CN117801491A - Polycarbonate composition and preparation method and application thereof - Google Patents

Polycarbonate composition and preparation method and application thereof Download PDF

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Publication number
CN117801491A
CN117801491A CN202311697701.0A CN202311697701A CN117801491A CN 117801491 A CN117801491 A CN 117801491A CN 202311697701 A CN202311697701 A CN 202311697701A CN 117801491 A CN117801491 A CN 117801491A
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10min
polycarbonate composition
polycarbonate
silicone
resin
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李万庆
张振威
陈晶斌
王文博
高卫强
颜晓捷
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses a polycarbonate composition, a preparation method and application thereof, wherein the composition comprises the following components in parts by weight: 65-92% of polycarbonate resin, 5-15% of siloxane copolycarbonate resin, 0.5-12% of fluoroalkyl quaternary phosphonium salt, 0-10% of scratch resistant agent and 0.5-10% of other auxiliary agents. The composition has the advantages of excellent scratch resistance, antibacterial property, good mechanical property and the like, and is suitable for medical equipment, consumer electronics, communication interphones, household appliances and the like.

Description

Polycarbonate composition and preparation method and application thereof
Technical Field
The invention relates to a composition for engineering plastics, in particular to a polycarbonate composition, a preparation method and application thereof.
Background
Polycarbonates (PC for short) are a class of polymers whose macromolecular chains consist of carbonate-type repeating structural units, and polycarbonates commercially available today are bisphenol A-type polycarbonates. As one of the most commonly used engineering plastics, PC has excellent impact resistance and transparency, and is excellent in heat resistance, flame resistance and insulation, and is widely used in the fields of electronic appliances, home appliances, automobiles, buildings, medical care, agriculture and the like.
It is well known that the surface of plastic materials is easily colonized by pathogenic microorganisms such as bacteria and fungi. When people contact contaminated surfaces, pathogens can be transferred to the human body, causing infections and health related problems, and thus, the need to impart antibacterial properties to PC is increasing.
Because the processing temperature of PC is higher (more than or equal to 260 ℃), most organic bactericides cannot be applied to PC materials because of low thermal stability. Accordingly, research on antibacterial PC has been mainly focused on the use of inorganic biocides such as silver or silver ion-containing nanoparticles, zinc oxide nanoparticles, and the like. However, when the following studies indicate that nano silver and zinc oxide nano particles are threatening to environmental microorganisms, nano silver has genotoxic effect on human cells, and zinc oxide nano particles also show toxic effect in mouse ovary germ cells; and the organic micromolecular antibacterial agent is easy to separate out, thereby influencing the service life and antibacterial effect of PC.
Quaternary Phosphonium Salts (QPS) are compounds with broad-spectrum antibacterial activity and excellent thermal stability, and some researches synthesize QPS with different alkyl chain lengths, such as the documents W.Zeng, et al, preparation and properties of antibacterial ABS plastics based on polymeric quaternary phosphonium salts antibacterial agents, polym.Adv.Technol.30 (2019) 2515-2522, and the quaternary phosphonium salts are added into ABS to obtain better antibacterial effect, but the thermal stability of the quaternary phosphonium salts still cannot meet the requirement of higher processing temperature of PC. Development of high Wen Ji salt-tolerant bactericides is an effective way to prepare antibacterial PC.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polycarbonate composition, and a preparation method and application thereof. The polycarbonate composition has excellent long-acting antibacterial property after higher processing temperature, and can be used for improving the scratch resistance of materials in a synergistic way unexpectedly, and ensuring that the mechanical properties of the materials are not reduced.
The method for improving the scratch resistance of the polycarbonate is to coat a high-hardness photo-curing coating after the polycarbonate is molded, but the method has complex process flow and low production efficiency, and the impact performance of the material can be influenced to a certain extent, so that the application of the polycarbonate is restricted. But a large amount of scratch-resistant auxiliary agents are added, and the problems of precipitation and loss of mechanical properties of products are solved. According to the invention, the polycarbonate composition with excellent scratch resistance and good mechanical property can be obtained simultaneously by only adding a small amount of scratch resistant agent and cooperating with the action of fluoroalkyl quaternary phosphonium salt.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a polycarbonate composition comprising the following components in weight ratio:
65 to 92% of a polycarbonate resin,
5-15% of a silicone copolycarbonate resin,
0.5-12% of fluoroalkyl quaternary phosphonium salt,
0-10% of scratch resistant agent,
0.5-10% of other auxiliary agents.
As a preferred embodiment of the present invention, the fluoroalkyl quaternary phosphonium salt has the following structural expression:
wherein R1 is selected from C 1-8 Alkyl, phenyl; m is an integer between 2 and 4, and n is an integer between 5 and 10.
The preparation method of the fluoroalkyl quaternary phosphonium salt does not play any limiting role in the invention, and the following is only a preferable example for providing a feasible process route:
the diphenyl alkyl phosphine and the fluorine-containing alkyl reactive monomer are mixed in a solvent according to the mol ratio of 1 (1-1.2), react for 24-36h at the temperature of 60-90 ℃, the reaction is ended, and the fluorine-containing alkyl quaternary phosphonium salt is obtained after purification.
The diphenyl alkyl phosphine is one or more of diphenyl methyl phosphine, diphenyl ethyl phosphine, diphenyl propyl phosphine, diphenyl tertiary butyl phosphine, diphenyl cyclohexyl phosphine and triphenyl phosphine.
The fluorine-containing alkyl reactive monomer is one or more of perfluorohexyl ethyl iodide, perfluoroheptyl ethyl iodide, perfluorooctyl ethyl iodide, perfluorononyl ethyl iodide, perfluorodecyl ethyl iodide, perfluorohexyl propyl iodide, perfluoroheptyl propyl iodide, perfluorooctyl propyl iodide, perfluorononyl propyl iodide and perfluorodecyl propyl iodide.
As a preferred embodiment of the invention, the polycarbonate is a mixture of linear PC and branched PC, wherein the branched PC mass content is 3-20%, preferably 5-20%, more preferably 8-20%;
preferably, the linear PC has a melt index of 3-65g/10min, preferably 5-50g/10min, more preferably 7-35g/10min at a test condition of 300℃and 1.2 kg;
preferably, the branched PC has a melt index of 1-10g/10min, preferably 1-8g/10min, more preferably 2-8g/10min at a test condition of 300℃and 1.2 kg.
As a preferred embodiment of the present invention, the melt index of the silicone copolycarbonate resin is 0.1 to 5g/10min, preferably 0.2 to 4g/10min, more preferably 0.2 to 3g/10min, at a test condition of 300℃and 1.2 kg.
Preferably, the mass content of the siloxane copolymerized units in the siloxane copolymerized polycarbonate resin is 15 to 40%, preferably 15 to 35%, more preferably 15 to 30%.
As a preferable scheme of the invention, the scraping resistant agent is one or two of Polytetrafluoroethylene (PTFE) and silicone powder. Wherein, the polytetrafluoroethylene preferably has a molecular weight of 10-50 ten thousand, the silicone powder is a mixed powder of polysiloxane with a molecular weight of 5-60 ten thousand and silicon dioxide, and the content of the polysiloxane is 40-75%.
As a preferable scheme of the invention, the other auxiliary agent is selected from one or more of lubricant, antioxidant and ultraviolet absorbent;
preferably, the lubricant is one or more selected from fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and derivatives thereof, amide waxes, saturated hydrocarbons, polyolefin waxes and derivatives thereof, silicone and silicone based, organofluorine based lubricants; more preferably pentaerythritol stearate, montan wax 6901, and the like;
preferably, the antioxidant is selected from one or more of hindered phenols, phosphites, thioesters, benzofurans, acrylated phenols and hydroxylamine antioxidants; preferably 1076, 168, PEP-36, etc.;
preferably, the ultraviolet absorber is selected from one or more of benzophenone, benzotriazole, triazine, benzoate, cyanoacrylate, phenylimidazole ultraviolet absorbers, preferably UV-234, UV-329, UV-360, UV-1577 and the like;
a method of preparing a polycarbonate composition as described hereinbefore, in particular: the raw materials of polycarbonate resin, siloxane copolycarbonate resin, fluoroalkyl quaternary phosphonium salt, scratch resistant agent and other auxiliary agents are mixed according to the weight ratio, and then are subjected to melt mixing, extrusion and pelleting under the condition that the processing temperature is 240-285 ℃ to obtain the polycarbonate composition.
The invention also provides an application of the polycarbonate composition in medical equipment and electronic appliances.
The beneficial effects of the invention are as follows:
the introduction of fluoroalkyl quaternary phosphonium salt into PC composition obviously enhances the long-acting antibacterial property of the composition, and the antibacterial agent has the advantages of good thermal stability and suitability for PC at higher processing temperature; in addition, the fluoroalkyl quaternary phosphonium salt and the scratch resistant agent are compounded in a synergistic way, so that the scratch resistant effect of the product is improved, the application field of the product is widened, the mechanical property of the PC composition is not adversely affected, the impact strength, the tensile strength, the elongation at break and the like are not reduced, and the PC composition has remarkable advantages compared with the prior art.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The main raw material information used in the following examples of the present invention is as follows, and other raw materials are purchased from commercial sources unless otherwise specified.
Polycarbonate resin (PC-1): clannate 2100, melt index (300 ℃,1.2 kg) =8.5 g/10min, wanhua chemical group Co., ltd
Polycarbonate resin (PC-2): clannate 2030, melt index (300 ℃,1.2 kg) =3.0 g/10min, wanhua chemical group Co., ltd
Polycarbonate resin (PC-3): CLARNATE 2600, melt index (300 ℃,1.2 kg) =60 g/10min, wanhua chemical group Co., ltd
Branched polycarbonate resin (PC-Y1): CLARNATE 2030-B, melt index (300 ℃,1.2 kg) =2.5 g/10min, wanhua chemical group Co., ltd
Branched polycarbonate resin (PC-Y2): CLARNATE 2020-B, melt index (300 ℃,1.2 kg) =2.0 g/10min, wanhua chemical Co., ltd
Branched polycarbonate resin (PC-Y3): CLARNATE 2070-B, melt index (300 ℃,1.2 kg) =7.0 g/10min, wanhua chemical group Co., ltd
Siloxane copolycarbonate resin (Si-PC-1): CLARNATE S2060, silicone copolymer unit content 20wt%, melt index (300 ℃,1.2 kg) =0.6 g/10min, wanhua chemical group Co., ltd
Siloxane copolycarbonate resin (Si-PC-2): CLARNATE S2040, silicone copolymer unit content 15wt%, melt index (300 ℃,1.2 kg) =2.5 g/10min, wanhua chemical group Co., ltd
Siloxane copolycarbonate resin (Si-PC-3): CLARNATE S2080 having a siloxane comonomer content of 30wt%, a melt index (300 ℃,1.2 kg) =0.2 g/10min, wanhua chemical group Co., ltd
Scratch resistance agent (PTFE-01): brand L-5F, molecular weight 30-50 ten thousand, japanese Dajin
Scratch resistance agent (Si-01): mark H-SI 6441P, germany win the creation of a win
Lubricant (WAX-1): pentaerythritol tetrastearate, hair based chemical (Zhangjigang Co., ltd.)
Antioxidant (AO-1): the weight ratio of the tri [2, 4-di-tert-butylphenyl ] phosphite to the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester is 4: 1.
The following examples of the present invention mainly employ the following performance test methods:
(1) Antibacterial test: injection molding into plastic samples of 50mm×50mm, and performing antibacterial test, antibacterial test standard: QB/T2591-2003 "antibacterial Plastic antibacterial Performance test method and antibacterial Effect", the test bacteria were Staphylococcus (ATCC 25923) and Escherichia coli (ATCC 25922) for antibacterial properties.
(2) Scratch resistance test: a200 mm by 150mm by 3mm template was injection molded, FLTM BN 108-02 test was performed, and the sample surface was visually evaluated for compliance grade, wherein grade 1 was no significant scratches on the surface, grade 5 was severe scratches on the surface, and the percent of scratches caused by external force was evaluated using an instrument.
(3) Impact properties: the notched Izod impact strength was measured according to GB/T1043.1-2008 in kJ/m using 4.0mm thick injection molded Izod test bars at 23℃using a notching machine to prepare 2.0mm deep notches 2 The results were recorded.
(4) Tensile properties: tensile strength was measured at 50mm/min according to GB/T1040.2 using 4.0mm thick injection molded tensile bars, the results were recorded in MPa and elongation at break was recorded in%.
[ preparation example 1 ]
The fluoroalkyl quaternary phosphonium salt QPS-01 was prepared as follows:
diphenylpropylphosphine and perfluorohexylethyl iodide were mixed in acetonitrile solvent at a molar ratio of 1:1 (diphenylpropylphosphine/acetonitrile=0.5 g/mL), added to a flask equipped with a magnetic stirrer, the reaction temperature was controlled at 65 ℃, after stirring for 24 hours, most of acetonitrile was removed by rotary evaporation, and the crude product was added to diethyl ether to obtain a precipitate, and the reaction product was washed three times with diethyl ether, and then dried under vacuum at 35 ℃ to obtain a powdery solid product QPS-01.
[ preparation example 2 ]
Fluoroalkyl quaternary phosphonium salt QPS-02 was prepared as follows:
diphenylpropylphosphine and perfluorodecylpropiodides were reacted in a molar ratio of 1:1.2 in acetonitrile solvent (diphenylpropylphosphine/acetonitrile=0.7 g/mL), adding to a flask equipped with a magnetic stirrer, controlling the reaction temperature at 60 ℃, stirring for 36 hours, removing most of acetonitrile by rotary evaporation, and adding the crude product to diethyl ether to obtain a precipitate, washing the reaction product three times with diethyl ether, and then drying in vacuo at 40 ℃ to obtain a powdery solid product QPS-02.
[ preparation example 3 ]
The fluoroalkyl quaternary phosphonium salt QPS-03 was prepared as follows:
diphenylpentylphosphine and perfluorodecylpropiodides were reacted in a molar ratio of 1:1.15 was dissolved in acetonitrile solvent (diphenylpentylphosphine/acetonitrile=0.75 g/mL), added to a flask equipped with a magnetic stirrer, the reaction temperature was controlled at 80 ℃, after stirring for 36 hours, most of acetonitrile was removed by rotary evaporation, and the crude product was added to diethyl ether to obtain a precipitate, the reaction product was washed three times with diethyl ether, and then dried under vacuum at 40 ℃ to obtain a powdery solid product QPS-03.
[ PREPARATION EXAMPLE 4 ]
Fluoroalkyl quaternary phosphonium salt QPS-04 was prepared as follows:
triphenylphosphine and perfluorohexyl ethyl iodide were combined in a molar ratio of 1:1.05 was dissolved in acetonitrile solvent (diphenylpentylphosphine/acetonitrile=0.8 g/mL), added to a flask equipped with a magnetic stirrer, the reaction temperature was controlled at 90 ℃, after stirring for 24 hours, most of acetonitrile was removed by rotary evaporation, and the crude product was added to diethyl ether to obtain a precipitate, the reaction product was washed three times with diethyl ether, and then dried under vacuum at 35 ℃ to obtain a powdery solid product QPS-04.
[ example 1 ]
66.3kg of PC-1, 8kg of PC-Y, 10kg of Si-PC-1, 5kg of QPS-01, 10kg of PTFE-01, 0.5kg of WAX-1 and 0.2kg of AO-1 are respectively weighed, mixed by a high-speed mixer, and melt-mixed by a Keplong STS-35 twin-screw extruder, wherein the processing temperature is 230 ℃ in one region, 260 ℃ in two regions, 285 ℃ in three regions, 280 ℃ in four regions, 275 ℃ in five regions to nine regions, 280 ℃ in a machine head, and the polycarbonate composition is obtained after extrusion and pelletization.
[ examples 2 to 6 ]
A polycarbonate composition was prepared under substantially the same conditions as in example 1, except that the raw material formulation shown in Table 1 was different.
Table 1, raw material formulation (kg) of examples 1-6
Comparative example 1
A polycarbonate composition was prepared under substantially the same conditions as in example 1, except that the starting material QPS-01 was replaced with (1-decyl) triphenylphosphine bromide.
Comparative example 2
A polycarbonate composition was prepared under substantially the same conditions as in example 1, except that the starting material QPS-01 was replaced with triphenylethyl phosphonium iodide.
[ comparative example 3 ]
A polycarbonate composition was prepared under substantially the same conditions as in example 1, except that the raw material QPS-01 was not added.
[ comparative example 4 ]
A polycarbonate composition was prepared under substantially the same conditions as in example 1, except that the starting materials QPS-01 and PTFE-01 were not added at the same time.
The polycarbonate compositions provided in the above examples and comparative examples were subjected to the performance test in Table 2, respectively, and the results were as follows:
TABLE 2 Performance test results
The experimental results in table 1 show that the product obtained by selecting the polycarbonate composition provided by the invention has excellent scratch resistance and antibacterial property, and the mechanical properties of the material are kept good, so that the product has obvious advantages compared with the scheme in the comparative example.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (8)

1. The polycarbonate composition is characterized by comprising the following components in parts by weight:
65 to 92% of a polycarbonate resin,
5-15% of a silicone copolycarbonate resin,
0.5-12% of fluoroalkyl quaternary phosphonium salt,
0-10% of scratch resistant agent,
0.5-10% of other auxiliary agents.
2. The polycarbonate composition of claim 1, wherein the fluoroalkyl quaternary phosphonium salt has the following structural expression:
wherein R1 is selected from C 1-8 Alkyl, phenyl; m is an integer between 2 and 4, and n is an integer between 5 and 10.
3. The polycarbonate composition according to claim 2, wherein the polycarbonate is a mixture of linear PC and branched PC, wherein the branched PC mass content is 3-20%, preferably 5-20%, more preferably 8-20%;
preferably, the linear PC has a melt index of 3-65g/10min, preferably 5-50g/10min, more preferably 7-35g/10min at a test condition of 300℃and 1.2 kg;
preferably, the branched PC has a melt index of 1-10g/10min, preferably 1-8g/10min, more preferably 2-8g/10min at a test condition of 300℃and 1.2 kg.
4. A polycarbonate composition according to any of claims 1-3, wherein the melt index of the silicone copolycarbonate resin is 0.1-5g/10min, preferably 0.2-4g/10min, more preferably 0.2-3g/10min at a test condition of 300 ℃ and 1.2 kg.
Preferably, the mass content of the siloxane copolymerized units in the siloxane copolymerized polycarbonate resin is 15 to 40%, preferably 15 to 35%, more preferably 15 to 30%.
5. The polycarbonate composition of claim 4, wherein the scratch resistant agent is one or both of polytetrafluoroethylene and silicone powder.
6. The polycarbonate composition according to claim 4, wherein the other auxiliary agent is one or more selected from the group consisting of a lubricant, an antioxidant, and an ultraviolet absorber;
preferably, the lubricant is one or more selected from fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and derivatives thereof, amide waxes, saturated hydrocarbons, polyolefin waxes and derivatives thereof, silicone and silicone based, organofluorine based lubricants;
preferably, the antioxidant is selected from one or more of hindered phenols, phosphites, thioesters, benzofurans, acrylated phenols and hydroxylamine antioxidants;
preferably, the ultraviolet absorber is selected from one or more of benzophenone, benzotriazole, triazine, benzoate, cyanoacrylate and phenylimidazole ultraviolet absorbers.
7. A method for producing the polycarbonate composition according to any one of claims 1 to 6, wherein the polycarbonate composition is obtained by mixing the raw material polycarbonate resin, the silicone copolycarbonate resin, the fluoroalkyl quaternary phosphonium salt, the scratch-resistant agent and the other auxiliary agent in a weight ratio, and then melt-kneading the mixture at a processing temperature of 240 to 285 ℃, extruding the mixture, and granulating the mixture.
8. Use of the polycarbonate composition of any of claims 1-6 in medical devices, electronic appliances.
CN202311697701.0A 2023-12-12 2023-12-12 Polycarbonate composition and preparation method and application thereof Pending CN117801491A (en)

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Application Number Priority Date Filing Date Title
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CN117801491A true CN117801491A (en) 2024-04-02

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