阅读说明：本技术 一种阻燃抗菌剂及其制法和应用及阻燃抗菌热塑性树脂组合物 (Flame-retardant antibacterial agent, preparation method and application thereof, and flame-retardant antibacterial thermoplastic resin composition ) 是由 王宇韬 初立秋 李�杰 张师军 高达利 尹华 郭鹏 邵静波 李长金 胡晨曦 白弈 于 2019-10-30 设计创作，主要内容包括：本发明涉及塑料加工领域的一种阻燃抗菌剂及其制法和应用及阻燃抗菌热塑性树脂组合物。所述阻燃抗菌剂,为表面接枝胍盐的聚合物微球,所述阻燃抗菌聚合物微球包含结构单元A、结构单元B和结构单元C的交联结构；其中,所述结构单元A为马来酸酐提供；所述结构单元B为单体M提供；所述结构单元C为交联剂提供；其中单体M由碳四和/或碳五提供；所述胍盐选自小分子胍盐以及胍盐聚合物中的一种或多种,且所述胍盐至少包括一种具有阻燃性的胍盐；制备得到的阻燃抗菌热塑性树脂组合物阻燃、抗菌、防霉效果好,通过配方调控制备得到一种兼具阻燃性与抗菌性能的热塑性树脂组合物；所制备的热塑性树脂组合物的综合性能优良。(The invention relates to a flame-retardant antibacterial agent, a preparation method and application thereof and a flame-retardant antibacterial thermoplastic resin composition in the field of plastic processing. The flame-retardant antibacterial agent is a polymer microsphere with guanidine salt grafted on the surface, and the flame-retardant antibacterial polymer microsphere comprises a cross-linked structure of a structural unit A, a structural unit B and a structural unit C; wherein the structural unit A is provided by maleic anhydride; the structural unit B is provided for a monomer M; the structural unit C provides a cross-linking agent; wherein monomer M is provided by carbon four and/or carbon five; the guanidine salt is selected from one or more of small molecule guanidine salt and guanidine salt polymer, and the guanidine salt at least comprises one guanidine salt with flame retardance; the prepared flame-retardant antibacterial thermoplastic resin composition has good flame-retardant, antibacterial and mildew-proof effects, and the thermoplastic resin composition with flame-retardant and antibacterial properties is prepared by regulating and controlling the formula; the thermoplastic resin composition prepared has excellent comprehensive performance.)

1. The flame-retardant antibacterial agent is a polymer microsphere with guanidine salt grafted on the surface, and the polymer microsphere comprises a cross-linked structure of a structural unit A, a structural unit B and a structural unit C; wherein the structural unit A is provided by maleic anhydride; the structural unit B is provided for a monomer M; the structural unit C provides a cross-linking agent; wherein monomer M is provided by carbon four and/or carbon five;

the guanidine salt is selected from one or more of small molecule guanidine salt and guanidine salt polymer, and the guanidine salt at least comprises one guanidine salt with flame retardance;

the average particle size of the polymer microspheres is 200-2000 nm.

2. The flame retardant, antimicrobial agent of claim 1, wherein:

the cross-linking agent is selected from vinyl-containing monomers with two or more functionalities and capable of free radical polymerization; preferably, the crosslinking agent is divinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups; the structural formula of the acrylate group is as follows: -O-C (O) -C (R') ═ CH₂R' is H or alkyl of C1-C4;

more preferably, the crosslinking agent is selected from one or more of divinylbenzene, propylene glycol-based di (meth) acrylate, ethylene glycol-based di (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid ethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate.

3. The flame retardant, antimicrobial agent of claim 1, wherein:

the small molecular guanidine salt is selected from one or more of guanidine phosphate, guanidine hydrochloride, guanidine nitrate, guanidine hydrobromide, guanidine oxalate, guanidine dihydrogen phosphate, diguanidine hydrogen phosphate and amino guanidine salt; wherein the amino guanidine salt is selected from one or more of carbonate, nitrate, phosphate, oxalate, hydrochloride, hydrobromide, sulfonate and other inorganic or organic salts of aminoguanidine, diaminoguanidine and triaminoguanidine; preferably one or more of nitrate, phosphate, hydrochloride, hydrobromide and sulfonate of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, biguanidine hydrogen phosphate and aminoguanidine, diaminoguanidine and triaminoguanidine;

the guanidine salt polymer is selected from one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine oxalate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyhexamethylene (bis) guanidine sulfonate, and other inorganic or organic salts of polyhexamethylene (bis) guanidine, and polyoxyethylene guanidine.

4. The flame retardant, antimicrobial agent of claim 1, wherein:

the flame-retardant guanidine salt is at least one selected from the group consisting of guanidine phosphate, guanidine hydrochloride, guanidine hydrobromide, guanidine dihydrogen phosphate, biguanidine hydrogen phosphate, and amino guanidine phosphate, hydrochloride, hydrobromide, nitrate, carbonate, oxalate, sulfonate, and polymers of the guanidine salts; at least one of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, diguanidine hydrogen phosphate, amino guanidine phosphate, hydrochloride, hydrobromide, nitrate, sulfonate, polyhexamethylene (bis) guanidine hydrochloride, and polyhexamethylene (bis) guanidine phosphate is preferable.

5. The flame retardant, antimicrobial agent of claim 1, wherein:

the molar ratio of the structural unit A to the structural unit B is in a range of 0.5: 1-1: 0.5, preferably 0.75: 1-1: 0.75; and/or the presence of a gas in the gas,

the weight percentage of the dissolved substance of the polymer microspheres in 5 times of acetone is less than or equal to 8 wt% at the temperature of 50 ℃ for 30 min; and/or the presence of a gas in the gas,

the crosslinking degree of the polymer microspheres is more than or equal to 50 percent.

6. A flame-retardant antibacterial agent according to any one of claims 1 to 5, characterized in that:

the flame-retardant guanidine salt accounts for 30-100 wt% of the total weight of the guanidine salt; preferably 50 to 100 wt%; more preferably 80 to 100 wt%.

7. The method for preparing a flame-retardant antibacterial agent according to any one of claims 1 to 6, comprising the steps of crosslinking and copolymerizing components including maleic anhydride, the monomer M and the crosslinking agent in the presence of an initiator to obtain polymer microspheres, and grafting the polymer microspheres with guanidine salt or a guanidine salt solution to obtain the flame-retardant antibacterial agent.

8. The method of producing a flame-retardant antibacterial agent according to claim 7, characterized by comprising the steps of:

(1) in an organic solvent, in the presence of a first part of initiator, maleic anhydride is contacted with a first part of monomer M for reaction, and then a solution containing a cross-linking agent is introduced for continuous reaction; wherein the crosslinker-containing solution contains a crosslinker, optionally a second portion of monomer M, and optionally a second portion of initiator;

(2) adding a guanidine salt or a guanidine salt solution into the product obtained in the step (1) to continue the reaction, so that the guanidine salt is grafted on the surface of the product obtained in the step (1).

9. The method of producing a flame-retardant antibacterial agent according to claim 8, wherein in the step (1):

the total amount of the first part of monomer M and the second part of monomer M in terms of terminal olefin is 50-150 mol relative to 100mol of maleic anhydride; and/or the presence of a gas in the gas,

the molar ratio of the second part of the monomers M to the first part of the monomers M is (0-100): 100; and/or the presence of a gas in the gas,

the amount of the cross-linking agent is 1-40 mol relative to 100mol of the maleic anhydride.

10. The method of preparing a flame-retardant antibacterial agent according to claim 8, characterized in that:

the organic solvent is selected from organic acid alkyl ester, or a mixture of the organic acid alkyl ester and alkane, or a mixture of the organic acid alkyl ester and aromatic hydrocarbon; wherein the organic acid alkyl ester is selected from at least one of methyl formate, ethyl formate, methyl propyl ester, methyl butyl ester, methyl isobutyl ester, amyl formate, methyl acetate, ethyl ester, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate.

11. The method of preparing a flame-retardant antibacterial agent according to claim 8, characterized in that:

the total dosage of the first part of initiator and the second part of initiator is 0.05-10 mol relative to 100mol of maleic anhydride; and/or the presence of a gas in the gas,

the molar ratio of the second part of the initiator to the first part of the initiator is (0-100): 100.

12. The method of preparing a flame-retardant antibacterial agent according to claim 8, characterized in that:

the initiator is at least one selected from dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.

13. The method of preparing a flame-retardant antibacterial agent according to claim 8, characterized in that:

in the step (1), the conditions for contacting the maleic anhydride and the first part of the monomer M to react comprise: an inert atmosphere, wherein the temperature is 50-90 ℃, and the pressure is 0.3-1 MPa; and/or the presence of a gas in the gas,

in the step (1), the conditions for introducing the solution containing the cross-linking agent again to continue the reaction comprise: the temperature is 50-90 ℃, and the pressure is 0.3-1 MPa; and/or the presence of a gas in the gas,

in the step (2), the reaction conditions include: the temperature is 0 to 100 ℃, preferably 2.5 to 90 ℃.

14. The method of preparing a flame-retardant antibacterial agent according to claim 8, characterized in that:

in the step (2), adding the guanidine salt or the guanidine salt aqueous solution into the product obtained in the step (1) for reaction; the dosage of the guanidine salt is 5g to 5000g, preferably 20g to 3000g, and more preferably 100g to 2000g relative to 1000g of maleic anhydride; the dosage of the guanidine salt aqueous solution is 500-10000 g, preferably 1000-8000 g, relative to 1000g of maleic anhydride; the concentration of the guanidine salt aqueous solution is 0.5 to 50 wt%, preferably 1 to 30 wt%.

15. The method of preparing a flame-retardant antibacterial agent according to claim 14, characterized in that:

and (2) drying the product obtained in the step (1), and directly adding the dried product into a guanidine salt water solution for reaction.

16. Use of a flame retardant antimicrobial agent according to any one of claims 1 to 6 or prepared by the method according to any one of claims 7 to 15 in a flame retardant antimicrobial material.

17. A flame-retardant antibacterial thermoplastic resin composition comprising the flame-retardant antibacterial agent according to any one of claims 1 to 6 or the flame-retardant antibacterial agent prepared by the method according to any one of claims 7 to 15 and a thermoplastic resin.

18. The flame retardant, antibacterial thermoplastic resin composition according to claim 17, characterized by comprising the following components in parts by weight:

100 parts by weight of a thermoplastic resin,

0 to 2.0 parts by weight, preferably 0.1 to 1.2 parts by weight, of an aluminum hypophosphite flame retardant;

0-2.0 parts by weight of melamine hydrobromide, preferably 0.1-1.2 parts by weight;

0-1.0 part by weight of flame retardant synergist, preferably 0.05-1 part by weight;

0.05-4.0 parts by weight of the flame-retardant antibacterial agent, preferably 0.1-2.8 parts by weight;

0 to 5.0 parts by weight of a mildew preventive, preferably 0.05 to 4.0 parts by weight.

19. The flame retardant, antibacterial thermoplastic resin composition according to claim 18, characterized in that:

the aluminum phosphinate flame retardant is inorganic aluminum hypophosphite and/or alkyl aluminum phosphinate; the aluminum alkyl phosphinate is at least one selected from aluminum diethyl phosphinate, aluminum dipropyl phosphinate and aluminum phenyl phosphinate; the aluminum phosphinate flame retardant is preferably inorganic aluminum hypophosphite and/or aluminum diethylphosphinate; and/or the presence of a gas in the gas,

the flame retardant synergist is at least one selected from 2, 3-dimethyl-2, 3-diphenyl butane and p-cumene polymer; and/or the presence of a gas in the gas,

the mildew inhibitor is at least one selected from pyridylthione, isothiazolinone, 10 ' -oxo-diphenol Oxazine (OBPA), 3-iodine-2-propynyl butyl carbamate (IPBC), 2,4,4' -trichloro-2 ' -hydroxydiphenyl ether (triclosan) and 2- (thiazole-4-yl) benzimidazole.

20. The flame retardant, antibacterial thermoplastic resin composition according to claim 19, characterized in that:

the pyrithione is selected from at least one of zinc pyrithione, copper pyrithione and dipyrithione; and/or the presence of a gas in the gas,

the isothiazolinone is at least one selected from 2-methyl-1-isothiazolin-3-one (MIT), 5-chloro-2-methyl-1-isothiazolin-3-one (CMIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-n-octyl-3-isothiazolinone (DCOIT), 1, 2-benzisothiazolin-3-one (BIT), 4-methyl-1, 2-benzisothiazolin-3-one (MBIT), and 4-n-butyl-1, 2-benzisothiazolin-3-one (BBIT).

21. A flame retardant antibacterial thermoplastic resin composition according to any one of claims 17 to 20, characterized in that:

the thermoplastic resin is selected from at least one of polyolefin, polystyrene, polyvinyl chloride, polyacrylonitrile/butadiene/styrene copolymer, polyacrylonitrile/styrene copolymer, polyformaldehyde, nylon, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenyl ether and polyphenylene sulfide and/or at least one of the alloys of the thermoplastic resin; the polyolefin is preferably polyethylene and/or polypropylene.

22. A method for producing a flame-retardant antibacterial thermoplastic resin composition according to any one of claims 17 to 21, comprising the step of melt-blending components including the thermoplastic resin, the flame-retardant antibacterial agent.

Technical Field

The invention relates to the field of plastic processing, in particular to a flame-retardant antibacterial agent, a preparation method and application thereof, and a flame-retardant antibacterial thermoplastic resin composition.

Background

In recent years, with technological progress, such as the rise of intelligent and electric revolution, the pursuit of high-quality and healthy life is continuously promoted. Intelligent household appliances (such as electric toilets, intelligent refrigerators, air conditioners, washing machines and the like) and new energy automobiles have also gradually entered the lives of people and play more and more important roles. The demands and standards of the scientific and technological products on safety and health are continuously increased, wherein fire safety and sanitation become more important concerns of people, and the scientific and technological products are widely researched and reported. The products have certain requirements on the flame retardance (UL-94 vertical burning test and glow wire flammability test) and the sanitation of the used materials.

Thermoplastic resins such as polypropylene (PP) are one of the most widely used and growing varieties of current general-purpose plastics. It has excellent properties of high rigidity, high strength, good heat resistance, easy processing and the like, and is one of the widely applied matrix materials in the new products. However, PP is flammable, generates a large amount of molten drops in the combustion process, and has rapid flame propagation and poor fire safety. In addition, PP also needs to be modified by antimicrobial to improve the hygiene of the material. The flame retardant modification of PP mainly comprises an intrinsic flame retardant modification method and an additive modification method. Among them, the additive modification method of additionally adding a high-efficiency flame retardant into PP is widely used due to the advantages of simple operation, controllable cost, easy popularization, industrialization and the like. The flame retardant used for PP mainly includes halogen flame retardants, inorganic flame retardants, Intumescent Flame Retardants (IFR), and the like. The halogen flame retardant has higher flame retardant efficiency on PP, but because the use of the halogen flame retardant has serious safety and environmental hazards, the application of singly adding a large amount of halogen flame retardant is increasingly limited. Although inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide are environmentally friendly, they have low flame retardant efficiency and require high addition levels to achieve a certain flame retardant effect. In addition, the dispersibility of the modified polypropylene in PP is poor, and the modified polypropylene has a large influence on the mechanical properties of a base material, so that the modified polypropylene is not suitable for separate application. The IFR flame retardant has the advantages of high flame retardant efficiency, low smoke, low toxicity and the like, and the flame retardant efficiency is synergistically improved by compounding a small amount of halogen flame retardants, phosphorus flame retardants and nitrogen flame retardants, so that the IFR flame retardant is known as one of effective ways for realizing low halogenation or non-halogenation of the flame retardant. The flame retardant synergist is introduced to improve the flame retardant efficiency and reduce the influence on the processability and mechanical properties of the material caused by the large addition of the flame retardant to a certain extent.

The preparation of the antibacterial plastic is mainly that the matrix resin, the antibacterial agent and the process auxiliary agent are uniformly mixed according to a certain proportion, then the modified resin with the antibacterial function is prepared by direct melt blending, and finally various antibacterial products are manufactured by various plastic molding processing methods (such as extrusion, injection molding, casting, blow molding, plastic suction and the like). Currently, the antimicrobial agents used in the market mainly include inorganic and organic antimicrobial agents. The inorganic antibacterial agent is mainly an inorganic substance loaded with antibacterial metal ions (such as one or more of silver ions, zinc ions, copper ions and the like), and can be used as a carrier for loading various carriers, including zeolite (natural or synthetic zeolite), zirconium phosphate, soluble glass, calcium phosphate, silica gel and the like. The organic antibacterial agents are classified according to their structures and include guanidinium salts, quaternary ammonium salts, quaternary phosphonium salts, imidazoles, pyridines, organic metals, and the like. The inorganic antibacterial agent has the characteristics of high safety, good heat resistance, long-lasting sterilization and the like, but the sterilization of the inorganic antibacterial agent is not immediate, and the price is high due to the adoption of noble metals. The organic antibacterial agent has the advantages of high sterilization speed, good antibacterial and mildewproof effects, wide application range and the like, but also has the problems of easy generation of drug resistance, poor heat resistance and the like.

At present, researchers mainly achieve the improvement of the flame retardant performance and the antibacterial performance of the material by respectively adding a flame retardant and an antibacterial agent (for example, chinese patents with publication numbers CN107151430A, CN 106149091a, and CN 106835328 a). Because the flame retardant and the antibacterial agent have poor dispersibility in the base material, the addition of the flame retardant and the antibacterial agent respectively may have certain influence on the comprehensive performance of the material. In particular, in order to realize multiple functions of a polymer material, a large amount of multi-component auxiliaries are often added, and the multi-component auxiliaries may affect each other, thereby affecting the comprehensive performance of the material. Therefore, development of a single-component multi-functionalization assistant with higher efficiency has become one of important ways to realize multi-functionalization of polymer materials.

Disclosure of Invention

In order to solve the above problems in the prior art, the present invention proposes a flame retardant antibacterial agent. In particular to a flame-retardant antibacterial agent, a preparation method and application thereof and a flame-retardant antibacterial thermoplastic resin composition. The obtained thermoplastic resin has good antibacterial effect and flame retardance.

One of the purposes of the invention is to provide a flame-retardant antibacterial agent, which is a polymer microsphere with guanidine salt grafted on the surface, wherein the polymer microsphere comprises a cross-linked structure of a structural unit A, a structural unit B and a structural unit C; wherein the structural unit A is provided by maleic anhydride; the structural unit B is provided for a monomer M; the structural unit C provides a cross-linking agent;

wherein monomer M is provided by carbon four and/or carbon five;

the guanidine salt is selected from one or more of small molecule guanidine salt and guanidine salt polymer, and the guanidine salt at least comprises one guanidine salt with flame retardance; the flame-retardant guanidine salt accounts for 30-100 wt% of the total weight of the guanidine salt; preferably 50 to 100 wt%; more preferably 80 to 100 wt%; specific examples thereof include: 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 100%.

The polymer microspheres have an eluted matter of less than or equal to 8 wt% (e.g., 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5.5 wt%, 6.5 wt%, 7.5 wt%, 8 wt% or any value therebetween) in 5 times the weight of acetone (50 ℃, 30 min);

the crosslinking degree of the flame-retardant antibacterial polymer microspheres is more than or equal to 50 percent (such as 50 percent, 55 percent, 60 percent, 65 percent, 70 percent, 75 percent, 80 percent, 85 percent, 90 percent or any value between the values), preferably more than or equal to 70 percent, and more preferably more than or equal to 90 percent;

the polymer microspheres are in a microsphere or sphere-like shape; the average particle size is 200-2000 nm (such as 2000nm, 250nm, 350nm, 450nm, 550nm, 650nm, 750nm, 850nm, 950nm, 1050nm, 1150nm, 1250nm, 1350nm, 1450nm, 1550nm, 1650nm, 1750nm, 1850nm, 2000nm or any value therebetween). The guanidine salt flame-retardant antibacterial microsphere has a shell cross-linked structure, so that the guanidine salt flame-retardant antibacterial microsphere has better solvent resistance and thermal stability.

The crosslinking degree of the guanidine salt flame-retardant antibacterial microspheres represents the gel content and is measured by a solvent extraction method. The average particle size is characterized by a number average particle size and is determined by means of a scanning electron microscope.

The molar ratio of structural unit a to structural unit B may range from 0.5: 1-1: 0.5, preferably 0.75: 1-1: 0.75.

the crosslinking agent may be any of various conventional vinyl-containing monomers having two or more functionalities capable of free radical polymerization. Preferably, the crosslinking agent is divinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups of the formula: -O-C (O) -C (R') ═ CH₂R' is H or C1-C4 alkyl (such as methyl).

More preferably, the crosslinking agent is selected from one or more of divinylbenzene, propylene glycol-based di (meth) acrylate, ethylene glycol-based di (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid ethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate.

The propylene glycol bis (meth) acrylate can be selected from one or more of 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate and 1, 2-propylene glycol diacrylate; the ethylene glycol type bi (methyl) acrylate is selected from one or more of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetraethylene glycol diacrylate. The guanidine salt can be selected from one or more of small molecule guanidine salt and guanidine salt polymer; the small molecule guanidine salt can be one or more of guanidine phosphate, guanidine hydrochloride, guanidine nitrate, guanidine hydrobromide, guanidine oxalate, guanidine dihydrogen phosphate, guanidine hydrogen phosphate and amino guanidine salt; wherein, the amino guanidine salt can be selected from one or more of carbonate, nitrate, phosphate, oxalate, hydrochloride, hydrobromide, sulfonate and other inorganic salt or organic salt of aminoguanidine, diaminoguanidine and triaminoguanidine; preferably one or more of nitrate, phosphate, hydrochloride, hydrobromide and sulfonate of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, biguanidine hydrogen phosphate and aminoguanidine, diaminoguanidine and triaminoguanidine; further, one or more of nitrate, phosphate, hydrochloride, hydrobromide and sulfonate of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, diguanidine hydrogen phosphate, aminoguanidine, diaminoguanidine and triaminoguanidine are preferable; still further, one or more of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, diguanidine hydrogen phosphate, guanidine hydrobromide, triaminoguanidine nitrate, aminoguanidine nitrate, triaminoguanidine phosphate, triaminoguanidine hydrochloride, triaminoguanidine hydrobromide, triaminoguanidine sulfonate are preferable.

The guanidine salt polymer can be selected from one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine oxalate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyhexamethylene (bis) guanidine sulfonate and other inorganic or organic salts of polyhexamethylene (bis) guanidine, and polyoxyethylene guanidine; preferably one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, hexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine oxalate.

The flame-retardant guanidine salt can be selected from at least one of guanidine phosphate, guanidine hydrochloride, guanidine hydrobromide, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, hydrochloride, hydrobromide, nitrate, carbonate, oxalate, sulfonate of amino guanidine and polymer of the guanidine salt; at least one of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, diguanidine hydrogen phosphate, amino guanidine phosphate, hydrochloride, hydrobromide, nitrate, sulfonate, polyhexamethylene (bis) guanidine hydrochloride, and polyhexamethylene (bis) guanidine phosphate is preferable. Wherein the aminoguanidine can be at least one of aminoguanidine, diaminoguanidine and triaminoguanidine.

The polyhexamethylene (bis) guanidine hydrochloride mentioned above refers to polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and the like.

The other object of the invention is to provide a preparation method of the flame-retardant antibacterial agent, which comprises the steps of crosslinking and copolymerizing components including maleic anhydride, the monomer M and the crosslinking agent in the presence of an initiator to obtain polymer microspheres, and grafting the polymer microspheres and guanidine salt or a guanidine salt solution to obtain the flame-retardant antibacterial agent.

Specifically, the following steps may be included:

(1) in an organic solvent, in the presence of a first part of initiator, maleic anhydride is contacted with a first part of monomer M for reaction, and then a solution containing a cross-linking agent is introduced for continuous reaction; wherein the crosslinker-containing solution contains a crosslinker, optionally a second portion of monomer M, and optionally a second portion of initiator;

(2) adding a guanidine salt or a guanidine salt solution into the product obtained in the step (1) to continue the reaction, so that the guanidine salt is grafted on the surface of the product obtained in the step (1).

Wherein the content of the first and second substances,

in the step (1), the step (c),

the ratio of the amount of the maleic anhydride to the amount of the monomer M may be conventionally selected, but in a preferred embodiment of the present invention, the total amount of the first part of the monomer M and the second part of the monomer M in terms of terminal olefin is 50 to 150mol, more preferably 75 to 100mol, relative to 100mol of the maleic anhydride.

In the step (1), the monomer M may be fed in one step (i.e., the amount of the second portion of the monomer M may be zero), or may be fed in two portions (i.e., the first portion of the monomer M and the second portion of the monomer M). According to a more preferred embodiment of the invention, the molar ratio between the second portion of monomers M and the first portion of monomers M is (0-100): 100 (e.g.0, 1:100, 5:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value between the above values).

In the preparation method of the guanidine salt flame-retardant antibacterial microsphere, the amount of the organic solvent can be selected conventionally as long as a medium is provided for the reaction in the step (1), and preferably, the amount of the organic solvent can be 50-150L relative to 100mol of maleic anhydride.

In step (1), the organic solvent may be any solvent commonly used in solution polymerization, for example, the organic solvent includes organic acid alkyl ester, that is, the organic solvent may be selected from organic acid alkyl ester, or a mixture of organic acid alkyl ester and alkane, or a mixture of organic acid alkyl ester and aromatic hydrocarbon; wherein the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, methyl propyl formate, methyl butyl formate, methyl isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate; such alkanes include, but are not limited to: n-hexane and/or n-heptane. The aromatic hydrocarbons include, but are not limited to: at least one of benzene, toluene and xylene.

In the preparation method of the flame-retardant antibacterial agent, the amount of the initiator is not particularly required, and preferably, the total amount of the first part of initiator and the second part of initiator can be 0.05-10 mol, preferably 0.5-5 mol, and more preferably 0.8-1.5 mol, relative to 100mol of maleic anhydride. The amount of the crosslinking agent is not particularly limited, and preferably, the amount of the crosslinking agent may be 1 to 40mol, preferably 6 to 20mol, relative to 100mol of maleic anhydride.

In the step (1), the initiator may be fed in one step (i.e. the amount of the second part of initiator may be zero), or may be fed in two parts (i.e. the first part of initiator and the second part of initiator). According to a more preferred embodiment of the present invention, the molar ratio between the second portion of initiator and the first portion of initiator may be (0-100): 100 (e.g. 0, 1:100, 5:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value between the above values).

The initiator may be a reagent commonly used in the art for initiating polymerization of maleic anhydride and olefin, and may be a thermal decomposition type initiator. Preferably, the initiator may be at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.

In the step (1), the maleic anhydride is contacted with the monomer M to react, that is, the maleic anhydride and the monomer M are not completely reacted, and only part of the maleic anhydride and the monomer M are subjected to polymerization reaction in the presence of the initiator. The conditions for the contact reaction of maleic anhydride and the monomer M may be conventional conditions as long as the maleic anhydride and the monomer M are controlled to be polymerized only partially, and preferably, the conditions for the contact reaction of maleic anhydride and the monomer M include: an inert atmosphere at a temperature of 50 to 90 ℃ (preferably 60 to 70 ℃), a pressure (gauge pressure or relative pressure) of 0.3 to 1MPa (preferably 0.4 to 0.5MPa), and a time of 0.5 to 4 hours (preferably 0.5 to 2 hours).

In the step (1), after the maleic anhydride is contacted with the monomer M for partial reaction, a solution containing a cross-linking agent is introduced for continuous reaction, so that a shell cross-linked structure is particularly favorably formed. The conditions for continuing the reaction may be conventional conditions as long as each substrate is allowed to participate in the reaction as much as possible, and preferably, the conditions for continuing the reaction include: the temperature is 50-90 ℃, the pressure is 0.3-1 MPa, and the time is 2-15 h. The temperature and pressure for continuing the reaction may be the same as or different from those for carrying out the reaction by contacting maleic anhydride with the monomer M as described above. According to a more preferred embodiment of the invention, the introduction of the solution containing the crosslinking agent continues the reaction in such a way that: and (3) dropwise adding the solution containing the cross-linking agent into the product obtained in the step (1) within 1-3 h at 50-90 ℃ (preferably 60-70 ℃), and continuing to perform heat preservation reaction for 1-4 h.

In the method for preparing the flame-retardant antibacterial agent, the type and content of the solvent in the solution containing the crosslinking agent are not particularly required, as long as the solute in the solution is sufficiently dissolved, and generally, the type of the solvent in the solution containing the crosslinking agent can be selected as the same as that of the organic solvent (i.e., the organic acid alkyl ester is included as described above), and the content of the crosslinking agent in the solution containing the crosslinking agent can be 0.2 to 3 mol/L.

In the step (2), the step (c),

adding the guanidine salt or the guanidine salt water solution into the product obtained in the step (1), and quickly stirring for reaction; the amount of the guanidine salt is selected conventionally, and preferably, the amount of the guanidine salt is 5g to 5000g, preferably 20g to 3000g, and more preferably 100g to 2000g, relative to 1000g of maleic anhydride; the amount of the guanidine salt aqueous solution is 500 to 10000g, preferably 1000 to 8000g, and more preferably 1000 to 6000g, per 1000g of maleic anhydride. The concentration of the guanidine salt aqueous solution may be 0.5 to 50 wt%, preferably 1 to 30 wt%, more preferably 1 to 20 wt%.

In the step (2),

the grafting reaction may be carried out under conventional conditions, for example, the conditions of the grafting reaction may include: the temperature is 0-100 ℃, preferably 2.5-90 ℃, more preferably 5-80 ℃, and further preferably 30-80 ℃; the reaction time is 0.5-10 h, preferably 0.5-8 h, and more preferably 0.5-6 h; the stirring speed is 50 to 1000rpm, preferably 50 to 500rpm, and more preferably 100 to 500 rpm.

In the step (2), the product (suspension) obtained in the step (1) may be subjected to a post-treatment (separation, washing and drying) and then to a grafting reaction. And directly adding the dried product into a guanidine salt water solution for reaction. The washing may employ a conventional washing solvent, for example, at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether. The concentration of the guanidine salt aqueous solution may be 0.5 to 50 wt%, preferably 1 to 30 wt%.

And (3) further separating the final product obtained in the step (2) to obtain a guanidine salt flame-retardant antibacterial microsphere product, for example, separating according to the following method: centrifuging, washing with water, washing with an organic solvent (the washing solvent as described above, i.e., at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether can be used), centrifuging, and drying (e.g., vacuum drying).

The inventor of the present invention finds in research that the guanidine salt flame-retardant antibacterial microsphere product of the present invention can be effectively prepared by directly performing a graft reaction on the suspension obtained in step (1) and a guanidine salt aqueous solution without performing an organic solvent removal step. Therefore, according to a preferred embodiment of the present invention, in the step (2) of the present invention, the product obtained in the step (1) can be directly reacted with the guanidine salt polymer aqueous solution (one-pot method), so that a mixed system containing guanidine salt flame-retardant antibacterial microspheres is obtained, and the mixed system can be further separated to obtain the guanidine salt flame-retardant antibacterial microspheres product, for example, the separation is performed according to the following manner: standing for layering, using the organic phase for recycling, and performing centrifugal separation, water washing-centrifugal separation and drying (such as vacuum drying) on the heavy phase to obtain the guanidine salt flame-retardant antibacterial microspheres. The optimized method adopts a one-pot process, and the product post-treatment only needs one-time liquid-liquid separation, solid-liquid separation, washing and drying, so that the time consumption of a single batch is effectively shortened, the process flow is simplified, unit equipment is reduced, and the energy consumption is effectively reduced; the process only needs one organic solvent as a reaction medium, the solvent can be recycled only through layering and drying operations, a special water distribution device is not needed, layering can be achieved in the reactor, the solvent can be recycled without distillation and purification, energy is saved, consumption is reduced, and pollution of the organic solvent to the environment can be effectively reduced.

The invention also aims to provide the application of the flame-retardant antibacterial agent in flame-retardant antibacterial materials.

It is a fourth object of the present invention to provide a flame-retardant antibacterial thermoplastic resin composition which may comprise a flame-retardant antibacterial agent and a thermoplastic resin. Preferably, the following components may be included in parts by weight:

100 parts of thermoplastic resin, namely 100 parts of thermoplastic resin,

0-2.0 parts of an aluminum hypophosphite flame retardant, preferably 0.1-1.2 parts, and more preferably 0-0.6 part;

0-2.0 parts of melamine hydrobromide, preferably 0.1-1.2 parts, more preferably 0-0.8 parts;

0-1.0 part of flame retardant synergist, preferably 0.05-1 part, more preferably 0.05-0.6 part;

0.05-4.0 parts of flame-retardant antibacterial agent, preferably 0.1-2.8 parts, and more preferably 0.5-2 parts;

0 to 5.0 parts of mildew preventive, preferably 0.05 to 4.0 parts, and more preferably 0.1 to 3.6 parts.

In specific use, other functional additives can be added, the thermoplastic resin is 100 parts by weight, the other functional additives can be used in an amount of 0.1-100 parts by weight, and the specific amount can be adjusted according to needs. The other functional auxiliary agents can comprise at least one of an antioxidant, a light stabilizer, a toughening agent, a compatilizer, a pigment, a dispersing agent and the like.

Wherein the content of the first and second substances,

the thermoplastic resin may be selected from at least one of polyolefin resin (such as at least one of polypropylene, polyethylene resin and copolymers thereof), polystyrene, polyvinyl chloride, polyacrylonitrile/butadiene/styrene copolymer, polyacrylonitrile/styrene copolymer, polyoxymethylene, nylon, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenylene oxide, polyphenylene sulfide, and/or alloys of the thermoplastic resins.

The aluminum phosphinate flame retardant can be inorganic aluminum hypophosphite and/or alkyl aluminum phosphinate; the aluminum alkyl phosphinate can be selected from at least one of aluminum diethyl phosphinate, aluminum dipropyl phosphinate, aluminum phenyl phosphinate and the like; the aluminum phosphinate flame retardant is preferably inorganic aluminum hypophosphite and/or aluminum diethylphosphinate.

The flame retardant synergist can be at least one of 2, 3-dimethyl-2, 3-diphenyl butane (DMDPB, called as paraquat for short) and cumin polymer (poly paraquat).

The mildew inhibitor can be at least one of pyridylthione, isothiazolinone, 10 ' -oxodiphenol Oxazine (OBPA), 3-iodine-2-propynyl butyl carbamate (IPBC), 2,4,4' -trichloro-2 ' -hydroxydiphenyl ether (triclosan), 2- (thiazole-4-yl) benzimidazole (thiabendazole) and the like with good mildew-proof effect;

wherein the content of the first and second substances,

the pyrithione may be at least one selected from zinc pyrithione, copper pyrithione, dipyrithione and the like;

the isothiazolinone may be at least one selected from 2-methyl-1-isothiazolin-3-one (MIT), 5-chloro-2-methyl-1-isothiazolin-3-one (CMIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-n-octyl-3-isothiazolone (DCOIT), 1, 2-benzisothiazolin-3-one (BIT), 4-methyl-1, 2-benzisothiazolin-3-one (MBIT), 4-n-butyl-1, 2-benzisothiazolin-3-one (BBIT), etc.

The fifth object of the present invention is to provide a method for preparing the flame-retardant antibacterial thermoplastic resin composition, comprising the step of melt-blending the components including the thermoplastic resin and the antibacterial flame retardant.

The method specifically comprises the following steps:

a. uniformly mixing components including thermoplastic resin, an aluminum phosphate flame retardant, melamine hydrobromide, the antibacterial flame retardant and a mildew preventive; high speed mixers may be used;

b. and (b) extruding and granulating the premix mixed in the step (a), and drying to obtain the flame-retardant antibacterial thermoplastic resin composition. Specifically, an apparatus commonly used in the art, such as a twin-screw extrusion granulator, etc., can be used. A large number of experiments show that the guanidine salt flame-retardant antibacterial microspheres have good fluidity and low moisture absorption, and in the preparation process of the flame-retardant antibacterial thermoplastic resin composition, the guanidine salt does not stick to the wall, is easy to discharge, is simple to produce and operate, and does not need excessive production condition control. The prepared flame-retardant antibacterial thermoplastic resin composition has good flame-retardant, antibacterial and mildew-proof effects and improved water resistance.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention provides a flame-retardant antibacterial polymer microsphere and a preparation method thereof, and prepares a single-component guanidine salt microsphere with flame-retardant and antibacterial functions through structural design and formula regulation. Compared with the existing method of respectively adding the flame retardant and the antibacterial agent, the guanidine salt microspheres are easy to disperse in the thermoplastic resin base material, and the flame retardant efficiency and the antibacterial efficiency are effectively improved.

(2) The invention provides a low-additive-amount flame-retardant antibacterial thermoplastic resin composition and a preparation method thereof. The thermoplastic resin composition with both flame retardance and antibacterial property is prepared by regulating the formula and introducing high-efficiency multifunctional single-component flame-retardant antibacterial microspheres. Due to the improvement of flame retardance and antibacterial efficiency of the auxiliary agent, the reduction of the addition amount of the auxiliary agent and the improvement of the dispersion property, the prepared thermoplastic resin composition has excellent comprehensive performance.

Detailed Description

The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.

Source of raw materials

Polyethylene (PE): trade name 7042, maocai petrochemical

Polypropylene (PP), Cangzhou refined GD-H-230

Nylon 6: trade mark B3S, Basff

PC: polycarbonate, trade name 3103, Bayer

ABS: polyacrylonitrile/butadiene/styrene copolymer, designation 3504, Shanghai Gaoqian

Polyhexamethylene guanidine phosphate and Foshan blue peak assistant

Guanidine dihydrogen phosphate, Baishun (Beijing) chemical technology Co., Ltd

Guanidine hydrobromide, Shanghai coconut Biotech Ltd

Aminoguanidine nitrate, chemistry of Guangdong Wengjiang

Chemical industry of paraquat Guangzhou Xijia

Melamine hydrobromide, Guangzhou Xijia chemical industry

Chemical industry of hypophosphorous acid phosphate, Guangzhou Xijia

Zinc pyrithione, copper pyrithione: peak Fine chemical Co Ltd

Compound antioxidant: mixing antioxidant 1010 (basf), antioxidant 168 (basf), and calcium stearate (Shandong Haonia) at a mass ratio of 2/2/1.

The performance test method of the flame-retardant antibacterial resin composition is carried out according to the following standards:

tensile strength: GB/T1040-2006

Flexural modulus: GB/T9341-

And (3) antibacterial testing: GB/T31402-

Vertical combustion test standard no: GN/T2408-

Limiting oxygen index test standard number: GB/T2406.1-2008

Glow wire flammability index test standard no: GB/T5961.11-2006

The method for testing the crosslinking degree of the flame-retardant antibacterial polymer comprises the following steps: the crosslinking degree of the guanidine salt antibacterial microspheres is represented by gel content and is measured by a solvent extraction method. The specific method comprises the following steps: weighing W of a sample to be measured₁Then placing the sample to be tested in acetone with the weight 5 times of that of the sample, extracting the sample at 50 ℃ for 30min, and then measuring, drying and weighing W after the extraction is finished₂A degree of crosslinking of W₂/W₁X 100%. The content of soluble substances is (1-W)₂/W₁)×100％。

1. Preparation of guanidine salt flame-retardant antibacterial microspheres

Example 1:

(1) the composition of the mixed butylene gas is as follows: trans-2-butene, 40.83 wt%; cis-2-butene, 18.18 wt%; n-butane, 24.29 wt.%; n-butenes, 9.52 wt%; isobutylene, 2.78 wt%; others, 4.4 wt%. Dissolving 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed butylene (the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:1), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;

(2) and dissolving 25g of divinylbenzene in 200mL of isoprene acetate to obtain a solution II, adding the solution II into the reaction system by a plunger pump, dropwise adding for 2 hours, and after dropwise adding, keeping the temperature of the reaction system for reaction for 3 hours.

(3) After the reaction, the pressure was released, and 200g (15 wt%) of each of the guanidine dihydrogen phosphate and the polyhexamethylene biguanide hydrochloride aqueous solution was added and the reaction was carried out at 80 ℃ for 3 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the flame-retardant antibacterial agent, namely the polymer microsphere with the guanidinium grafted on the surface 1 #. The average particle size of the obtained polymer microspheres is 1280 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 5.5%.

Example 2:

the flame-retardant antibacterial agent is prepared according to the method of example 1, except that the system reacted in the step (2) is centrifuged and separated for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain the crosslinked mixed butylene/maleic anhydride polymer microspheres, and the crosslinked mixed butylene/maleic anhydride polymer microspheres are washed and purified by normal hexane and dried in vacuum. Then, the dried microspheres of the crosslinked mixed butene/maleic anhydride polymer were added to 400g of a mixed aqueous solution of guanidine dihydrogen phosphate (20 wt%), polyhexamethylene biguanide hydrochloride (20 wt%), and reacted at 80 ℃ for 3 hours. And centrifuging the reacted system for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging the solid for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the flame-retardant antibacterial agent, namely the polymer microsphere with the guanidinium grafted on the surface No. 2. The average particle size of the obtained polymer microspheres was 1310 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 5.6%.

Example 3:

(1) dissolving 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed butene (the composition is the same as that in example 1, the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:1), and reacting for 2 hours at 70 ℃ and 0.4MPa in a nitrogen atmosphere;

(2) and dissolving 15g of divinylbenzene in 200mL of isoprene acetate to obtain a solution II, adding the solution II into the reaction system by a plunger pump, dropwise adding for 2 hours, and after dropwise adding, keeping the temperature of the reaction system for reaction for 3 hours.

(3) After the reaction, the pressure was released, and 200g (20 wt%) of guanidine hydrobromide and 200g (20 wt%) of polyhexamethylene guanidine phosphate aqueous solution were added, respectively, and the reaction was carried out at 60 ℃ for 7 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the flame-retardant antibacterial agent, namely the polymer microsphere 3# with the guanidinium grafted on the surface. The average particle size of the obtained polymer microspheres is 1210 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 6.5%.

Example 4:

(1) dissolving 100g of maleic anhydride and 1.5g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed butylene (the composition is the same as that of example 1, the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:0.75), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;

(2) 0.5g of azodiisobutyronitrile and 18g of divinylbenzene are dissolved in 200mL of isoamyl acetate to form a second solution, the second solution is added into the reaction system by a plunger pump, the dropwise addition is carried out for 2 hours, and after the dropwise addition is finished, the reaction system is kept for reaction for 3 hours.

(3) After the reaction, the pressure was released, and 200g (20 wt%) of guanidine dihydrogen phosphate, 200g (20 wt%) of guanidine hydrobromide, and 200g (20 wt%) of an aqueous solution of polyhexamethylene guanidine phosphate were added, and the reaction was carried out at 60 ℃ for 10 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the flame-retardant antibacterial agent, namely the polymer microsphere 4# with the guanidinium grafted on the surface. The average particle size of the obtained polymer microspheres was 1510 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 5.8%.

Example 5:

(1) the mixed carbon five gas comprises the following components: dienes (isoprene, cyclopentadiene, 1, 4-pentadiene, piperylene), 47.83 wt%; monoolefin (1-pentene, 2-pentene, cyclopentene, 2-methyl-1-butene, 2-methyl-2-butene), 13.18% by weight; alkanes (n-pentane, isopentane, cyclopentane, 2-methylbutane), 21.29 wt%; alkyne (butyne-2, 3-penten-1-yne), 0.92 wt%; others, 16.78 wt%. Dissolving 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed carbon five (the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:0.5), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;

(2) and (3) dissolving metered mixed carbon five (the molar ratio of maleic anhydride to the effective component (terminal olefin) in the part of mixed olefin is 1:0.5) and 15g of divinylbenzene in 200mL of isoprene acetate to obtain a solution II, adding the solution II into the reaction system by a plunger pump, dropwise adding for 2 hours, and after dropwise adding is finished, keeping the temperature of the reaction system for reaction for 3 hours.

(3) And (2) after reaction, pressure relief is carried out, the system is static and layered, the heavy phase is centrifugally separated for 20 minutes by a centrifuge under the condition of 5000rad/min, 400mL of water is added into the solid for stirring and washing, the solid is centrifugally separated for 20 minutes by the centrifuge under the condition of 5000rad/min, and the solid is dried in vacuum to obtain the crosslinked mixed pentene/maleic anhydride polymer microspheres.

(4) 100g of crosslinked mixed pentene/maleic anhydride polymer microspheres were added to 400g of a mixed solution of aminoguanidine nitrate (15 wt%) and polyhexamethylene biguanide phosphate (15 wt%), and reacted at 50 ℃ for 6 hours. And centrifuging the reacted system for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging the solid for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the flame-retardant antibacterial agent, namely the polymer microsphere 5# with the guanidinium polymer grafted on the surface. The average particle size of the obtained polymeric microspheres was 1458 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 5.6%.

Example 6:

the flame-retardant antibacterial agent was prepared according to the method of example 5, except that the amount of divinylbenzene used in the step (2) was changed to 10g, to finally obtain polymer microspheres # 6. The average particle size of the obtained polymer microspheres was 1200 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 7.0%.

Example 7:

the flame-retardant antibacterial agent was prepared according to the method of example 1, except that divinylbenzene in the step (1) was changed to 36.0g of pentaerythritol tetraacrylate, to finally obtain polymer microspheres # 7. The average particle size of the obtained polymer microspheres was 1320 nm. The weight percentage of the obtained polymer microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min was 5.2%.

2. Preparation of flame-retardant antibacterial thermoplastic resin plastic

The formulations of the thermoplastic resin compositions used in the examples are shown in Table 1 (the amounts in Table 4 are in parts by weight).

Example 8:

100 parts by weight of polypropylene, 1.0 part by weight of polymer microsphere No. 1, 0.2 part by weight of aluminum hypophosphite, 0.35 part by weight of MHB, 0.1 part by weight of flame retardant synergist DMDPB, 0.2 part by weight of zinc pyrithione and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the extruded granules are extruded and granulated, dried for 3 hours in a constant temperature oven at 90 ℃, then injected into standard sample strips with specified dimensions at the injection temperature of 200-220 ℃ to carry out flame retardant and antibacterial tests.

Comparative example 1:

100 parts by weight of polypropylene and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, then injection molding is carried out at the injection molding temperature of 200-220 ℃ to form standard sample strips with specified dimensions, and flame retardance and antibacterial test are carried out.

Comparative example 2:

100 parts by weight of polypropylene, 1.0 part by weight of a zeolite silver-loaded antibacterial agent, 0.2 part by weight of aluminum hypophosphite, 0.35 part by weight of MHB, 0.1 part by weight of a flame-retardant synergist DMDPB, 0.2 part by weight of zinc pyrithione and 0.25 part by weight of a composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the extruded granules are extruded and granulated, dried for 3 hours in a constant-temperature oven at 90 ℃, and then injected into standard sample strips with specified dimensions at the injection temperature of 200-220 ℃ to carry out flame-retardant and antibacterial tests.

Example 9:

100 parts by weight of polypropylene, 1.0 part by weight of polymer microsphere No. 2, 0.2 part by weight of aluminum hypophosphite, 0.35 part by weight of MHB, 0.1 part by weight of flame retardant synergist DMDPB, 0.2 part by weight of zinc pyrithione and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the extruded granules are extruded and granulated, dried for 3 hours in a constant temperature oven at 90 ℃, then injected into standard sample strips with specified dimensions at the injection temperature of 200-220 ℃ to carry out flame retardant and antibacterial tests.

Example 10:

100 parts by weight of polypropylene, 0.9 part by weight of polymer microsphere No. 3, 0.25 part by weight of aluminum hypophosphite, 0.2 part by weight of MHB, 0.1 part by weight of DMDPB, 0.2 part by weight of zinc pyrithione and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m to extrude and granulate, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, and then are injected into standard sample strips with specified sizes at the injection temperature of 200-220 ℃ to carry out an antibacterial test.

Example 11:

100 parts of polypropylene, 1.6 parts of polymer microsphere No. 4, 0.1 part of DMDPB, 0.2 part of zinc pyrithione and 0.25 part of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m to extrude and granulate, the extruded granules are dried in a constant-temperature oven of 90 ℃ for 3 hours, and then are injected into standard sample strips with specified dimensions at the injection molding temperature of 200-220 ℃ to carry out flame retardant and antibacterial tests.

Comparative example 3:

100 parts by weight of polypropylene, 1.6 parts by weight of a zeolite silver-loaded antibacterial agent, 0.1 part by weight of DMDPB, 0.2 part by weight of zinc pyrithione and 0.25 part by weight of a composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the extruded particles are extruded and granulated, the extruded particles are dried in a constant-temperature oven at 90 ℃ for 3 hours, then the particles are injected into standard sample strips with specified dimensions at the injection temperature of 200-220 ℃ to carry out flame retardant and antibacterial tests.

Example 12:

100 parts of polypropylene, 1.0 part of polymer microsphere No. 5, 0.25 part of aluminum hypophosphite, 0.3 part of MHB, 0.1 part of DMDPB, 0.2 part of zinc pyrithione and 0.25 part of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m to be extruded and granulated, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, and then are injected into standard sample strips with specified sizes at the injection temperature of 200-220 ℃ to carry out flame retardant and antibacterial tests.

Example 13:

100 parts of polypropylene, 1.0 part of polymer microsphere No. 6, 0.25 part of aluminum hypophosphite, 0.3 part of MHB, 0.1 part of DMDPB, 0.2 part of zinc pyrithione and 0.25 part of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m to be extruded and granulated, the extruded granules are dried in a constant-temperature oven at 90 ℃ for 3 hours, then injection molding is carried out at the injection molding temperature of 200-220 ℃ to form a standard sample strip, and the flame retardant and antibacterial tests are carried out.

Example 14:

100 parts of polypropylene, 1.2 parts of polymer microsphere 7#, 0.2 part of aluminum hypophosphite, 0.3 part of MHB, 0.1 part of DMDPB, 0.2 part of zinc pyrithione and 0.25 part of composite antioxidant, putting the mixture into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 190-220 ℃ and the rotating speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting into a standard sample strip at the injection temperature of 200-220 ℃, and carrying out flame retardant and antibacterial tests.

The formulation of the PP composition used in the comparative example is shown in Table 2 (the amounts used in Table 2 are parts by weight).

The properties of the compositions prepared in the examples and comparative examples are shown in Table 3.

Example 15:

100 parts by weight of polyethylene, 1#2 parts by weight of polymer microspheres, 0.2 part by weight of zinc pyrithione and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-210 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, and then the mixture is injected into a sample at the injection temperature of 190-200 ℃ to carry out flame retardant and antibacterial tests.

Comparative example 4:

putting 100 parts by weight of polyethylene and 0.25 part by weight of composite antioxidant into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 190-210 ℃ and the rotating speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting the granules into a sample at the injection temperature of 190-200 ℃, and carrying out flame retardance and antibacterial test.

Example 16:

putting nylon 6100 weight parts, polymer microsphere 2#2.5 weight parts, zinc pyrithione 0.3 weight parts and composite antioxidant 0.3 weight parts into a low-speed mixer for fully stirring, then melting and blending the mixed materials through a double-screw extruder, extruding and granulating at the temperature of 220-240 ℃ and the rotating speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting into a sample at the injection molding temperature of 230-240 ℃ for flame retardance and antibacterial test.

Comparative example 5:

putting nylon 6100 weight parts and composite antioxidant 0.3 weight parts into a low-speed mixer to be fully and uniformly stirred, then melting and blending the mixed materials through a double-screw extruder, wherein the temperature of the extruder is 220-240 ℃, the rotating speed is 350r.p.m, extruding and granulating, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting into a sample at the injection molding temperature of 230-240 ℃, and carrying out flame retardant and antibacterial tests.

Example 17:

placing 80 parts by weight of PC, 20 parts by weight of ABS, 4# parts by weight of polymer microspheres, 0.3 part by weight of zinc pyrithione and 0.3 part by weight of composite antioxidant into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 230-260 ℃ and the rotating speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting the granules into a sample at the injection molding temperature of 230-240 ℃, and carrying out flame retardant and antibacterial tests.

Comparative example 6:

putting 80 parts by weight of PC, 20 parts by weight of ABS and 0.3 part by weight of composite antioxidant into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials through a double-screw extruder, extruding and granulating at the temperature of 230-260 ℃ and the rotating speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting the granules into a sample at the injection temperature of 230-240 ℃, and carrying out flame retardance and antibacterial test.

The formulations of the compositions used in examples 15, 16 and 17 and comparative examples 4,5 and 6 are shown in Table 4 (the amounts in Table 4 are parts by weight).

The properties of the compositions prepared in the examples and comparative examples are shown in Table 5.

Table 1: formulation of PP compositions used in the examples

Table 2: formulation of PP composition for comparative example

Table 3: comparison of the Properties of the flame retardant PP compositions obtained in examples and comparative examples

Table 4: formulation of the compositions of examples and comparative examples

Table 5: comparison of the Properties of compositions prepared in examples and comparative examples

As can be seen from the test results of comparative example 1 and Table 3, the PP resin itself is extremely flammable and has no antibacterial property. Examples 8 to 13 are low addition flame retardant antimicrobial thermoplastic resin compositions prepared by the method of the present invention. As can be seen from Table 3, the prepared composition not only has excellent antibacterial performance, but also can reach UL-94 test V-2 level with the addition of a low flame retardant, and shows good self-extinguishing performance, and the composition can pass the test of 750 ℃ of glow wire flammability index. Compared with pure PP, the flame retardant antibacterial composite material has the advantages that the flame retardant antibacterial property is realized, the tensile strength and the flexural modulus of the composite material are improved, and the technical difficulty that the comprehensive performance of the material is reduced due to poor dispersibility of the flame retardant and the antibacterial agent in a base material is overcome. In addition, by comparing example 8 with comparative example 2, example 11 with comparative example 3, it can be seen that the compositions prepared by the present invention have more excellent flame retardant and antibacterial properties under the condition of the same additive amount. Table 5 shows that the flame-retardant antibacterial microspheres improve the flame retardance and the antibacterial performance of the material in PE, PA6 and PC/ABS. In conclusion, the single-component flame-retardant antibacterial microsphere not only has higher flame-retardant antibacterial efficiency, but also has good dispersibility in the base material, and overcomes the technical difficulty that the comprehensive performance of the material is reduced due to the poor dispersibility of the flame retardant and the antibacterial agent in the base material.

Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.