阅读说明：本技术 一种具有持久抗菌性的hips材料及其制备方法与应用 (HIPS material with lasting antibacterial property and preparation method and application thereof ) 是由 �谷洋 宾丽敏 于 2021-08-02 设计创作，主要内容包括：本发明公开了一种具有持久抗菌性的HIPS材料,其包括如下重量份的组分：HIPS 85～95份、抗菌剂1～10份、偶联剂0.5～2份、增容剂1～5份、润滑剂0.1～1份和抗氧化剂0.1～0.5份；所述抗菌剂为聚六亚甲基胍与苯乙烯的共聚物。本发明通过将PHMG与苯乙烯的共聚物加入HIPS中,有效解决了PHMG与HIPS的相容性问题,还通过添加特定种类的偶联剂和增容剂,进一步增加了PHMG与HIPS的相容性和相界面相互作用力,使PHMG牢固地锚定在HIPS基体中,不易析出,从而获得具有高安全性和高效持久抗菌性的HIPS材料,并保留了HIPS本身优良的加工性能、力学性能和高光泽特性。本发明的HIPS材料可作为冰箱内胆材料,用于制备具有抗菌功能的冰箱内胆。(The invention discloses a HIPS material with a lasting antibacterial property, which comprises the following components in parts by weight: 85-95 parts of HIPS, 1-10 parts of an antibacterial agent, 0.5-2 parts of a coupling agent, 1-5 parts of a compatibilizer, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant; the antibacterial agent is a copolymer of polyhexamethylene guanidine and styrene. The invention effectively solves the problem of compatibility of the PHMG and the HIPS by adding the copolymer of the PHMG and the styrene into the HIPS, and further increases the compatibility and the interaction force of the phase interface of the PHMG and the HIPS by adding the coupling agent and the compatibilizer of specific types, so that the PHMG is firmly anchored in the HIPS matrix and is not easy to precipitate, thereby obtaining the HIPS material with high safety, high efficiency and lasting antibacterial property, and keeping the excellent processing performance, mechanical property and high gloss characteristic of the HIPS. The HIPS material can be used as a refrigerator liner material and is used for preparing a refrigerator liner with an antibacterial function.)

1. The HIPS material with the durable antibacterial property is characterized by comprising the following components in parts by weight: 85-95 parts of HIPS, 1-10 parts of an antibacterial agent, 0.5-2 parts of a coupling agent, 1-5 parts of a compatibilizer, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant; the antibacterial agent is a copolymer of polyhexamethylene guanidine and styrene.

2. The HIPS material with a lasting antibacterial property as set forth in claim 1, wherein the PHMG has a molecular weight of 800 to 1500g/mol, and the content of the PHMG in the antibacterial agent is 1 to 10 wt%.

3. The HIPS material having a persistent antimicrobial property according to claim 1, wherein the method for preparing the antimicrobial agent comprises: uniformly mixing polyhexamethylene guanidine and dimethyl sulfoxide to form a solution with the concentration of 0.1-0.6 mol/L, then adding GMA with the same mole as the polyhexamethylene guanidine, reacting for 48-60 h at the temperature of 60-80 ℃, after the reaction is finished, adding the reaction solution into excessive acetone for complete precipitation, removing unreacted GMA and dimethyl sulfoxide, and drying to obtain the polyhexamethylene guanidine with double bonds at the chain end; adding polyhexamethylene guanidine with double bonds at the chain end and a styrene monomer into 0.3-2.0% of hexadecyl trimethyl ammonium chloride aqueous solution by mass percent, reacting for 20-40 min at 60-80 ℃, then adding 0.5-1.5% of potassium peroxodisulfate by mass percent, and continuing to react for 3-5 h to obtain the copolymer of the polyhexamethylene guanidine and the styrene.

4. The HIPS material having a persistent antimicrobial property according to claim 1, wherein the coupling agent is at least one of KH792, DL602, KH550, KH560 and KH 570.

5. The HIPS material having a persistent antibacterial property according to claim 1, wherein the compatibilizer is at least one of EPDM-g-MA and SBS.

6. The HIPS material having a persistent antibacterial property according to claim 1, wherein the lubricant is at least one of butyl stearate, liquid paraffin, zinc stearate, dipentaerythritol, silicone oil, polyethylene wax.

7. The HIPS material having a persistent antimicrobial property according to claim 1, wherein the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant PKY-168, antioxidant JC-242.

8. The method for preparing the HIPS material with the lasting antibacterial property according to any one of claims 1 to 7, comprising:

(1) uniformly mixing an antibacterial agent, a coupling agent and a compatibilizer to obtain a mixture A;

(2) uniformly mixing the mixture A, HIPS, the lubricant and the antioxidant to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material.

9. Use of the HIPS material with persistent antibacterial property as defined in any one of claims 1 to 7 in plastic products.

10. A plastic product, characterized in that, it is made of the HIPS material with durable antibacterial property as claimed in any one of claims 1 to 7.

Technical Field

The invention belongs to the technical field of modified plastics, and particularly relates to a HIPS material with a lasting antibacterial property, and a preparation method and application thereof.

Background

HIPS (high impact polystyrene) is a copolymer of styrene monomer and polybutadiene rubber by graft reaction, and is a white opaque thermoplastic resin. HIPS has good processing performance, the fluidity of HIPS is reduced compared with that of common polystyrene, but the HIPS is superior to acrylic plastics and most of thermoplastic engineering plastics, has the molding performance similar to that of ABS, and can be used for injection molding, extrusion, thermal molding, blow molding, foam molding and the like. In addition, HIPS modified by polybutadiene rubber graft improves the brittleness of PS, and has the advantages of high strength, high rigidity, high gloss and the like, so that HIPS products are more and more emphasized as engineering plastics which are widely applied to the fields of electronics, household appliances, food packaging, building materials, medical appliances and the like, particularly in the aspects of producing shells of household appliances, inner containers of refrigerators, fittings and the like.

Under the influence of new crown epidemic situation, a stock of antibacterial household wind is raised in the market. As one of the most common household appliances for storing food in daily life, the refrigerator has an increasingly demanded antibacterial function. Therefore, the development of the refrigerator with the antibacterial function, such as the refrigerator carrying the antibacterial function module, the refrigerator liner with the antibacterial function and the like, has a very good market prospect, and is a trend for the development of the refrigerator industry in the future.

The existing antibacterial agents are mainly divided into two categories of inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent has poor dispersibility in the HIPS material, is easy to agglomerate, and is easy to generate stress concentration points, so that the mechanical property of the material is reduced, and the application of the inorganic antibacterial agent is limited. In addition, the silver ion antibacterial agent with the widest application and the best antibacterial effect is easy to oxidize, so that the material is easy to yellow, the appearance of the product is affected, the content of silver ions is reduced along with the aggravation of oxidation, and the antibacterial effect of the silver ion antibacterial agent is greatly weakened. Secondly, the currently used organic antibacterial agents are generally small molecular substances, such as triclosan, zinc pyrithione, isothiazolinones and the like, and although the organic antibacterial agents are good in compatibility with HIPS and strong in antibacterial effect, the organic antibacterial agents are easy to precipitate, so that on one hand, the durability of the antibacterial effect of the materials is poor, and on the other hand, the precipitated organic substances can damage human health.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a HIPS material with a lasting antibacterial property, and a preparation method and application thereof.

In order to realize the purpose, the technical scheme adopted by the invention is as follows:

a HIPS material with durable antibacterial property comprises the following components in parts by weight: 85-95 parts of HIPS, 1-10 parts of an antibacterial agent, 0.5-2 parts of a coupling agent, 1-5 parts of a compatibilizer, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant; the antibacterial agent is a copolymer of polyhexamethylene guanidine and styrene.

Polyhexamethylene guanidine (PHMG) is a novel cationic polymer, has efficient broad-spectrum bactericidal property, low effective concentration, high thermal stability and decomposition temperature of more than 350 ℃, can completely kill bacteria such as staphylococcus aureus, escherichia coli and the like at the concentration of 0.02 percent, and is harmless to human bodies. However, since PHMG is a strongly polar polymer and HIPS is a non-polar polymer, the compatibility of PHMG with HIPS is less than ideal. Therefore, the invention effectively solves the problem of compatibility of the PHMG and the HIPS by copolymerizing the PHMG and the styrene monomer, so that the PHMG is not easy to precipitate in the HIPS material and has durable antibacterial property. Meanwhile, the invention further increases the compatibility and the phase interface interaction force of the PHMG and the HIPS by adding the coupling agent and the compatibilizer with the characteristic types, so that the PHMG is firmly anchored in the HIPS matrix.

Preferably, the molecular weight of the PHMG is 800-1500 g/mol.

Researches show that the PHMG with low molecular weight is favorable for realizing copolymerization with styrene monomer. If the molecular weight of the PHMG is too high, it tends to cause uneven copolymerization with the styrene monomer or to result in too low a PHMG content in the copolymer.

Preferably, the content of the PHMG in the antibacterial agent is 1 wt% to 10 wt%. When the content of the PHMG in the antibacterial agent is up to the content, the HIPS material prepared by the formula can achieve better antibacterial property.

Preferably, the method for preparing the antibacterial agent (PHMG-co-St) comprises the following steps:

mixing PHMG and dimethyl sulfoxide to form a uniformly dispersed solution with the concentration of 0.1-0.6 mol/L, then adding Glycidyl Methacrylate (GMA) which is equal to the PHMG in mole, reacting for 48-60 h at the temperature of 60-80 ℃, after the reaction is finished, adding the reaction solution into excessive acetone for complete precipitation, removing unreacted GMA and dimethyl sulfoxide, and drying to obtain the PHMG with a double bond at the chain end;

adding the prepared PHMG and styrene monomer into 0.3-2.0% hexadecyl trimethyl ammonium chloride aqueous solution by mass fraction, reacting for 20-40 min at 60-80 ℃, then adding 0.5-1.5% potassium peroxodisulfate by mass fraction, and continuing to react for 3-5 h to obtain PHMG-co-St.

Preferably, the HIPS is selected from one of the following commercial designations: qimei HIPS88sf, Yangba HIPS2720, Dada HIPS8265, and Shengxi HIPS 1173. The HIPS with the mark has a good use effect in the formula, and can exert good processing performance, mechanical property and high glossiness.

Preferably, the coupling agent is at least one of KH792, DL602, KH550, KH560, KH 570.

Preferably, the compatibilizer is at least one of EPDM-g-MA and SBS.

By adopting the coupling agent and the compatibilizer in the above types, the compatibility and the phase interface interaction force of the PHMG and the HIPS can be effectively increased, so that the PHMG is firmly anchored in the HIPS matrix.

Preferably, the lubricant is at least one of butyl stearate, liquid paraffin, zinc stearate, dipentaerythritol, silicone oil and polyethylene wax.

Preferably, the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant PKY-168 and antioxidant JC-242.

The invention also provides a preparation method of the HIPS material with the lasting antibacterial property, which comprises the following steps:

(1) uniformly mixing an antibacterial agent, a coupling agent and a compatibilizer to obtain a mixture A;

(2) uniformly mixing the mixture A, HIPS, the lubricant and the antioxidant to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material.

Preferably, the mixing condition of the step (2) is that the mixture is stirred and mixed for 10-20 min in a high-speed mixer at 75-90 ℃.

Preferably, in the step (3), the blending extrusion temperature of the twin-screw extruder is: the nozzle is 190-200 ℃, the first zone is 170-180 ℃, the second zone is 180-190 ℃, the third zone is 190-200 ℃, the fourth zone is 190-200 ℃, the fifth zone is 190-200 ℃, the sixth zone is 200-210 ℃, the seventh zone is 200-210 ℃, the eighth zone is 210-220 ℃, the ninth zone is 210-220 ℃, and the rotating speed of the screw is 400-500 r/min.

The invention also provides application of the HIPS material in plastic products, including but not limited to plastic products in the refrigerator, such as refrigerator liners.

The invention also provides a plastic product which is made of the HIPS material, and the plastic product comprises but is not limited to a refrigerator inner container.

Compared with the prior art, the invention has the beneficial effects that: the invention effectively solves the problem of compatibility of the PHMG and the HIPS by adding the copolymer of the PHMG and the styrene into the HIPS, and further increases the compatibility and the interaction force of the phase interface of the PHMG and the HIPS by adding the coupling agent and the compatibilizer of specific types, so that the PHMG is firmly anchored in the HIPS matrix and is not easy to precipitate, thereby obtaining the HIPS material with high safety, high efficiency and lasting antibacterial property, and keeping the excellent processing performance, mechanical property and high gloss characteristic of the HIPS. The HIPS material can be used as a refrigerator liner material and is used for preparing a refrigerator liner with an antibacterial function.

Detailed Description

The present invention will be described in detail with reference to specific embodiments in order to make the above objects, features and advantages more comprehensible. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. The methods employed in the examples of the present invention are all conventional in the art, and the equipment, reagents, and starting materials used therein are commercially available, unless otherwise specified. The HIPS used in the examples and comparative examples was Tadaka HIPS8265, and also Qimei HIPS88sf, Yangba HIPS2720, and Shengxi Australian HIPS 1173; EPDM-g-MA compatibilizer, CG700, morning gloss.

The antibacterial agent (PHMG-co-St) of the example was prepared by the following steps:

mixing PHMG (with the molecular weight of 1200g/mol and purchased from Taanglin chemical industry) with dimethyl sulfoxide to form a uniformly dispersed solution with the concentration of 0.3mol/L, then adding GMA with the same mol as PHMG, reacting for 55h at 70 ℃, after the reaction is finished, adding the reaction solution into excessive acetone for complete precipitation, removing unreacted GMA and dimethyl sulfoxide, and drying to obtain PHMG with a double bond at the chain end;

adding a certain amount of the prepared PHMG and styrene monomer into a proper amount of 1% hexadecyl trimethyl ammonium chloride aqueous solution by mass fraction, reacting for 30min at 70 ℃, then adding a proper amount of 1% potassium peroxodisulfate by mass fraction, and continuously reacting for 4h to obtain PHMG-co-St.

Example 1

The HIPS material with the durable antibacterial property comprises the following components in parts by weight: 90 parts of HIPS, 5 parts of antibacterial agent (the content of PHMG is 5 wt%), 1 part of KH792 coupling agent, 4 parts of EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 10100.5 parts of antioxidant.

The preparation method of the HIPS material comprises the following steps:

(1) adding the antibacterial agent, the coupling agent and the compatibilizer into a high-speed mixer, and stirring and mixing for 15min to obtain a mixture A;

(2) placing the mixture A, HIPS, lubricant (polyethylene wax) and antioxidant into a high-speed mixer, and stirring and mixing at 90 ℃ for 10min to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material. Wherein the blending extrusion temperature of the double-screw extruder is as follows: the nozzle is 200 ℃, the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 195 ℃, the fourth zone is 200 ℃, the fifth zone is 200 ℃, the sixth zone is 205 ℃, the seventh zone is 210 ℃, the eighth zone is 210 ℃, the ninth zone is 215 ℃ and the rotating speed of the screw is 450 r/min.

Example 2

The HIPS material with the durable antibacterial property comprises the following components in parts by weight: HIPS 85 parts, antibacterial agent (PHMG content 2 wt%) 8 parts, KH792 coupling agent 1 part, EPDM-g-MA compatibilizer 5 parts, dipentaerythritol 0.5 part and antioxidant 1680.5 part.

The preparation method of the HIPS material comprises the following steps:

(1) adding the antibacterial agent, the coupling agent and the compatibilizer into a high-speed mixer, and stirring and mixing for 10min to obtain a mixture A;

(2) placing the mixture A, HIPS, a lubricant (dipentaerythritol) and an antioxidant into a high-speed mixer, and stirring and mixing for 15min at 80 ℃ to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material. Wherein the blending extrusion temperature of the double-screw extruder is as follows: the nozzle is 190 ℃, the first zone is 175 ℃, the second zone is 190 ℃, the third zone is 195 ℃, the fourth zone is 200 ℃, the fifth zone is 200 ℃, the sixth zone is 205 ℃, the seventh zone is 210 ℃, the eighth zone is 220 ℃, the ninth zone is 220 ℃, and the screw rotation speed is 400 r/min.

Example 3

The HIPS material with the durable antibacterial property comprises the following components in parts by weight: HIPS 85 parts, antibacterial agent (PHMG content 1 wt%) 10 parts, KH792 coupling agent 2 parts, EPDM-g-MA compatibilizer 4 parts, polyethylene wax 0.5 parts and antioxidant 10100.5 parts.

The HIPS material was prepared in the same manner as in example 2.

Example 4

The HIPS material with the durable antibacterial property comprises the following components in parts by weight: 95 parts of HIPS, 2 parts of antibacterial agent (the content of PHMG is 10 wt%), 1 part of KH792 coupling agent, 2 parts of EPDM-g-MA compatibilizer, 0.5 part of silicone oil and 0.5 part of antioxidant. The antioxidant consists of an antioxidant 1010 and an antioxidant JC-242, and the mass ratio of the antioxidant 1010 to the antioxidant JC-242 is 1: 1.

The preparation method of the HIPS material comprises the following steps:

(1) adding the antibacterial agent, the coupling agent and the compatibilizer into a high-speed mixer, and stirring and mixing for 15min to obtain a mixture A;

(2) placing the mixture A, HIPS, lubricant (silicone oil) and antioxidant into a high-speed mixer, and stirring and mixing at 90 deg.C for 10min to obtain mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material. Wherein the blending extrusion temperature of the double-screw extruder is as follows: the nozzle temperature is 200 ℃, the first zone is 170 ℃, the second zone is 185 ℃, the third zone is 200 ℃, the fourth zone is 200 ℃, the fifth zone is 195 ℃, the sixth zone is 205 ℃, the seventh zone is 210 ℃, the eighth zone is 210 ℃, the ninth zone is 220 ℃, and the screw rotation speed is 450 r/min.

Example 5

The HIPS material with the durable antibacterial property comprises the following components in parts by weight: 95 parts of HIPS, 1 part of antibacterial agent (the content of PHMG is 10 wt%), 0.5 part of KH792 coupling agent, 1 part of EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 10100.5 parts of antioxidant.

The HIPS material was prepared in the same manner as in example 4.

Comparative example 1

The HIPS material comprises the following components in parts by weight: 95 parts of HIPS, 0.5 part of KH792 coupling agent, 1 part of EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 10100.5 parts of antioxidant.

The preparation of the HIPS material is described in example 4.

Comparative example 2

A HIPS material differing from example 5 only in the kind of coupling agent added, all other things being equal. Comparative example 2 the coupling agent added was SP-1800.

Comparative example 3

A HIPS material differing from example 5 only in the kind of compatibilizer added, all other things being equal. The compatibilizer added in comparative example 3 was K gum.

Comparative example 4

A HIPS material which differs from example 5 only in that: the antibacterial agent of example 5 was replaced by direct addition of an amount of PHMG (molecular weight 1200g/mol) equivalent to that of example 5.

And (3) performance testing:

the HIPS materials prepared in examples 1-5 and comparative examples 1-4 were subjected to performance tests, and the test results are shown in the following table:

note: tensile strength and elongation at break were tested according to ISO 527; notched izod impact strength testing is in accordance with ISO 1801A; according to GB/T21551.2, a test sample is placed in water at 50 ℃ for 48 hours and then a material is subjected to a persistent antibacterial test according to the test standard.

And (4) analyzing results: from the performance test data of the HIPS materials prepared in the examples 1-5 and the comparative examples 1-4, the PHMG-co-St has better compatibility with the HIPS matrix, and can realize the unification of the excellent mechanical property and high antibacterial property of the HIPS, while the HIPS is hardly provided with lasting antibacterial property and the HIPS is reduced in mechanical property because the HIPS is aggregated to a certain extent and is easy to precipitate by simply adding the PHMG. Meanwhile, as other kinds of coupling agents and compatibilizers are added in the comparative examples 2 and 3, the compatibility and the phase interface interaction force of the PHMG and the HIPS cannot be effectively enhanced, and the mechanical property and the antibacterial property of the HIPS are reduced.

In addition, the inventors also conducted experimental tests on the use effects of the coupling agents DL602, KH550, KH560 and KH570, and the compatibilizer SBS in the formulations of the present invention. The results show that: the use effects of the coupling agents DL602, KH550, KH560 and KH570 are similar to that of KH792, and the use effects of the compatibilizer SBS are similar to that of EPDM-g-MA, and are not described herein.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.