An anti-drip agent and its preparation method and application

Abstract

The present invention discloses an anti-dripping agent and a preparation method and application thereof, and belongs to the technical field of thermoplastic resin products. The content of polyoxyethylene ether surfactant in the anti-dripping agent provided by the present invention does not exceed 3100 ppm. When the anti-dripping agent is used to prepare thermoplastic resin products, polyoxyethylene ether surfactant that is easily decomposed will not or substantially will not be introduced into the thermoplastic resin products, and the obtained thermoplastic resin products can be guaranteed to have good appearance and surface quality.

Description

Technical Field

[0001] This invention relates to the field of thermoplastic resin products technology, specifically to an anti-dripping agent, its preparation method and application, particularly its application in thermoplastic resin products. Background Technology

[0002] During combustion, the dripping of plastics is a major cause of the rapid spread of fire. Anti-dripping agents are commonly used in plastic products to inhibit dripping formation. A commonly used anti-dripping agent is tetrafluoroethylene (TEF) anti-dripping agent with a molecular weight of approximately 4-5 million. These anti-dripping agents are added to thermoplastic engineering plastics such as PC, PC / ABS alloys, PBT, ABS, and HIPS. Under certain conditions, they can effectively disperse into a fibrous network structure, providing anti-dripping properties and improving flame retardant performance. Furthermore, they can meet the ULV-0 standard requirements while reducing the amount of flame retardant used. Currently, the most widely used anti-dripping agents on the market are emulsion-type fluoropolymer (e.g., polytetrafluoroethylene emulsion) anti-dripping agents, pure fluoropolymer powder anti-dripping agents, and coated fluoropolymer anti-dripping agents.

[0003] However, regardless of whether it's an emulsion-type or coated fluoropolymer antidrip agent, the preparation process involves a fluoropolymer emulsion (usually a concentrated aqueous dispersion of the fluoropolymer). Surfactants are added during the preparation of these emulsions to help the fluoropolymer particles maintain a stable concentration (typically 40-70% solids) in the aqueous phase to form the emulsion. Currently, commercially available fluoropolymer (generally polytetrafluoroethylene) emulsions primarily use polyoxyethylene ether surfactants, such as trimethylnonyl polyoxyethylene ether (TMN series), fatty alcohol polyoxyethylene ether (APEO series), and alkylphenol polyoxyethylene ether (NPEO, OPEO) nonionic surfactants. These surfactants typically constitute about 2-5 wt% of the fluoropolymer emulsion. During the preparation of the antidrip agent, most of these surfactants remain in the antidrip agent and may subsequently enter the thermoplastic resin product along with it. These polyoxyethylene ether surfactants decompose during the processing of thermoplastic resin products, leading to defects such as yellowing and silver streaks on the surface, especially in high-gloss mirror PC. Summary of the Invention

[0004] In view of one or more problems existing in the prior art, the first aspect of the present invention provides an anti-dripping agent, wherein the content of polyoxyethylene ether surfactant does not exceed 3100 ppm.

[0005] In some embodiments, the content of polyoxyethylene ether surfactants in the anti-dripping agent does not exceed 2000 ppm, preferably not more than 1600 ppm.

[0006] In some embodiments, the anti-dripping agent may comprise a fluoropolymer and a polymer formed by polymerization of vinyl monomers and / or acrylate monomers; wherein, based on the weight of the anti-dripping agent, the content of the fluoropolymer may be 40-70 wt%, optionally 45-60 wt%, and the content of the polymer formed by polymerization of vinyl monomers and / or acrylate monomers may be 30-60 wt%, optionally 40-55 wt%.

[0007] In some embodiments, the anti-dripping agent further comprises a non-polyoxyethylene ether surfactant, wherein the content of the non-polyoxyethylene ether surfactant is 0-5 wt%, optionally 0-1 wt%, based on the weight of the anti-dripping agent.

[0008] In some embodiments, the anti-dripping agent may be a coating structure, wherein the fluoropolymer forms the inner layer of the coating structure, and the polymer formed by polymerization of vinyl monomers and / or acrylate monomers forms the outer layer of the coating structure.

[0009] In some embodiments, the molecular weight of the fluoropolymer may be 1 million to 10 million, and it may include a homopolymer or copolymer of several fluorinated monomers selected from: tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, perfluoroethylene propylene, vinylidene fluoride, C 1-4 fluoroalkyl ethylene and C 1-4 Fluoroalkyl vinyl ethers.

[0010] In some embodiments, the vinyl polymerizing monomer may be selected from one or more of the following: ethylene, propylene, butene, isobutene, butadiene, styrene, α-C 1-4 Alkyl styrene, acrylonitrile, and methacrylonitrile; and / or, the acrylate polymeric monomers are selected from one or more of the following: acrylic acid C 1-4 Alkyl esters and methacrylic acid C 1-4 Alkyl esters.

[0011] In some embodiments, the non-polyoxyethylene ether surfactant may be selected from one or more of ionic surfactants, polymeric surfactants, non-polyoxyethylene ether nonionic surfactants, or combinations thereof.

[0012] In some embodiments, the ionic surfactant may be selected from one or more of the following: alkyl sulfates, polyoxyethylene fatty alcohol ether sulfates, fatty acid salts, alcohol ether carboxylates, alkylphenol ether carboxylates, stearates, alkylbenzene sulfonates, α-olefin sulfonates, α-sulfonyl monocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkylnaphthalene sulfonates, alkyl glycerol ether sulfonates, petroleum sulfonates, lignin sulfonates, and alkyl carboxylates; further optionally, the ionic surfactant may be selected from one or more of the following: sodium dodecyl sulfate (SDS), ammonium dodecyl sulfate (AESA-70), sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl diphenyl ether disulfonate (SLDED), disodium dodecyl alcohol polyoxyethylene ether sulfosuccinate (MES), sodium dihexyl sulfonate, sodium dioctyl sulfosuccinate (OT-75), potassium stearate, sodium dodecyl carboxylate, and sodium dodecyl alcohol polyoxyethylene ether carboxylate.

[0013] In some embodiments, the polymeric surfactant is selected from one or more of the following: polyolefin polymers, polyvinylpyrrolidone (PVP) polymers, polyoxyethylene polymers, polyether polymers, polyurethane polymers, polyvinyl alcohol polymers, polysilicon-modified polyether polymers, polycarboxylic acid polymers, and organometallic polymeric surfactants (e.g., silicone surfactants).

[0014] In some embodiments, the non-polyoxyethylene ether-based nonionic surfactant is selected from one or more of the following: glyceryl monolaurate, hexyl alcohol ester, sucrose ester, and diethanolamide laurate.

[0015] A second aspect of the present invention provides a method for preparing an anti-dripping agent, comprising the following steps:

[0016] S1: Mix fluoropolymer emulsion, coagulant, initiator, vinyl polymer monomer and / or acrylate polymer monomer and distilled water, and react to obtain a reaction mixture;

[0017] S2: The reaction mixture is centrifuged, washed, and dried to obtain an anti-dripping agent;

[0018] The content of polyoxyethylene ether surfactant in the anti-dripping agent does not exceed 3100 ppm, preferably not more than 2000 ppm, and the anti-dripping agent comprises a fluoropolymer and a polymer formed by polymerization of vinyl polymer monomers and / or acrylate polymer monomers; wherein, based on the weight of the anti-dripping agent, the content of the fluoropolymer is 40-70 wt%, optionally 45-60 wt%, and the content of the polymer formed by polymerization of vinyl polymer monomers and / or acrylate polymer monomers is 30-60 wt%, optionally 40-55 wt%.

[0019] In some embodiments, the solid content of the fluoropolymer emulsion in step S1 may be 40-70 wt%, optionally 55-65 wt%, and the fluoropolymer emulsion contains a non-polyoxyethylene ether surfactant.

[0020] In some embodiments, the content of the non-polyoxyethylene ether surfactant may be 2-16 wt%, optionally 2-12 wt%, and further optionally 4-10 wt%, depending on the solid content of the fluoropolymer emulsion.

[0021] In some embodiments, the fluoropolymer emulsion further comprises a polyoxyethylene ether surfactant, wherein the content of the polyoxyethylene ether surfactant is no more than 1 wt%, preferably no more than 0.5 wt%, based on the solid content of the fluoropolymer emulsion.

[0022] In some embodiments, the coagulant in step S1 may be selected from one or more of the following solutions: sodium chloride, magnesium chloride, calcium chloride, ferric chloride, ferrous chloride, aluminum chloride, copper chloride, magnesium sulfate, aluminum sulfate, calcium acetate, copper sulfate, ferric sulfate, ferrous sulfate, sodium phosphate, calcium phosphate, and magnesium phosphate.

[0023] In some embodiments, the initiator in step S1 may include a free radical thermal polymerization initiator and a redox polymerization initiator; optionally, the initiator may be selected from one or more of the following: hydrogen peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, cumene hydrogen peroxide, tert-butyl hydrogen peroxide, and benzoyl peroxide.

[0024] In some embodiments, the reaction conditions in step S1 may include: a reaction temperature of 40-80°C, optionally 50-70°C, and a reaction time of 2-10 hours, optionally 3-6 hours.

[0025] A third aspect of the present invention provides a thermoplastic resin composition comprising the following raw materials in parts by weight:

[0026]

[0027] The anti-drip agent is the anti-drip agent provided in the first aspect of the present invention or the anti-drip agent prepared by the preparation method provided in the second aspect of the present invention.

[0028] In some embodiments, the thermoplastic resin may include: acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber-modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), copolymers thereof, or combinations thereof.

[0029] In some embodiments, the flame retardant may include halogenated flame retardants, organophosphorus flame retardants, inorganic flame retardants, intumescent flame retardants, and sulfonate flame retardants; optionally, the flame retardant may be selected from one or more of the following: bis(hexachlorocyclopentadiene)cyclooctyl (DCRP), tetrabromobisphenol A (TBBA), resorcinol (diphenyl phosphate) (RDP), bisphenol A-bis(diphenyl phosphate) (BDP), aluminum hydroxide (ATH), magnesium hydroxide (MTH), potassium perfluorobutyl sulfonate (KPFBS), and potassium benzenesulfonylbenzenesulfonate (KSS).

[0030] In a fourth aspect, the present invention provides a thermoplastic resin article produced from the thermoplastic resin composition provided in the third aspect of the present invention.

[0031] Based on the above technical solutions, the content of polyoxyethylene ether surfactants in the anti-dripping agent does not exceed 3100 ppm, preferably not more than 2000 ppm. When used to prepare thermoplastic resin products, it will not or will not introduce easily decomposed polyoxyethylene ether surfactants into the thermoplastic resin products. Therefore, it can ensure that the prepared thermoplastic resin products have good appearance and surface quality, and even have better flame retardant and anti-dripping properties and superior appearance and surface quality than thermoplastic resin products prepared by anti-dripping agents containing more than 3100 ppm of polyoxyethylene ether surfactants in the prior art. Detailed Implementation

[0032] The following detailed description of the concentrated aqueous dispersion of fluoropolymers provided by the present invention, its preparation method, and its applications will illustrate these embodiments. However, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter of the claims.

[0033] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0034] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0035] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0036] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0037] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0038] In the description of this article, it should be noted that, unless otherwise stated, "one or more" means two or more.

[0039] In the field of anti-dripping agent preparation technology for fluoropolymers (such as polytetrafluoroethylene), whether it is an emulsion-type fluoropolymer anti-dripping agent, a pure powder-type fluoropolymer anti-dripping agent, or a coated type, a fluoropolymer emulsion is used in the preparation process. Surfactants are added during the preparation of fluoropolymer emulsions to help the fluoropolymer particles exist stably in the aqueous phase at a certain concentration to form an emulsion. Currently, the surfactants in commercially available fluoropolymer emulsions are mainly polyoxyethylene ether surfactants, such as trimethylnonyl polyoxyethylene ether (TMN series), fatty alcohol polyoxyethylene ether (AEO series), and alkylphenol polyoxyethylene ether (NPEO, OPEO) nonionic surfactants. However, when these surfactants are used to prepare anti-dripping agents, most of them remain in the anti-dripping agent and may subsequently enter thermoplastic resin products along with the anti-dripping agent. These polyoxyethylene ether surfactants decompose during the processing of thermoplastic resin products, leading to defects such as yellowing and silver streaks on the surface, especially in high-gloss mirror PC.

[0040] Through extensive research, the inventors have observed that fluoropolymer emulsions with good stability can be prepared by using surfactants containing little or no polyoxyethylene ether surfactants (based on a solid content of no more than 1 wt%) in the preparation of fluoropolymer emulsions. Furthermore, the physicochemical properties of anti-dripping agents prepared using these fluoropolymer emulsions are comparable to those of anti-dripping agents prepared under the same conditions that contain a large amount of polyoxyethylene ether surfactants. In addition, the inventors were surprised to find that, compared to anti-dripping agents containing a large amount of polyoxyethylene ether surfactants, thermoplastic resin products prepared using these fluoropolymer anti-dripping agents containing little or no polyoxyethylene ether surfactants exhibit better flame retardant and anti-dripping properties, as well as superior appearance and surface quality.

[0041] In a first aspect of the invention, an anti-dripping agent is provided, wherein the content of a polyoxyethylene ether surfactant does not exceed 3100 ppm.

[0042] In some embodiments, the content of polyoxyethylene ether surfactants in the anti-dripping agent does not exceed 2000 ppm, preferably not more than 1600 ppm.

[0043] In some embodiments, the anti-dripping agent may comprise a fluoropolymer and a polymer formed by polymerization of vinyl monomers and / or acrylate monomers; wherein, based on the weight of the anti-dripping agent, the content of the fluoropolymer may be 40-70 wt%, optionally 45-60 wt%, and the content of the polymer formed by polymerization of vinyl monomers and / or acrylate monomers may be 30-60 wt%, optionally 40-55 wt%.

[0044] In some embodiments, based on the weight of the anti-dripping agent, the anti-dripping agent further comprises no more than 5 wt%, preferably no more than 1 wt%, of a non-polyoxyethylene ether surfactant. Such non-polyoxyethylene ether surfactants can be introduced from the fluoropolymer emulsion used to prepare the anti-dripping agent and exist as impurities in the resulting anti-dripping agent; therefore, it is preferable that the anti-dripping agent does not contain such surfactants.

[0045] In some embodiments, the anti-dripping agent may be a coating structure, that is, the anti-dripping agent is a coated fluoropolymer anti-dripping agent, wherein the fluoropolymer forms the inner layer of the coating structure, and the polymer formed by polymerizing vinyl monomers and / or acrylate monomers forms the outer layer of the coating structure.

[0046] In some embodiments, the molecular weight of the fluoropolymer may be 1 million to 10 million, and it may include a homopolymer or copolymer of several fluorinated monomers selected from the following: tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, perfluoroethylene propylene, vinylidene fluoride, C 1-4 fluoroalkyl ethylene and C 1-4 Fluoroalkyl vinyl ethers.

[0047] In some embodiments, the particle size of the fluoropolymer is not particularly limited, and is typically 0.15-0.40 μm.

[0048] In some embodiments, the vinyl polymerizable monomer may be selected from one or more of the following: ethylene, propylene, butene, isobutene, butadiene, styrene, α-C 1-4 Alkyl styrene, acrylonitrile, and methacrylonitrile.

[0049] In some embodiments, the acrylate polymer monomer may be selected from one or more of the following: acrylic acid C 1-4 Alkyl esters and methacrylic acid C 1-4 Alkyl esters.

[0050] In some embodiments, the non-polyoxyethylene ether surfactant is selected from one or more of ionic surfactants, polymeric surfactants, non-polyoxyethylene ether nonionic surfactants, or combinations thereof.

[0051] In some embodiments, the ionic surfactant is selected from one or more of the following: alkyl sulfates, polyoxyethylene fatty alcohol ether sulfates, fatty acid salts, alcohol ether carboxylates, alkylphenol ether carboxylates, stearates, alkylbenzene sulfonates, α-olefin sulfonates, α-sulfonyl monocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkylnaphthalene sulfonates, alkyl glycerol ether sulfonates, petroleum sulfonates, lignin sulfonates, and alkyl carboxylates; further optionally, the ionic surfactant is selected from one or more of the following: sodium dodecyl sulfate (SDS), ammonium dodecyl sulfate (AESA-70), sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl diphenyl ether disulfonate (SLDED), disodium dodecyl alcohol polyoxyethylene ether sulfosuccinate (MES), sodium dihexyl sulfonate, sodium dioctyl sulfosuccinate (OT-75), potassium stearate, sodium dodecyl carboxylate, and sodium dodecyl alcohol polyoxyethylene ether carboxylate.

[0052] In some embodiments, the polymeric surfactant is selected from one or more of the following: polyolefin polymers, polyvinylpyrrolidone (PVP, for example, polyvinylpyrrolidone polymers with a molecular weight of 1,000-100,000, such as those selected from one or more of the following: K12, K15, K17, K25, K30) polymers, polyoxyethylene polymers (polyoxyethylene, polyoxypropylene, polyoxybutenyl, polyoxypentenyl, etc.) polymers, polyether polymers, polyurethane polymers, polyvinyl alcohol polymers, polysilicon-modified polyether polymers, polycarboxylic acid polymers, and organometallic polymeric surfactants (referring to macromolecular main chains that do not contain carbon atoms but are composed of atoms such as silicon, boron, aluminum, oxygen, nitrogen, sulfur, and phosphorus, but whose side groups are composed of organic groups such as methyl, ethyl, and aryl, typically organosilicon surfactants).

[0053] In some embodiments, the non-polyoxyethylene ether-based nonionic surfactant is selected from one or more of the following: glyceryl monolaurate, hexyl alcohol ester, sucrose ester, and diethanolamide laurate.

[0054] In a second aspect of the present invention, a method for preparing an anti-dripping agent is provided, comprising the following steps:

[0055] S1: Mix fluoropolymer emulsion, coagulant, initiator, vinyl polymer monomer and / or acrylate polymer monomer and distilled water, and react to obtain a reaction mixture;

[0056] S2: The reaction mixture is centrifuged, washed, and dried to obtain an anti-dripping agent;

[0057] The content of polyoxyethylene ether surfactant in the anti-dripping agent does not exceed 3100 ppm, preferably not more than 2000 ppm, and the anti-dripping agent comprises a fluoropolymer and a polymer formed by polymerization of vinyl polymer monomers and / or acrylate polymer monomers; wherein, based on the weight of the anti-dripping agent, the content of the fluoropolymer is 40-70 wt%, optionally 45-60 wt%, and the content of the polymer formed by polymerization of vinyl polymer monomers and / or acrylate polymer monomers is 30-60 wt%, optionally 40-55 wt%.

[0058] In some embodiments, the mixing in step S1 can be carried out by stirring at a temperature of 50-80°C and a rotation speed of ≥200 rpm.

[0059] In some embodiments, the solid content of the fluoropolymer emulsion in step S1 may be 40-70 wt%, optionally 55-65 wt%, and the fluoropolymer emulsion contains a non-polyoxyethylene ether surfactant.

[0060] In some embodiments, the content of the non-polyoxyethylene ether surfactant may be 2-16 wt%, optionally 2-12 wt%, and further optionally 4-10 wt%, depending on the solid content of the fluoropolymer emulsion.

[0061] In some embodiments, the fluoropolymer emulsion may further contain polyoxyethylene ether surfactants, wherein the content of the polyoxyethylene ether surfactants is no more than 1 wt%, preferably no more than 0.5 wt%, based on the solid content of the fluoropolymer emulsion.

[0062] In some embodiments, the coagulant may be selected from one or more of the following solutions: sodium chloride, magnesium chloride, calcium chloride, ferric chloride, ferrous chloride, aluminum chloride, copper chloride, magnesium sulfate, aluminum sulfate, calcium acetate, copper sulfate, ferric sulfate, ferrous sulfate, sodium phosphate, calcium phosphate, and magnesium phosphate.

[0063] In some embodiments, the amount of coagulant added in step S1 may be such that the final salt concentration is 0.05-10 wt% of the total solution.

[0064] In some embodiments, the initiator in step S1 includes a free radical thermal polymerization initiator and a redox polymerization initiator; optionally, the initiator is selected from one or more of the following: water-soluble initiators such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble initiators such as azobisisobutyronitrile, cumene hydrogen peroxide, tert-butyl hydrogen peroxide, and benzoyl peroxide.

[0065] In some embodiments, the reaction conditions in step S1 include: a reaction temperature of 40-80°C, optionally 50-70°C, and a reaction time of 2-10 hours, optionally 3-6 hours. A reaction temperature below 40°C may make it difficult to initiate the reaction, while a temperature above 80°C may easily trigger explosive polymerization. A reaction time of less than 2 hours may make it difficult to complete the reaction, and a reaction time exceeding 10 hours will reduce efficiency and increase production costs.

[0066] In a third aspect of the invention, a thermoplastic resin composition is provided, comprising the following raw materials in parts by weight:

[0067]

[0068] The anti-dripping agent mentioned therein is the anti-dripping agent provided in the first aspect of the present invention that does not contain polyoxyethylene ether surfactants.

[0069] In some embodiments, the thermoplastic resin composition comprises the following raw materials in parts by weight:

[0070]

[0071] In some embodiments, the thermoplastic resin includes: acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber-modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), copolymers thereof, or combinations thereof.

[0072] In some embodiments, the flame retardant includes halogenated flame retardants, organophosphorus flame retardants, inorganic flame retardants, intumescent flame retardants, and sulfonate flame retardants.

[0073] In some embodiments, the flame retardant is selected from one or more of the following: bis(hexachlorocyclopentadiene)cyclooctyl (DCRP), tetrabromobisphenol A (TBBA), resorcinol (diphenyl phosphate) (RDP), bisphenol A-bis(diphenyl phosphate) (BDP), aluminum hydroxide (ATH), magnesium hydroxide (MTH), potassium perfluorobutyl sulfonate (KPFBS), and potassium benzenesulfonylbenzenesulfonate (KSS).

[0074] In a fourth aspect of the invention, a thermoplastic resin article is also provided, which is produced from the thermoplastic resin composition provided in the third aspect of the invention.

[0075] Example

[0076] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0077] Example 1: Preparation of anti-dripping agent

[0078] (1) Preparation of polytetrafluoroethylene emulsion containing 2 wt% (relative to the dry basis of the prepared polytetrafluoroethylene emulsion, the same below) polyvinylpyrrolidone (BASF PVP K12) as a surfactant

[0079] In a 5L stainless steel high-pressure reactor equipped with a jacket and horizontal stirrer, 3000g of deionized water and 80g of paraffin wax were added. The contents of the reactor were heated to 70°C, and the reactor was evacuated, purged with nitrogen, and then purged with tetrafluoroethylene (TFE). 0.02g of ammonium persulfate (polymer initiator) and 3g of fluorinated emulsifier (sodium perfluorohexylacetate) were added. The reaction pressure was controlled at 2.5MPa, and TFE was continuously introduced through a compressor. An initial aqueous dispersion of polytetrafluoroethylene (PTFE) particles was obtained via emulsion polymerization. The solid content of this dispersion was approximately 20wt%, and the average particle size of the PTFE particles was approximately 250nm.

[0080] Take 2 kg of the initial aqueous dispersion of polytetrafluoroethylene particles, add 2 wt% (based on the weight of the polytetrafluoroethylene particles, the same below) of BASF PVP K12, and concentrate under vacuum. The resulting polytetrafluoroethylene emulsion has a solid content of about 60.1 wt% and good storage stability.

[0081] (2) Preparation of anti-dripping agent

[0082] S1: The polytetrafluoroethylene emulsion containing 2wt% polyvinylpyrrolidone (PVP) prepared in (1) above, coagulant (calcium chloride salt solution), initiator (potassium persulfate), styrene polymer monomer (with a mass ratio of approximately 1:1 to the solid content in the polytetrafluoroethylene emulsion) and distilled water are added to the reaction vessel, sheared and stirred at 300 rpm, and reacted at 40-80℃ for 3-6 h to obtain the reaction mixture;

[0083] S2: Centrifuge the reaction mixture using a three-legged centrifuge at a speed of not less than 600 rpm, collect the centrifuged precipitate, wash the precipitate with 0.2-5 times the weight of the precipitate with water, and then dry it in a drying oven at 70-120℃ to obtain anti-dripping agent A containing BASF PVPK12. The physicochemical characteristics test results are shown in Table 1 below.

[0084] Physicochemical characteristic test methods for anti-dripping agents:

[0085] (1.1) Content of polyoxyethylene ether surfactants

[0086] Detection was performed using liquid chromatography-high resolution mass spectrometry (LC-HRMS). The presence of a series of fragment peaks with mass numbers differing by an integer multiple of 44.052 in the HRMS spectrum indicates the presence of polyoxyethylene ether surfactants. The detection limit for this method is 1 ppm; therefore, when the content of polyoxyethylene ether surfactants is below 1 ppm, the detection result is expressed as no change (ND).

[0087] (1.2) Polytetrafluoroethylene content

[0088] Take 2.0g of anti-dripping agent sample, add 200g of methanol, heat under reflux for 8 hours, cool, filter, and dry the remaining solid. The percentage of the remaining solid to the sample is the content of polytetrafluoroethylene.

[0089] (1.3) Polymer content formed by polymerization of vinyl or acrylate monomers

[0090] Take 2.0g of sample and add 200g of tetrahydrofuran, heat under reflux for 4h, cool and filter, and dry the remaining solid. The difference between the sample amount and the remaining solid amount divided by the sample amount is the content of the polymer formed by the polymerization of vinyl or acrylate monomers.

[0091] (1.4) Content of volatile components

[0092] Take approximately 0.10g of sample, place it in a rapid moisture analyzer, and dry it at 105℃ until constant weight. The percentage of weight loss is the content of volatile components.

[0093] (1.5) Particle size distribution

[0094] Take 100g of sample and pour it into the top layer of the grading vibrating screen. Turn on the vibrating screen for 10s, weigh the sample in each layer, and calculate its percentage of the total sample.

[0095] Example 2-10

[0096] Examples 2-10 were carried out according to the method steps of Example 1, except that different surfactants were used in the method for preparing the anti-dripping agent, specifically:

[0097] Example 2 prepared a polytetrafluoroethylene emulsion containing 4 wt% polyvinylpyrrolidone (BASF PVP K12). The solid content of the obtained polytetrafluoroethylene emulsion was about 61.5 wt%, and it had good storage stability. Anti-dripping agent B was prepared using the polytetrafluoroethylene emulsion, and the physicochemical characteristics test results are shown in Table 1 below.

[0098] Example 3 prepared a polytetrafluoroethylene emulsion containing 1 wt% polyvinylpyrrolidone (BASF PVP K17) and 3 wt% glyceryl monolaurate. The solid content of the obtained polytetrafluoroethylene emulsion was about 61.7 wt%, and it had good storage stability. Anti-dripping agent C was prepared using the polytetrafluoroethylene emulsion, and the physicochemical characteristics test results are shown in Table 1 below.

[0099] Example 4 prepared a polytetrafluoroethylene emulsion containing 1 wt% polyvinylpyrrolidone (BASF PVP K12) and 5 wt% glyceryl monolaurate. The solid content of the obtained polytetrafluoroethylene emulsion was about 62.1 wt%, and it had good storage stability. Anti-dripping agent D was prepared using the polytetrafluoroethylene emulsion (the mass ratio of styrene monomer to solid content in the polytetrafluoroethylene emulsion during the preparation process was about 60:40). The physicochemical characteristics test results are shown in Table 1 below.

[0100] Example 5 prepared a polytetrafluoroethylene emulsion containing 6 wt% polyvinylpyrrolidone (BASF PVP K12) and 4 wt% glyceryl monolaurate. The solid content of the obtained polytetrafluoroethylene emulsion was about 63.2 wt%, and it had good storage stability. Anti-dripping agent E was prepared using the polytetrafluoroethylene emulsion (the mass ratio of styrene monomer to solid content in the polytetrafluoroethylene emulsion during the preparation process was about 45:55). The physicochemical characteristics test results are shown in Table 1 below.

[0101] Example 6 prepared a polytetrafluoroethylene emulsion containing 4 wt% polyvinylpyrrolidone (BASF PVP K30) and 0.5 wt% sodium dodecyl sulfate (SDS). The solid content of the obtained polytetrafluoroethylene emulsion was about 61.6 wt%, and it had good storage stability. Anti-dripping agent F was prepared using the polytetrafluoroethylene emulsion, and the physicochemical characteristics test results are shown in Table 1 below.

[0102] Example 7 prepared a polytetrafluoroethylene emulsion containing 2 wt% sodium dodecylbenzenesulfonate (SDBS). The solid content of the obtained polytetrafluoroethylene emulsion was about 61.0 wt%, and it had good storage stability. Anti-dripping agent G was prepared using the polytetrafluoroethylene emulsion, and the physicochemical characteristics test results are shown in Table 1 below.

[0103] Example 8 prepared a polytetrafluoroethylene emulsion containing 2 wt% sodium dihexyl sulfonate. The solid content of the obtained polytetrafluoroethylene emulsion was about 61.1 wt%, and it had good storage stability. Anti-dripping agent H was prepared using the polytetrafluoroethylene emulsion, and the physicochemical characteristics test results are shown in Table 1 below.

[0104] Example 9 prepared a polytetrafluoroethylene emulsion containing 3 wt% polyvinylpyrrolidone (BASF PVP K12) and 1 wt% trimethylnonyl polyoxyethylene ether-10 (TMN-10), with a solid content of approximately 60.3 wt%. Anti-dripping agent I was prepared using this polytetrafluoroethylene emulsion, and its physicochemical characteristics are shown in Table 1 below.

[0105] Example 10 prepared a polytetrafluoroethylene emulsion containing 4 wt% polyvinylpyrrolidone (BASF PVP K12) and 0.5 wt% trimethylnonyl polyoxyethylene ether-10 (TMN-10), with a solid content of approximately 59.1 wt%. Anti-dripping agent J was prepared using the polytetrafluoroethylene emulsion, and its physicochemical characteristics are shown in Table 1 below.

[0106] Comparative Examples 1-8

[0107] Comparative Examples 1-8 were carried out according to the method steps of Example 1, except that different surfactants were used in the method for preparing the anti-dripping agent, specifically:

[0108] Comparative Example 1 prepared a polytetrafluoroethylene emulsion containing 5 wt% trimethylnonyl polyoxyethylene ether-6 (TMN-6), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent K containing TMN-6. The physicochemical characteristics test results are shown in Table 1 below.

[0109] Comparative Example 2 prepared a polytetrafluoroethylene emulsion containing 5 wt% trimethylnonyl polyoxyethylene ether-10 (TMN-10), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent L containing TMN-10.

[0110] Comparative Example 3 prepared a polytetrafluoroethylene emulsion containing 5 wt% octylphenol polyoxyethylene ether (OPEO), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent M containing OPEO. The physicochemical characteristics test results are shown in Table 1 below.

[0111] Comparative Example 4 prepared a polytetrafluoroethylene emulsion containing 5 wt% nonylphenol polyoxyethylene ether (NPEO), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent N containing NPEO. The physicochemical characteristics test results are shown in Table 1 below.

[0112] Comparative Example 5 prepared a polytetrafluoroethylene emulsion containing 2.5 wt% trimethylnonyl polyoxyethylene ether-10 (TMN-10), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent O containing TMN-10. The physicochemical characteristics test results are shown in Table 1 below.

[0113] Comparative Example 6 prepared a polytetrafluoroethylene emulsion containing 2.5 wt% nonylphenol polyoxyethylene ether (NPEO), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent N containing NPEO. The physicochemical characteristics test results are shown in Table 1 below.

[0114] Comparative Example 7 prepared a polytetrafluoroethylene emulsion containing 1 wt% polyvinylpyrrolidone (BASF PVP K12) and 3 wt% trimethylnonyl polyoxyethylene ether-10 (TMN-10), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent P. The physicochemical characteristics test results are shown in Table 1 below.

[0115] Comparative Example 8 prepared a polytetrafluoroethylene emulsion containing 1 wt% polyvinylpyrrolidone (BASF PVP K12) and 2 wt% trimethylnonyl polyoxyethylene ether-10 (TMN-10), and used the polytetrafluoroethylene emulsion to prepare an anti-dripping agent Q. The physicochemical characteristics test results are shown in Table 1 below.

[0116] Table 1: Physicochemical characteristics of the anti-dripping agents prepared in Examples 1-10 and Comparative Examples 1-8

[0117]

[0118] As can be seen from the physicochemical characteristic test results of the anti-dripping agents described in Examples 1-10 above, when the surfactant used in the preparation of polytetrafluoroethylene emulsion does not contain polyoxyethylene ether surfactants or contains only a small amount (not exceeding 1 wt%) of polyoxyethylene ether surfactants, a polytetrafluoroethylene emulsion with good stability and a solid content of about 60% (optionally 40-70%, further optionally 55-65%) can also be obtained. Furthermore, a coated polytetrafluoroethylene anti-dripping agent can be successfully prepared using the polytetrafluoroethylene emulsion containing no or a small amount of polyoxyethylene ether surfactants. Moreover, the various physicochemical characteristic indicators of this polytetrafluoroethylene anti-dripping agent are basically no different from those of the anti-dripping agent prepared using a polytetrafluoroethylene emulsion containing polyoxyethylene ether surfactants (wherein the content of polyoxyethylene ether surfactants exceeds 1 wt%). Therefore, the present invention successfully prepared a fluoropolymer anti-dripping agent without using or with a small amount of polyoxyethylene ether surfactants, wherein the agent contains no more than 3100 ppm, preferably no more than 2000 ppm, of polyoxyethylene ether surfactants.

[0119] Example 11: Preparation of thermoplastic resin products containing anti-dripping agents

[0120] The thermoplastic resin article containing an anti-dripping agent provided in this embodiment is made from a thermoplastic resin composition comprising the following raw materials in parts by weight:

[0121]

[0122]

[0123] The thermoplastic resin composition consisting of the above-mentioned raw materials in parts by weight was extruded and granulated at 270°C using a Nanjing JENT SHJ-36 plastic extruder, and then injection molded at 280°C using a Haitian SA860 injection molding machine to obtain thermoplastic resin products containing anti-drip agents. The physicochemical properties (including flame retardancy, mechanical properties, surface gloss, and high-gloss mirror effect) of the thermoplastic resin products were tested, and the results are shown in Table 2 below.

[0124] Test methods for the physicochemical properties of thermoplastic resin products:

[0125] (2.1) Flame retardant properties (vertical burning 1 / 8', vertical burning 1 / 16')

[0126] Testing standard: UL 94-2020;

[0127] Test equipment: RH-6033B horizontal combustion test apparatus;

[0128] Test conditions:

[0129] Pretreatment: Place the test sample at 23±2℃ and 50±10%RH for 48h; age at 70℃ for 168h; and then place it in a desiccator for at least 4h to cool to room temperature.

[0130] Test Procedure: Place the Bunsen burner (flame height 20±1mm) directly below and in the center of the sample, with the burner nozzle 10±1mm from the bottom of the sample. Ignite for 10±0.5s. After 10±0.5s of ignition, move the Bunsen burner away at least 150mm at a speed of 300mm / sec. Simultaneously, record the afterflame time t1. When the afterflame stops, immediately ignite for 10±0.5s. After 10±0.5s of ignition, move the Bunsen burner away at least 150mm at a speed of 300mm / sec. Simultaneously, record the afterflame time t2 and the afterburn time t3. Calculate the flame retardant performance of the test sample according to the UL94-2020 test standard.

[0131] (2.2) Impact strength of cantilever beam with notch

[0132] Test standard: ASTM D256-10(2018);

[0133] Testing equipment: Zwick HIT 25P plastic pendulum impact tester;

[0134] (2.3) Melt mass flow rate

[0135] Test standard: ASTM D1238-13;

[0136] Testing equipment: MFLOW melt flow rate tester / FD-115 drying oven;

[0137] (2.4) Vicat softening temperature

[0138] Test standard: ASTM D1525-17;

[0139] Testing equipment: Type 40-197-100 heat distortion Vicat testing machine;

[0140] (2.5) Surface gloss

[0141] Test standard: ASTM D523;

[0142] Testing equipment: 3nh gloss meter;

[0143] (2.6) High-gloss mirror effect

[0144] Testing standards: Based on defects in the high-gloss mirror surface, such as silver streaks and pitting, it is divided into 5 levels, with level 1 being the best and level 5 being the worst.

[0145] Test method: Visual inspection.

[0146] Examples 12-20

[0147] Examples 12-20 were carried out according to the method and steps of Example 11, except that different anti-drip agents were used in the preparation of the thermoplastic resin products. Specifically, Example 12 used anti-drip agent B, Example 13 used anti-drip agent C, Example 14 used anti-drip agent D, Example 15 used anti-drip agent E, Example 16 used anti-drip agent F, Example 17 used anti-drip agent G, Example 18 used anti-drip agent H, Example 19 used anti-drip agent I, and Example 20 used anti-drip agent J. The test results of the physicochemical properties of the thermoplastic resin products are shown in Table 2 below.

[0148] Comparative Examples 9-16

[0149] Comparative Examples 9-16 were prepared according to the method and steps of Example 9, except that different anti-drip agents were used in the preparation of the thermoplastic resin products. Specifically, Comparative Example 9 used anti-drip agent K, Comparative Example 10 used anti-drip agent L, Comparative Example 11 used anti-drip agent M, Comparative Example 12 used anti-drip agent N, Comparative Example 13 used anti-drip agent O, Comparative Example 14 used anti-drip agent P, Comparative Example 15 used anti-drip agent R, and Comparative Example 16 used anti-drip agent R. The test results of the physicochemical properties of the thermoplastic resin products are shown in Table 2 below.

[0150] Table 2: Test results of the physicochemical properties of the thermoplastic resin articles prepared in Examples 11-20 and Comparative Examples 9-16

[0151]

[0152] As can be seen from the test results of the physicochemical properties of the thermoplastic resin products recorded in Table 2 above, the thermoplastic resin products prepared in Examples 11-20 are essentially no different from those prepared in Comparative Examples 9-16 in terms of impact performance (cantilever beam notched impact strength), melt flow rate (melt mass flow rate), Vicat softening temperature, and vertical flame retardancy at 1 / 8'. This indicates that the thermoplastic resin products prepared with anti-dripping agents containing no or a small amount (not exceeding 3100 ppm) of polyoxyethylene ether surfactants are comparable to those prepared with anti-dripping agents containing (more than 3100 ppm) of polyoxyethylene ether surfactants in terms of impact performance, melt flow rate, Vicat softening temperature, and vertical flame retardancy at 1 / 8', and both have good properties. However, compared to the thermoplastic resin articles prepared in Comparative Examples 9-16, the thermoplastic resin articles prepared in Examples 11-18 using anti-dripping agents without polyoxyethylene ether surfactants, or in Example 20 using anti-dripping agents containing no more than 1600 ppm of polyoxyethylene ether surfactants, exhibited superior flame retardant performance at 1 / 16' vertical direction. This indicates that anti-dripping agents containing no or a small amount (no more than 2000 ppm, preferably no more than 1600 ppm) of polyoxyethylene ether surfactants in thermoplastic resin articles exhibit superior flame retardant and anti-dripping properties. Furthermore, compared to the thermoplastic resin articles prepared in Comparative Examples 9-16, the thermoplastic resin articles prepared in Examples 11-18 using anti-dripping agents without polyoxyethylene ether surfactants, or in Examples 19-20 using anti-dripping agents containing no more than 3100 ppm of polyoxyethylene ether surfactants, exhibited superior surface gloss and high-gloss mirror effect. Furthermore, the results of Comparative Examples 15-16 and Examples 19-20 also show that the higher the content of polyoxyethylene ether surfactants in the anti-drip agent, the worse the high-gloss mirror effect of the corresponding thermoplastic resin product. Therefore, compared with the anti-drip agents in the prior art containing more than 3100 ppm of polyoxyethylene ether surfactants, the anti-drip agent provided by the present invention, which contains no or a small amount (not exceeding 3100 ppm) of polyoxyethylene ether surfactants, can produce thermoplastic resin products with superior overall performance.

[0153] Examples 21-23

[0154] Examples 21-23 were carried out according to the method and steps of Example 11, except that the formulation of the thermoplastic resin composition used was different, as shown in Table 3 below. The test results of the physicochemical properties of the obtained thermoplastic resin products are shown in Table 4 below.

[0155] Table 3: Formulations of the thermoplastic resin compositions in Examples 21-23 (by weight)

[0156] Components polycarbonate EM500A BDP 1076 Antioxidant 168 Co-antioxidant PETS lubricant Anti-dripping agent A Example 21 100 2 8 0 0.4 1 1 Example 22 100 8 5 1 0 0.4 0.05 Example 23 100 10 1 0.4 1 0.2 0.5

[0157] Table 4: Test results of the physicochemical properties of the thermoplastic resin products prepared in Examples 21-23

[0158]

[0159] As can be seen from the test results of the physicochemical properties of the thermoplastic resin products recorded in Tables 3 and 4 above, thermoplastic resin products with excellent comprehensive properties can be obtained by using the thermoplastic resin compositions of Examples 21-23.

[0160] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An anti-drip agent, characterized in that The anti-dripping agent is composed of a fluorine-containing polymer, a polymer formed by polymerization of vinyl monomers and / or acrylate monomers, a non-polyoxyethylene ether surfactant and an optional polyoxyethylene ether surfactant, wherein the non-polyoxyethylene ether surfactant is composed of a polyvinyl pyrrolidone polymer with a molecular weight of 1000-100000 and one or more surfactants selected from the following: alkyl sulfate, alkylbenzene sulfonate, dihexyl sodium sulfosuccinate, lauric acid monoglyceride, hexitol ester, sucrose ester and lauric acid diethanolamide; and wherein: Based on the weight of the anti-drip agent, the content of the fluorine-containing polymer is 40-70wt%, the content of the polymer formed by polymerization of vinyl polymerization monomers and / or acrylate polymerization monomers is 30-60wt%, the content of the optional polyoxyethylene ether surfactant is not more than 1600ppm, and the content of the non-polyoxyethylene ether surfactant is not more than 5wt%.

2. The anti-dripping agent according to claim 1, characterized in that The content of the fluorine-containing polymer is 45-60 wt %, and the content of the polymer formed by polymerizing the vinyl polymerized monomer and / or the acrylic ester polymerized monomer is 40-55 wt %.

3. The anti-dripping agent according to claim 1, characterized in that The content of the non-polyoxyethylene ether surfactant in the anti-dripping agent is no more than 1 wt %.

4. The anti-dripping agent according to claim 1, characterized in that The anti-drip agent is a coating structure, wherein the fluorine-containing polymer forms the inner layer of the coating structure, and the polymer formed by polymerizing vinyl monomers and / or acrylic ester monomers forms the outer layer of the coating structure.

5. The anti-dripping agent according to claim 1, characterized in that The molecular weight of the fluorine-containing polymer is 1 million to 10 million, and it includes any one of the following fluorine-containing monomer homopolymers or copolymers of several fluorine-containing monomers: tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroethylene propylene, vinylidene fluoride, C 1-4 Fluoroalkylethylene and C 1-4 Fluoroalkyl vinyl ether.

6. The anti-dripping agent according to claim 1, characterized in that The vinyl polymerizable monomer is selected from one or more of the following: ethylene, propylene, butylene, isobutylene, butadiene, styrene, α-C 1-4 Alkyl styrenes, acrylonitrile and methacrylonitrile; and / or, The acrylic acid ester polymerizable monomer is selected from one or more of the following: acrylic acid C 1-4 Alkyl esters and methacrylate C 1-4 Alkyl esters.

7. The anti-dripping agent according to any one of claims 1 to 6, characterized in that The anti-dripping agent is prepared by the following steps: S1: mixing a fluorine-containing polymer emulsion, a coagulant, an initiator, a vinyl polymerization monomer and / or an acrylate polymerization monomer and distilled water to obtain a reaction mixture after reaction; S2: centrifuging, washing, and drying the reaction mixture to obtain an anti-dripping agent; Wherein in step S1, the solid content of the fluoropolymer emulsion is 40-70wt%, and the fluoropolymer emulsion is composed of fluoropolymer particles dispersed in an aqueous solvent, the non-polyoxyethylene ether surfactant and an optional polyoxyethylene ether surfactant, wherein the content of the non-polyoxyethylene ether surfactant is 2-16wt%, and the content of the polyoxyethylene ether surfactant is not more than 0.5wt%, wherein the content is based on the solid content of the fluoropolymer emulsion.

8. The method for preparing the anti-dripping agent according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: S1: mixing a fluorine-containing polymer emulsion, a coagulant, an initiator, a vinyl polymerization monomer and / or an acrylate polymerization monomer and distilled water to obtain a reaction mixture after reaction; S2: centrifuging, washing, and drying the reaction mixture to obtain an anti-dripping agent; The solid content of the fluoropolymer emulsion in step S1 is 40-70wt%, and the fluoropolymer emulsion is composed of fluoropolymer particles dispersed in an aqueous solvent, the non-polyoxyethylene ether surfactant and an optional polyoxyethylene ether surfactant, wherein the content of the non-polyoxyethylene ether surfactant is 2-16wt%, and the content of the polyoxyethylene ether surfactant is no more than 0.5wt%, wherein the content is based on the solid content of the fluoropolymer emulsion.

9. The preparation method according to claim 8, characterized in that: The solid content of the fluorine-containing polymer emulsion in step S1 is 55-65 wt %.

10. The preparation method according to claim 9, characterized in that: Based on the solid content of the fluorine-containing polymer emulsion, the content of the non-polyoxyethylene ether surfactant is 2-12 wt %.

11. The preparation method according to claim 10, characterized in that: The content of the non-polyoxyethylene ether surfactant is 4-10wt%.

12. The preparation method according to claim 8, characterized in that: In step S1, the coagulant is selected from one or more of the following solutions: sodium chloride, magnesium chloride, calcium chloride, ferric chloride, ferrous chloride, aluminum chloride, cupric chloride, magnesium sulfate, aluminum sulfate, calcium acetate, cupric sulfate, ferric sulfate, ferrous sulfate, sodium phosphate, calcium phosphate, magnesium phosphate; and / or, The initiator in step S1 includes a free radical thermal polymerization initiator and a redox polymerization initiator.

13. The preparation method according to claim 12, characterized in that: The initiator is selected from one or more of the following: hydrogen peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, cumene hydroperoxide, tert-butyl hydroperoxide, and benzoyl peroxide.

14. The preparation method according to any one of claims 8 to 13, characterized in that: The reaction conditions in step S1 include: reaction temperature of 40-80° C., and reaction time of 2-10 hours.

15. The preparation method according to claim 14, characterized in that: The reaction temperature in step S1 is 50-70°C.

16. The preparation method according to claim 14, characterized in that: The reaction time in step S1 is 3-6 hours.

17. A thermoplastic resin composition, characterized in that The thermoplastic resin composition comprises the following raw materials in parts by weight: Thermoplastic resin 100 parts Toughener 2-10 parts Flame retardant 0.1-15 parts Anti-drip agent 0.01-5 parts Primary antioxidant 0-1 part Auxiliary antioxidant 0-1 part Lubricant 0-1 part; The anti-dripping agent is the anti-dripping agent according to any one of claims 1 to 7 or the anti-dripping agent prepared by the preparation method according to any one of claims 8 to 16.

18. The thermoplastic resin composition according to claim 17, characterized in that The thermoplastic resin includes: acrylonitrile-butadiene-styrene copolymer resin, rubber-modified polystyrene resin, acrylonitrile-styrene-acrylate copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, acrylonitrile-ethyl acrylate-styrene copolymer resin, polycarbonate resin, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polymethyl methacrylate, or a combination thereof.

19. The thermoplastic resin composition according to claim 17 or 18, characterized in that: The flame retardant includes a halogen flame retardant, an organic phosphorus flame retardant, an inorganic flame retardant, an intumescent flame retardant and a sulfonate flame retardant.

20. The thermoplastic resin composition according to claim 19, characterized in that The flame retardant comprises: bis(hexachlorocyclopentadiene)cyclooctane, tetrabromobisphenol A, resorcinol (diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), aluminum hydroxide, magnesium hydroxide, potassium perfluorobutyl sulfonate, and potassium benzenesulfonylbenzenesulfonate.

21. A thermoplastic resin article produced from the thermoplastic resin composition according to any one of claims 17 to 20.

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