the high-molecular sulfonate flame retardant with lasting flame retardance and anti-dripping characteristics, wherein the poly (tetrafluoroethylene) used in the invention can effectively improve the dripping resistance during combustion and prevent the fire spread during combustion of thermoplastic resin, and the poly (tetrafluoroethylene) is subjected to coagulation coating with a high-molecular sulfonate graft copolymer to improve the dispersion effect of the poly (tetrafluoroethylene) in the thermoplastic resin and improve the flame retardance of the thermoplastic resin, and meanwhile, the high-molecular sulfonate flame retardant overcomes the defects that the organic sulfonate micromolecule flame retardant applied industrially in the prior art is lack of physical entanglement and easy to precipitate during the polymerization of the organic sulfonate micromolecule, application limitation and the like.

The invention also aims to provide a preparation method of the anti-dripping high-molecular sulfonate flame retardant, which utilizes an emulsion polymerization method to copolymerize unsaturated monomers and unsaturated sulfonates to prepare high-molecular sulfonate copolymer emulsion, and adopts a co-coagulation coating process to compound the high-molecular sulfonate copolymer and polytetrafluoroethylene, so that the prepared high-molecular sulfonate flame retardant has high-efficiency flame retardance and anti-dripping performance and can resist flame for a long time; the method has the advantages of convenient control, high production efficiency and low production cost, and is suitable for large-scale production.

the purpose of the invention is realized by the following technical scheme: a preparation method of an anti-dripping macromolecular sulfonate flame retardant is characterized by comprising the following steps: the method comprises the following steps:

1) Mixing the emulsifier, the unsaturated sulfonate, the unsaturated monomer and part of deionized water according to the parts by weight, heating to 40-80 ℃, and stirring at the speed of 180-;

2) adding an initiator into the mixture A obtained in the step 1), stirring and heating to 40-80 ℃, and carrying out free radical reaction for 2-4h to obtain a high-molecular sulfonate copolymer emulsion for later use;

3) Adding the other part of deionized water and the polytetrafluoroethylene emulsion into the high-molecular sulfonate copolymer emulsion obtained in the step 2), heating to 70-90 ℃, and stirring for 2-4 hours to obtain a mixture B for later use; the mass ratio of the deionized water added in the step 1) to the deionized water added in the step 3) is 3-6: 6-10.

4) and adding a coagulant into the mixture B, stirring uniformly, heating to 60-80 ℃, demulsifying for 3-7h, washing the obtained precipitate, drying at the temperature of 100-120 ℃, and crushing to obtain the anti-dripping high-molecular sulfonate flame retardant.

the macromolecular sulfonate flame retardant with the anti-dripping function is prepared by the method, has high-efficiency flame retardance and anti-dripping performance and can be used for realizing durable flame retardance, and simultaneously solves the problems of lack of physical entanglement, easy precipitation, application limitation and the like when the organic sulfonate micromolecular flame retardant applied to the existing industrialization is blended with a polycarbonate material substrate. According to the preparation method, an unsaturated monomer and unsaturated sulfonate are copolymerized by an emulsion polymerization method to prepare a high-molecular sulfonate copolymer emulsion, and a co-coagulation coating process is adopted to compound the high-molecular sulfonate copolymer and the polytetrafluoroethylene emulsion, so that the prepared high-molecular sulfonate flame retardant has high-efficiency flame retardance and anti-dripping performance and can be flame-retarded permanently. In addition, the stirring speed in the step 1) needs to be strictly controlled to be 180-220r/min in the preparation process, and if the stirring speed is too high, the contact reaction time between the emulsifier and the unsaturated sulfonate is too short, so that the emulsification of the unsaturated sulfonate cannot be realized; in the step 2), the heating temperature needs to be controlled to be 40-80 ℃, if the temperature is too high, the half-life period of the initiator is too short, and if the temperature is too low, the initiation of the free radical reaction is not facilitated; in the step 4), the temperature of the coagulant after addition needs to be strictly controlled to be 60-80 ℃, which is beneficial to coagulation of colloid particles after polymerization of polytetrafluoroethylene emulsion and high molecular sulfonate, if the heating temperature is too high, the activity of the colloid particles is increased, which is not beneficial to coagulation of the colloid particles, if the temperature is too low, the colloid particles are easy to coagulate into colloid, which is not beneficial to forming precipitates, and the high molecular sulfonate flame retardant is prepared by separation.

Preferably, the anti-dripping macromolecular sulfonate flame retardant comprises the following raw materials in parts by weight:

Preferably, each part of the unsaturated sulfonate is at least one of sodium styrene sulfonate, sodium allyl sulfonate, sodium vinyl sulfonate, sodium methallyl sulfonate, sodium 3-allyloxy-2-hydroxy-1-propane sulfonate and sodium 2-acrylamido-2-methylpropane sulfonate; more preferably, the unsaturated sulfonate is a mixture of sodium styrene sulfonate, sodium vinyl sulfonate and sodium methallyl sulfonate in a weight ratio of 0.8-1.2:0.4-0.8: 0.1-0.5.

The unsaturated sulfonate has a catalytic flame-retardant effect on a polycarbonate material, but the unsaturated sulfonate has small molecules, is easy to separate out due to lack of physical entanglement with the polycarbonate material, and limits the application of the unsaturated sulfonate, so that the unsaturated sulfonate needs to be polymerized to form high-molecular sulfonate.

preferably, each unsaturated monomer is a vinyl monomer, a styrene monomer, an acrylate monomer or an acrylonitrile monomer; the vinyl monomer is at least one of 5-vinyl-2-norbornene, vinyl imidazole, vinyl methyl ether, vinyl ethyl ether, vinyl acetate, vinyl butyrate, vinyl furan, N-vinyl carbazole, vinyl pyrrolidine and diallyl phthalate; the styrene monomer is at least one of styrene, alpha-methylstyrene, alpha-ethylstyrene, p-methylstyrene and o-tert-butylstyrene; the acrylic ester monomer is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, n-pentyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate; the acrylonitrile monomer is acrylonitrile and/or methacrylonitrile. More preferably, the unsaturated monomer is a mixture of vinyl ethyl ether, styrene and acrylonitrile in a weight ratio of 0.8-1.2:0.1-0.5: 0.4-0.8.

The unsaturated monomer adopts the vinyl monomer, the styrene monomer and the acrylonitrile monomer, is polymerized with the unsaturated sulfonate emulsion, and is coagulated and coated with the polytetrafluoroethylene emulsion, so that the flame retardance, the heat resistance and the impact resistance of the polycarbonate material can be improved.

Preferably, each part of the initiator is at least two of ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide-sodium bisulfite redox system; more preferably, the initiator is a mixture of ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide-sodium bisulfite redox system in a weight ratio of 0.5-0.9:0.8-1.2: 0.4-0.8.

the initiator used in the invention has good initiating effect, can efficiently initiate free radical rapid polymerization and copolymerization reaction in the unsaturated sulfonic acid polymerization process, and simultaneously can improve the copolymerization between unsaturated sulfonate and unsaturated monomer, thereby generating high-molecular sulfonate copolymer emulsion which is beneficial to coating with polytetrafluoroethylene emulsion.

preferably, each part of the coagulant is at least one of an inorganic acid, an organic acid and an inorganic salt; the inorganic acid is at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, the organic acid is formic acid and acetic acid, and the inorganic salt is at least one of aluminum sulfate, magnesium sulfate, calcium acetate and calcium chloride; more preferably, the coagulant is a mixture of sulfuric acid, acetic acid and calcium chloride in a weight ratio of 0.4-0.8:0.1-0.5:0.8-1.2, and further, the coagulant is calcium chloride.

preferably, each part of the emulsifier is a mixture consisting of anionic surfactant, cationic surfactant and nonionic surfactant according to the weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0; the anionic surfactant is at least one of sodium dodecyl benzene sulfonate, alpha-olefin sulfonate, alkyl sulfonate, alpha-sulfo monocarboxylic ester, fatty acid sulfoalkyl ester, succinate sulfonate, alkyl naphthalene sulfonate, petroleum sulfonate, lignosulfonate and alkyl glyceryl ether sulfonate; the cationic surfactant is at least one of cetyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride, polyethylene polyamine salt, alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzyl alkyl dimethyl quaternary ammonium salt, monoalkyl quaternary ammonium salt, alkylphenol polyoxyethylene quaternary ammonium salt, N-alkyl diethanol amine salt, pyridine salt and imidazoline; the nonionic surfactant is at least one of alkylphenol ethoxylate, sorbitan ester isomeric alcohol ethoxylate, fatty acid methyl ester ethoxylate, trimethyl nonanol ethoxylate, glycerol monostearate, fatty acid polyoxyethylene ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid vinegar, polyglycerol fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester and polyoxyethylene modified organopolysiloxane.

The flocculant can effectively make the polytetrafluoroethylene emulsion and the high-molecular sulfonate emulsion form an aggregate and settle together in the process of coagulation, and is favorable for separating to prepare the high-molecular sulfonate flame retardant. The adopted emulsifier has good emulsifying effect, is beneficial to the emulsifying dispersion between the sulfonate emulsion and the unsaturated monomer, is convenient for the subsequent coating action with the polytetrafluoroethylene emulsion, and is further beneficial to the rapid and efficient preparation of the high-molecular sulfonate flame retardant.

the invention has the beneficial effects that: the anti-dripping macromolecular sulfonate flame retardant is prepared by utilizing an emulsion polymerization method to prepare a macromolecular sulfonate copolymer and polytetrafluoroethylene to be subjected to co-coagulation coating, so that the macromolecular sulfonate flame retardant with lasting flame retardance and anti-dripping characteristics is prepared.

According to the preparation method of the anti-dripping high-molecular sulfonate flame retardant, the unsaturated monomer and the unsaturated sulfonate are copolymerized through an emulsion polymerization method to prepare the high-molecular sulfonate copolymer emulsion, and the high-molecular sulfonate copolymer and the polytetrafluoroethylene emulsion are compounded through a co-coagulation coating process, so that the prepared high-molecular sulfonate flame retardant has high-efficiency flame retardance and anti-dripping performance and can be used for realizing lasting flame retardance.

Detailed Description

The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.