CN107573667B - High-temperature-resistant polycarbonate composition and preparation method thereof - Google Patents
High-temperature-resistant polycarbonate composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant polycarbonate composition, which comprises PC resin, PET resin, a compatilizer, a toughening agent, a phosphate flame retardant, an antioxidant, other auxiliaries and 1.0-60.0ppm of calcium element based on the total weight of the polycarbonate composition. According to the high-temperature-resistant polycarbonate composition, DBP containing trace TPP is used as a flame retardant, 1.0-60.0ppm of calcium element is added into the composition, the calcium element can be matched with the trace TPP remained in the DBP flame retardant, the reaction between PC resin and PET resin is inhibited to the greatest extent, meanwhile, the influence of the flame retardant on the toughness of the polycarbonate composition can be weakened to the greatest extent, the color stability of the composition is improved, the mechanical property and the long-term color stability of the polycarbonate composition are greatly optimized, and the high-temperature-resistant polycarbonate composition is particularly suitable for occasions with high molding temperature and high use environment requirements.
Description
Technical Field
The invention relates to a polycarbonate composition and a preparation method thereof, in particular to a high-temperature-resistant polycarbonate composition and a preparation method thereof, belonging to the technical field of composite polymers.
Background
polycarbonate resin (PC resin) is a colorless and transparent amorphous thermoplastic material, and is widely used in many fields such as packaging, daily necessities, electronic appliances, toys, instruments, transportation, and machine manufacturing because it is easily processed and suitable for various molding methods such as injection, extrusion molding, blow molding, and has good mechanical and optical properties, but pure PC resin has a large melt viscosity, poor solvent resistance, high notch sensitivity, and high cost.
Polyethylene terephthalate resin (PET resin) is a translucent crystalline thermoplastic polyester, and has the advantages of high heat resistance, high toughness, high fatigue resistance, self-lubrication, low friction coefficient, and the like, but PET has low notched impact strength, is easily corroded by halogenated hydrocarbons, has poor hydrolysis resistance, and has a large molding shrinkage. In the prior art, technicians blend PC resin and PET resin to obtain composite resin, and the composite resin has the rigidity and heat resistance of the PC resin and the solvent resistance of the PET resin.
However, since the PET resin is a crystalline polymer and the PC resin is an amorphous polymer, the alloy compatibility between the PC resin and the PET resin is very poor, and the mechanical properties of the composite material are greatly reduced by mixing the two. In addition, because the PC resin contains terminal hydroxyl, the PC resin and carboxyl, hydroxyl and the like which are remained in the PET resin are easy to generate two-phase reaction under the condition of high temperature and existence of titanium-based residual catalyst, the compatibility of the reaction can be improved, but the uncertainty is very large, the reaction can cause rapid deterioration of the performance of the composite material in the later use process, and the practicability of the application of the PC/PET alloy is greatly reduced. Although a small amount of triphenyl phosphate (TPP) contained in tetraphenyl (bisphenol-A) diphosphate (BDP) which is a commonly used flame retardant at present can effectively complex titanium catalysts, the reaction between PC resin and PET resin is still serious under many conditions, particularly under the condition of higher molding temperature, and the popularization and application of PC/PET alloy are influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-temperature-resistant polycarbonate composition and a preparation method thereof.
The technical scheme of the invention is as follows:
The invention discloses a high-temperature-resistant polycarbonate composition, which comprises the following components in parts by weight: 50-85 parts of PC resin, 5-20 parts of PET resin, 0.01-5.0 parts of compatilizer, 0.1-13.0 parts of flexibilizer, 8.0-20.0 parts of phosphate flame retardant, 0.01-2.0 parts of antioxidant, 0.01-8.0 parts of other auxiliary agents and 1.0-60.0ppm of calcium element based on the total weight of the polycarbonate composition.
The PC resin (polycarbonate resin) is a polymer or copolymer of a thermoplastic aromatic polycarbonate having a branched chain obtained by reacting an aromatic hydroxy compound with phosgene or a carbonic acid diester, or by reacting an aromatic hydroxy compound and a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and a known method such as a phosgene method (interfacial polymerization method), a melting method (transesterification method) or the like can be used. The molecular weight of the polycarbonate resin in the present invention is appropriately selected for improving the appearance and flowability of the molded article, and the viscosity average molecular weight [ Mv ] obtained by converting the solution viscosity is usually 10000 or more, preferably 12000 or more, and usually 40000 or less, preferably 30000 or less, and more preferably 25000 or less. By setting the viscosity average molecular weight within the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be ensured, and the polycarbonate resin composition is more suitable for use in a field where a high requirement for mechanical strength is imposed.
Wherein the PET resin is a virgin PET resin with the intrinsic viscosity of 0.5-0.9dl/g, or a regenerated PET resin prepared by separation, cleaning, crushing, cleaning again, drying and extrusion granulation, and the intrinsic viscosity of the regenerated PET resin is also 0.5-0.9 dl/g.
Wherein the compatilizer is at least one of methacrylate-acrylate copolymer, styrene-maleic anhydride random copolymer and styrene-acrylonitrile-glycidyl methacrylate, and preferably styrene-acrylonitrile-glycidyl methacrylate.
The toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer, acrylic toughening agent and organic silicon rubber graft toughening agent, and preferably is organic silicon rubber graft toughening agent. The organic silicon rubber graft toughening agent refers to a copolymer formed by organic siloxane, vinyl polymer rubber and vinyl monomer for grafting, wherein the volume average particle diameter of the rubber is 200-2000nm, preferably 220-1500nm, more preferably 280-1000nm, and even more preferably 290-600nm, and the resin composition with better impact resistance and small influence on the ignition temperature can be obtained by ensuring the volume average particle diameter of the rubber to be in the range of 290-600 nm.
The phosphate flame retardant is a flame retardant mainly comprising tetraphenyl (bisphenol-A) Diphosphate (DBP), and the DBP also comprises trace triphenyl phosphate (TPP), the DBP flame retardant conventionally used in the market is selected in the invention, trace TPP usually remains in the flame retardant, and specific trace amount of TPP remains in the production process of the DBP flame retardant, which is well known by the technicians in the field and is not described in detail in the application.
Wherein the calcium element can be obtained by directly adding calcium element or calcium-containing compound into the polycarbonate composition during the production process of the polycarbonate composition, and the calcium-containing compound is at least one of calcium sulfate, calcium chloride, calcium nitrate, calcium carbonate, calcium phosphate and calcium-containing complex. The amount of the calcium element and the calcium-containing compound added may be such that the content of the calcium element in the polycarbonate composition is 1.0 to 60.0ppm, preferably 6.0 to 20.0 ppm.
Wherein the antioxidant can be propionate antioxidant, such as octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; organic phosphite antioxidants, such as tris (nonylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenol or polyphenol antioxidants; antioxidants of the class of reaction products of the alkylation of polyphenols with dienes, such as tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane; butylated reaction products of p-cresol or dicyclopentadiene as antioxidants; alkylated hydroquinone as an antioxidant; hydroxylated thiodiphenyl ether as antioxidant; alkylidene bisphenols as antioxidants; a benzyl compound as an antioxidant; esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols as antioxidants; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols as antioxidants; esters of thioalkyl or thioaryl compounds as antioxidants, such as distearylthiopropionate, dilaurylthiopropionate, tricosylthiodipropionate, pentaerythrityl-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; an amide of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid as an antioxidant, or a combination comprising at least one of the foregoing antioxidants.
Other additives such as at least one of anti-dripping agents, plasticizers, fillers, and colorants may also be added as appropriate in the present application. The anti-dripping agent is preferably fluorinated polyolefin, and specifically may include vinylidene fluoride resin, tetrafluoroethylene/hexafluoropropylene copolymer resin, among which tetrafluoroethylene resin is preferred. The lubricant is glyceryl stearate; the filler comprises mineral fillers such as titanium dioxide, barium sulfate and the like; the colorant includes various pigments and dyes.
The invention also provides a preparation method of the high-temperature-resistant polycarbonate composition, which comprises the following steps: weighing the raw materials according to the formula dosage, putting the raw materials into a mixer, and blending uniformly to obtain a premix; then putting the premix into a double-screw extruder for melt mixing and extrusion granulation to obtain the high-temperature-resistant polycarbonate composition; wherein the ratio of the long diameter of the screw of the double-screw extruder is (40-45):1, the temperature of the screw cylinder is 240-260 ℃, and the rotating speed of the screw is 400-500 rpm.
The beneficial technical effects of the invention are as follows: according to the high-temperature-resistant polycarbonate composition, DBP containing trace TPP is used as a flame retardant, 1.0-60.0ppm of calcium element is added into the composition, the calcium element can be matched with the trace TPP remained in the DBP flame retardant, the reaction between PC resin and PET resin is inhibited to the greatest extent, meanwhile, the influence of the flame retardant on the toughness of the polycarbonate composition can be weakened to the greatest extent, the color stability of the composition is improved, the mechanical property and the long-term color stability of the polycarbonate composition are greatly optimized, and the high-temperature-resistant polycarbonate composition is particularly suitable for occasions with high molding temperature and high use environment requirements.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
The raw materials used in the following specific examples and comparative examples are as follows:
PC resin: the viscosity average molecular weight is 20000, the brand is S-3000F, and the manufacturer is Mitsubishi Japan.
PET resin: the intrinsic viscosity is 0.68dl/g, the trade mark is PET SB500, and the manufacturer is characterized by petrochemical industry.
A compatilizer: styrene-acrylonitrile-glycidyl methacrylate, under the designation SAG-002, was manufactured by Nissan Daisy.
A toughening agent: s-2001, manufactured by Mitsubishi yang, Japan.
Flame retardant: phireguard BDP, manufactured by Jiangsu Yake.
Antioxidant: chinox 1076; the manufacturer is Taiwan double bond chemical industry.
Lubricant: UNISTER-M9676, manufactured by Nissan oil Co.
Anti-dripping agent: the brand is A3800 and the manufacturer is Mitsubishi Yangyang.
Calcium-containing simple substance or calcium-containing compound: calcium phosphate and calcium carbonate, both commercially available.
Weighing the raw materials according to the formula dosage in the following tables 1 and 2, and putting the weighed raw materials into a mixer to blend uniformly to obtain a premix; then putting the premix into a double-screw extruder for melt mixing and extrusion granulation to obtain the polycarbonate composition; wherein the ratio of the long diameter of the screw of the double-screw extruder is 40:1, the temperature of the screw cylinder is 240-260 ℃, and the rotating speed of the screw is 400-500 rpm.
TABLE 1 EXAMPLES 1-8 the amounts of the respective components (unit: kg)
TABLE 2 comparative examples 1 to 4 amounts of the respective components (unit: kg)
the polycarbonate composition prepared by the method is subjected to calcium content measurement, notched izod impact strength measurement and color stability measurement, and the measurement method or the measurement standard is as follows:
(1) And (3) measuring the content of calcium element: 2g of particles of the polycarbonate composition are accurately weighed in an analytical balance, poured into a 100ml digestion bottle, then added with 5ml of 97 wt.% concentrated sulfuric acid, heated for 10min in an iron plate heating instrument with a preset temperature of 300 ℃, then added with 5ml of 68 wt.% nitric acid, kept heated for 20min, cooled to room temperature after the particles are completely decomposed, added with 20ml of hydrogen peroxide to neutralize the acidity until the pH value is 7, diluted with deionized water, and introduced into an ICP detection instrument through a sample inlet pipe to measure the concentration of calcium.
(2) Notched Izod impact strength determination: notched Izod impact strength was measured at 23 ℃ using a 3.2mm thick molded notched Izod impact bar, measured according to ASTM D256, and reported in J/m.
(3) Color stability measurement the polycarbonate composition of the present invention was injection-molded using an 80 ton injection molding machine manufactured by Nichisu resin industries, at a cylinder temperature of 300 ℃ for 0 and 20 minutes, to produce a sheet having a thickness of 2mm, a width of 40 mm and a length of 100 mm, wherein the mold temperature was set at 80 ℃ and the injection-molded sheet was subjected to a humidity adjustment of 50% at room temperature of 23 ℃ for 48 hours, and then the Color tones (L, a, b) of the molded sheet after the hot retention for 0 and 20 minutes were measured by a D 65 illuminant reflection method using a Color Eye 7000A manufactured by Iwako, and the Color difference Δ E was determined by the following equation, and it was found that the larger the Color stability of the molding was, the smaller the Δ E { (L-L ') 2 + (a-a ') 2 + (b ') 2 } 1/2.
The results of the above tests are shown in tables 3 and 4.
TABLE 3 results of measuring Properties of examples 1 to 8
TABLE 4 results of performance measurements of comparative examples 1-4
As can be seen from the above tables 3 and 4, the polycarbonate compositions obtained in examples 1 to 8 are inferior to those obtained in comparative examples 1 to 4 in both of high or low deterioration in notched impact resistance and color difference after heat retention, failing to satisfy some service conditions which require toughness and are severe in molding conditions. Different from comparative examples 1-4, the polycarbonate composition prepared in the examples of the present invention, after adding calcium element, was compounded with the residual TPP in the flame retardant, which greatly inhibited the reaction between the PC resin and the PET resin, and at the same time, the influence of the flame retardant on the toughness of the composition was minimized, and the color stability of the composition after heat retention was also improved.
The high-performance polycarbonate composition product prepared by the invention can be widely applied to household appliances, wall switches, kitchen appliances, housing materials, automobile materials, materials for manufacturing parts in other industrial fields and the like.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (7)
1. A high temperature resistant polycarbonate composition characterized by: comprises the following components in parts by weight: 50-85 parts of PC resin, 5-20 parts of PET resin, 0.01-5.0 parts of compatilizer, 0.1-13.0 parts of flexibilizer, 8.0-20.0 parts of phosphate flame retardant, 0.01-2.0 parts of antioxidant, 0.01-8.0 parts of other auxiliary agents and 1.0-60.0ppm of calcium element based on the total weight of the polycarbonate composition,
Wherein the calcium element is derived from a calcium simple substance or a calcium-containing compound, and the calcium-containing compound is at least one of calcium sulfate, calcium chloride, calcium nitrate, calcium carbonate, calcium phosphate and a calcium-containing complex;
Wherein the phosphate flame retardant is mainly tetraphenyl (bisphenol-A) diphosphate, and trace triphenyl phosphate is also included in the phosphate flame retardant.
2. The high temperature resistant polycarbonate composition of claim 1, wherein: the calcium element is used in an amount of 6.0 to 20.0ppm based on the total weight of the polycarbonate composition.
3. The high temperature resistant polycarbonate composition of claim 1, wherein: the PC resin is at least one of aromatic polycarbonate with viscosity average molecular weight of 10000-; the PET resin is a virgin PET resin or a regenerated PET resin with the intrinsic viscosity of 0.5-0.9 dl/g.
4. The high temperature resistant polycarbonate composition of claim 1, wherein: the compatilizer is at least one of methacrylate-acrylate copolymer, styrene-maleic anhydride random copolymer and styrene-acrylonitrile-glycidyl methacrylate.
5. the high temperature resistant polycarbonate composition of claim 1, wherein: the toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer, acrylic toughening agent and organic silicon rubber graft toughening agent.
6. The high temperature resistant polycarbonate composition of claim 1, wherein: the toughening agent is an organic silicon rubber graft toughening agent, and the volume average particle size of the rubber is 200-2000 nm.
7. A method for preparing the high temperature resistant polycarbonate composition of any of claims 1-6, wherein: the method comprises the following steps: weighing the raw materials according to the formula dosage, putting the raw materials into a mixer, and blending uniformly to obtain a premix; then putting the premix into a double-screw extruder for melt mixing and extrusion granulation to obtain the high-temperature-resistant polycarbonate composition; wherein the ratio of the long diameter of the screw of the double-screw extruder is (40-45):1, the temperature of the screw cylinder is 240-260 ℃, and the rotating speed of the screw is 400-500 rpm.
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| CN115948040B (en) * | 2022-09-30 | 2024-04-16 | 江苏金发科技新材料有限公司 | Polycarbonate composition and preparation and application thereof |
| CN115651387B (en) * | 2022-11-11 | 2023-08-11 | 万华化学（宁波）有限公司 | Polycarbonate composition capable of being stably produced and preparation method thereof |
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| CN101565538A (en) * | 2008-04-22 | 2009-10-28 | 金发科技股份有限公司 | Halogen free flame retardant PC/polyester alloy and preparation method thereof |
| CN104987691A (en) * | 2015-06-09 | 2015-10-21 | 金发科技股份有限公司 | Polycarbonate composition and preparation method thereof |
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| CN101565538A (en) * | 2008-04-22 | 2009-10-28 | 金发科技股份有限公司 | Halogen free flame retardant PC/polyester alloy and preparation method thereof |
| CN104987691A (en) * | 2015-06-09 | 2015-10-21 | 金发科技股份有限公司 | Polycarbonate composition and preparation method thereof |
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