WO2016202192A1 - Polycarbonate composition and preparation method and application thereof - Google Patents

Abstract

Disclosed in the present invention is a polycarbonate composition, comprising the following components in parts by weight: a. 86-99.9 parts polycarbonate; and b. 0.1-14 parts flame retardant; the sum total parts by weight of the two components a and b is 100 parts. By means of selectively adding to the polycarbonate composition formulation perfluorinated alkyl acid and derivatives thereof, the amount thereof being ≤ 100 ppm based on the total weight of the polycarbonate composition, and because the fluorinated alkyl acid and the derivatives thereof have low aqueous solubility and do not easily lose effectiveness in the presence of water, the present invention can significantly improve the mechanical performance and flame retardancy of the polycarbonate composition in high temperatures and high humidity, the flame retardancy thereof reaching 1.5 mm/v-zero, and the mechanical performance and flame retardancy remaining high in 85% humidity and 85°C temperature; the present invention is particularly suited for use in the charger and battery forming industry.

Description

Polycarbonate composition and preparation method and application thereof Technical field

The invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method and application thereof.

Background technique

Polycarbonate flame retardant materials are widely used in the charger and battery industry due to their excellent performance, but the flame retardant properties and mechanical properties of polycarbonate flame retardant materials in wet environments will be greatly reduced, which cannot meet the high temperature requirements of these industries. Industry requirements for wet conditions.

A large number of documents describe methods for improving the flame retardancy of aromatic polycarbonate resins, including the addition of halogenated flame retardants or halogen free flame retardants. Halogen-based flame retardants include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy group Resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromotricyclopentadecane or brominated aromatic crosslinked polymer; halogen-free flame retardant including nitrogen-containing flame retardant, Phosphorus-containing flame retardants, sulfonate flame retardants, etc.

In JP-A 62199654, tetrabromobisphenol A oligomer is used to impart flame retardancy. The compositions mentioned in US-A 2003/0069338 comprise in particular perfluorinated salts, silicones and certain UV absorbers. The same is true for WO 01/83606, in which perfluorosulfonate is disclosed.

However, up to now, it has not been reported about which kind of additive or additive mixture is added to the polycarbonate resin formulation, and the polycarbonate resin can maintain good mechanical properties and flame retardancy after long-term damp heat; There is also no literature mentioning how to improve the hydrolysis resistance of flame retardant polycarbonate resins.

The inventors have surprisingly found through extensive experimentation that the content of the perfluoro-substituted alkyl acid and its derivative added in the polycarbonate composition formulation is ≤100 ppm based on the total weight of the polycarbonate composition, due to the perfluoro-substituted alkane. The base acid and its derivatives have low water solubility and are not easily ineffective in the presence of water, and can significantly improve the mechanical properties and flame retardancy of the polycarbonate composition under high temperature and high humidity conditions, and the flame retardancy reaches 1.5 mm/ V-0, high mechanical and flame retardant retention at 85% humidity and 85°C, and is especially suitable for molding chargers and battery industries.

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art, it is a primary object of the present invention to provide a polycarbonate composition having high mechanical properties and high flame retardant retention under high temperature and high humidity conditions.

Another object of the present invention is to provide a process for the preparation of the above polycarbonate composition.

A further object of the invention is to provide the use of the above polycarbonate compositions.

The invention is achieved by the following technical solutions:

A polycarbonate composition comprising, by weight, the following composition:

a, 86 parts to 99.9 parts of polycarbonate;

b, 0.1 part to 14 parts of flame retardant;

Wherein, the sum of the weight fractions of the two components a and b is 100 parts.

Preferably, a polycarbonate composition, by weight, comprises the following composition:

a, 95 parts to 99.9 parts of polycarbonate;

b, 0.1 parts - 5 parts of flame retardant;

Wherein, the sum of the weight fractions of the two components a and b is 100 parts;

The content of the perfluoro-substituted alkyl acid and its derivative in the total weight of the polycarbonate composition is from 5 ppm to 100 ppm.

Test method for the content of perfluoro-substituted alkyl acid and its derivatives: The sample is cut into small pieces of about 1 cm ² , 20 g (accurate to 0.0001 g) sample is weighed, carbon tetrachloride/methanol is used as an extraction solvent, and placed in Soxhlet In the extraction filter cartridge, Soxhlet extraction for 16 hours, the extract was purified by filtration, and then dehydrated and concentrated by sodium sulfate, and the volume was adjusted to 10 mL. The mobile phase was methanol and tested by liquid chromatography-mass spectrometry (LC-MS).

Column: HP-Innowax capillary (column 30m × 0.25mmi.d., 0.25μm); column temperature: 50 ° C (5min) 30 ° C Π min 240 ° C (5min); injection method: splitless injection; interface temperature: 280 ° C; carrier gas: high purity helium (99.999%); flow rate: 0.8 mL Π min; injection volume: 1 μL.

Mass Spectrometry Condition Ion Source: Negative Chemical Source (NCI). Ion source and quadrupole temperature: 150 °C. Determination method: Select ion scan (SIM), solvent delay: 315 min.

Wherein the perfluoro-substituted alkyl acid and its derivative have a water solubility of ≤700 mg·L ^{-1 as} measured according to the OECD 105 method.

OECD 105 test method: Weigh 2.5020g sample dissolved in 50mL pure water, shake at 30 °C for 24h, take it out and rest at 20 °C for 24h; filter, take 2mL of supernatant from each sample, measure it by UPLC-MS/MS concentration.

Preferably, the perfluoro-substituted alkyl acid and its derivative are based on the total weight of the polycarbonate composition The content is from 10 ppm to 90 ppm, preferably from 15 ppm to 80 ppm; more preferably from 20 ppm to 50 ppm.

The perfluoro-substituted alkyl acid and its derivative are selected from one or more of a perfluoro-substituted alkyl acid, a perfluoro-substituted alkyl acid halide, a perfluoro-substituted alkyl acid amino compound, and a perfluoro-substituted sulfonic acid. Species; preferably C ₈ F ₁₇ I, C ₈ F ₁₇ CH ₂ CH ₂ I, C ₈ F ₁₇ CH=CH ₂ , C ₄ F ₉ CH ₂ CH ₂ OH, C ₆ F ₁₃ CH ₂ CH ₂ OOCCH=CH ₂ , C ₈ F ₁₇ CH ₂ CH ₂ OOCC(CH ₃ )=CH ₂ , C ₈ F ₁₇ CH ₂ COOH, C ₇ F ₁₅ CF=CHCOOH, C ₇ F ₁₅ COOH, C ₄ F ₉ SO ₂ OH, C _{One or more of 8} H ₄ F ₁₅ NO ₂ , C ₈ F ₁₇ SO ₂ ONH _3, C ₄ F ₉ I, C ₄ F ₉ CH ₂ CH ₂ OH, C ₇ F ₁₅ COOHNH ₃ ; more preferably C ₄ F ₉ I, C ₄ F ₉ CH ₂ CH ₂ OH, C ₆ F ₁₃ CH ₂ CH ₂ OOCCH=CH ₂ , C ₇ F ₁₅ CF=CHCOOH, C ₄ F ₉ SO ₂ OH, C ₈ F ₁₇ I One or more of C ₈ F ₁₇ SO ₂ ONH ₃ , C ₇ F ₁₅ COOH, C ₇ F ₁₅ COOHNH ₃ .

Wherein the polycarbonate is selected from one or the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, a branched polycarbonate, and a siloxane copolycarbonate; It is preferably an aromatic polycarbonate.

Preferably, the aromatic polycarbonate has an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, more preferably an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000. When the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained. Among them, the viscosity average molecular weight was calculated by using a solution of dichloromethane as a solvent at a test temperature of 25 ° C.

The preparation method of the above polycarbonate:

Bisphenol A and sodium hydroxide solution form bisphenol A sodium salt, which is sent to phosgenation reactor, and phosgene is introduced in the presence of dichloromethane solvent to react with bisphenol A sodium salt at the interface. The low molecular weight polycarbonate was then polycondensed into a high molecular polycarbonate by adding triethylamine and caustic soda solution in a polycondensation kettle. Further, the polycarbonate resin may contain a resin prepared by transesterification of a phenol compound (for example, a dihydric phenol compound) and a carbonate precursor (for example, diphenyl carbonate).

Wherein the flame retardant is selected from the group consisting of a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant; the halogen-based flame retardant is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, and bromine Bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate One or more of a perfluorotricyclopentadecane or a brominated aromatic crosslinked polymer; the halogen-free flame retardant is selected from the group consisting of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant, and a nitrogen-containing and phosphorus-containing One or more of a flame retardant, a silicon-containing flame retardant, a boron-containing flame retardant, and a sulfonate flame retardant.

The polyester composition may further comprise 0 to 4.9 parts of rubber, and the rubber may be at least one selected from the group consisting of C ₄ -C ₆ diene rubber, (meth) acrylate rubber, and silicone rubber. A rubber monomer; the rubber may also be a silicone rubber which comprises only a silicone rubber and/or a (meth) acrylate rubber, thereby improving the structural stability of the polycarbonate.

The polyester composition may further comprise 0-3 parts of other auxiliary agents; the other auxiliary agents are selected from one or more of an antioxidant, a light stabilizer, an anti-drip agent, a lubricant, and a colorant. Kind.

The anti-drip agent is selected from the group consisting of polytetrafluoroethylene, pure polytetrafluoroethylene powder, AS coated modified polytetrafluoroethylene powder, and PMMA coated modified polytetrafluoroethylene powder. .

The antioxidant is selected from one or more of a complex of phenols, phosphites, thioesters.

The light stabilizer can improve the photoaging resistance of the material during use, and can be selected from one or more compounds of hindered amines, benzotriazoles, and benzoxazinone complexes.

The lubricant is selected from one or more of a polyol ester, a metal soap, a stearic acid complex ester or an amide.

The colorant is selected from one or more of inorganic and organic colorants such as titanium dioxide, carbon black, phthalocyanine, ultramarine blue, azo, naphthalenone, and the like.

The preparation method of the above polycarbonate composition comprises the following steps:

The polycarbonate resin, the flame retardant, the perfluoro-substituted alkyl acid and the derivative thereof are uniformly mixed in a high-mixer, and the speed of the mixer is 450 rpm to 500 rpm, and the mixture is added to the twin-screw extruder. In the machine, melt-mixing is carried out at a temperature of from 240 ° C to 260 ° C, followed by granulation, cooling, and drying to obtain a polycarbonate composition.

The polycarbonate compositions of the present invention are useful in the molding charger and battery industries.

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

The present invention is characterized in that the content of the perfluoro-substituted alkyl acid and its derivative added in the polycarbonate composition formulation is ≤100 ppm based on the total weight of the polycarbonate composition, and the water is replaced by the perfluoro-substituted alkyl acid and its derivative. Low solubility, not easy to fail in the presence of water, can significantly improve the mechanical properties and flame retardant properties of polycarbonate compositions under high temperature and high humidity conditions, and its flame retardant performance reaches 1.5mm/v-0, at 85% humidity And 85 ° C, mechanical properties and flame retardant retention rate, and is particularly suitable for molding chargers and battery industry.

detailed description

The invention will be further illustrated by the following specific embodiments, the following examples of which are preferred The embodiment is not limited by the following embodiments.

Test criteria or methods for each performance:

Test method for the content of perfluoro-substituted alkyl acids and their derivatives:

The sample was cut into small pieces of about 1 cm ² , and 20 g (accurate to 0.0001 g) sample was weighed, carbon tetrachloride/methanol was used as an extraction solvent, placed in a Soxhlet extraction cartridge, Soxhlet extraction for 16 hours, and the extract was filtered and purified. , dehydrated and concentrated with sodium sulfate, and concentrated to 10 mL. The mobile phase was methanol and tested by liquid chromatography-mass spectrometry (LC-MS).

Column: HP-Innowax capillary (column 30m × 0.25mmi.d., 0.25μm); column temperature: 50 ° C (5min) 30 ° C Π min 240 ° C (5min); injection method: splitless injection; interface temperature: 280 ° C; carrier gas: high purity helium (99.999%); flow rate: 0.8 mL Π min; injection volume: 1 μL.

Mass Spectrometry Condition Ion Source: Negative Chemical Source (NCI). Ion source and quadrupole temperature: 150 °C. Determination method: Select ion scan (SIM), solvent delay: 315 min.

Test Method for Water Solubility: Water solubility test was performed according to the OECD 105 method. 2.5020 g of the sample was dissolved in 50 mL of pure water, shaken at 30 ° C for 24 h, taken out and placed at 20 ° C for 24 h; filtered, each sample was taken 2 mL of the supernatant, and its concentration was determined by UPLC-MS/MS.

Tensile strength: determined according to ISO 527-2, the test conditions are 23 ° C, 50 mm / min;

Tensile strength retention rate: tensile strength retention rate = tensile strength (after boiled or damp heat aging) / tensile strength × 100%;

Cantilever notched impact strength: measured according to ISO 180;

Cantilever beam notched impact strength retention rate: impact strength retention rate = tensile strength (after boiled or damp heat aging) / impact strength × 100%;

Flame retardant test: according to the UL94 standard, the test strip thickness is 1.5mm;

Flame-retardant boiling test: according to UL746C, the test condition is 70 ° C, 7 days, the medium is deionized water;

Flame retardant damp heat aging test: According to ASTM D2126-04, the test conditions were 85 ° C, 85% humidity, 1000 hours.

The raw materials used in the examples and comparative examples are described below, but are not limited to these materials:

The polycarbonate used in the present invention is prepared as follows:

Bisphenol A and sodium hydroxide solution form bisphenol A sodium salt, which is sent to phosgenation reactor, and phosgene is introduced in the presence of dichloromethane solvent to react with bisphenol A sodium salt at the interface. The low molecular weight polycarbonate is then polycondensed into a high molecular polycarbonate by adding a solution of triethylamine and caustic soda in a polycondensation kettle. In addition, gather The carbonate resin may contain a resin prepared by transesterification of a phenol compound (for example, a dihydric phenol compound) and a carbonate precursor (for example, diphenyl carbonate).

Flame retardant used in the present invention:

The flame retardant of Example 1 is KSS (diphenyl sulfone sulfonate, METRO KSS, Metropolitan Eximchem Limited);

The flame retardant of Example 2 and Example 7 to Example 10 is BDP (bisphenol A bis(diphenyl phosphate); FP-600, Edike);

The flame retardant of Example 3 - Example 6 is FG-8500 (tetrabromobisphenol A-polycarbonate oligomer, Teijin);

The flame retardant of Comparative Example 1 is KSS;

The flame retardant of Comparative Example 2 is BDP;

The flame retardant of Comparative Example 3 is BDP;

The flame retardant of Comparative Example 4 to Comparative Example 7 was BDP.

Perfluoro-substituted alkyl acids and derivatives thereof for use in the present invention:

PF1 is C ₇ F ₁₅ COOH, water solubility is 600 mg·L ^-1 (perfluorooctanoic acid, 3 M);

PF2 is C ₄ F ₉ I/C ₄ F ₉ CH ₂ CH ₂ OH=1:1, water solubility is 650 mg·L ^-1 (iodofluorobutane, homemade);

PF3 is C ₄ F ₉ SO ₂ OH, water solubility is 350 mg·L ^-1 (perfluorobutyl sulfonic acid, homemade);

PF4 is C ₄ F ₉ CH ₂ CH ₂ SO ₃ K, water solubility is 350 mg·L ^-1 (potassium perfluoropentyl sulfonate, homemade);

PF5 is C ₇ F ₁₅ COOH, water solubility is 750 mg·L ^-1 (perfluorooctanoic acid, 3 M);

Examples 1-10 and Comparative Examples 1-7: Preparation of Polycarbonate Compositions

According to the formulation of Table 1, the polycarbonate, flame retardant, perfluoro-substituted alkyl acid and its derivatives are uniformly mixed in a high-mixer, and the speed of the mixer is from 450 rpm to 500 rpm, and is added to the double. In a screw extruder, melt-mixing is carried out at a temperature of 240 ° C to 260 ° C, followed by granulation, cooling, and drying to obtain a polycarbonate composition; tensile strength and retention of the polycarbonate composition, and cantilever gap The impact strength and retention, flame retardancy and retention were tested. The data is shown in Table 1.

Table 1 Specific ratios (parts by weight) of Examples 1-10 and Comparative Examples 1-7 and their test performance results

[Correct according to Rule 26 07.07.2016]

[Correct according to Rule 26 07.07.2016]

Continued Table 1

[Correct according to Rule 26 07.07.2016]

[Correct according to Rule 26 07.07.2016]

As can be seen from the comparison of the examples of Table 1 and the comparative examples, the present invention selects the addition of perfluoro-substituted alkyl acid and its derivative content in the polycarbonate composition formulation to ≤100 ppm based on the total weight of the polycarbonate composition. When the perfluoro-substituted alkyl acid and its derivatives have low water solubility, they are not easily ineffective in the presence of water, and the mechanical properties and flame retardancy of the polycarbonate composition under high temperature and high humidity conditions can be remarkably improved. The flame retardant performance reaches 1.5mm/v-0. Under the conditions of 85% humidity and 85°C, the mechanical properties and flame retardant performance are high, and it is especially suitable for the molding charger and battery industry.

Claims (11)

1. A polycarbonate composition comprising, by weight, the following composition:

   a, 86 parts to 99.9 parts of polycarbonate;

   b, 0.1 part to 14 parts of flame retardant;

   Wherein, the sum of the weight fractions of the two components a and b is 100 parts.
2. A polycarbonate composition according to claim 1 comprising, by weight, the following composition:

   a, 95 parts to 99.9 parts of polycarbonate;

   b, 0.1 parts - 5 parts of flame retardant;

   Wherein, the sum of the weight fractions of the two components a and b is 100 parts;

   The content of the perfluoro-substituted alkyl acid and its derivative in the total weight of the polycarbonate composition is from 5 ppm to 100 ppm.
3. The polycarbonate composition according to claim 2, wherein the perfluoro-substituted alkyl acid and its derivative have a water solubility of ≤ 700 mg·L ^{-1 as} measured according to the OECD 105 method.
4. The polycarbonate composition according to claim 2, wherein the content of the perfluoro-substituted alkyl acid and its derivative in the total weight of the polycarbonate composition is from 10 ppm to 90 ppm, preferably 15 ppm - 80 ppm; more preferably 20 ppm to 50 ppm.
5. The polycarbonate composition according to any one of claims 2 to 4, wherein the perfluoro-substituted alkyl acid and its derivative are selected from the group consisting of perfluoro-substituted alkyl acids and perfluoro-substituted alkyl acid halides. One or more of a perfluoro-substituted alkyl acid amino compound and a perfluoro-substituted sulfonic acid; preferably C ₈ F ₁₇ I, C ₈ F ₁₇ CH ₂ CH ₂ I, C ₈ F ₁₇ CH=CH ₂ , C ₄ F ₉ CH ₂ CH ₂ OH, C ₆ F ₁₃ CH ₂ CH ₂ OOCCH=CH ₂ , C ₈ F ₁₇ CH ₂ CH ₂ OOCC(CH ₃ )=CH ₂ , C ₈ F ₁₇ CH ₂ COOH, C ₇ F ₁₅ CF=CHCOOH, C ₇ F ₁₅ COOH, C ₄ F ₉ SO ₂ OH, C ₈ H ₄ F ₁₅ NO ₂ , C ₈ F ₁₇ SO ₂ ONH _3, C ₄ F ₉ I, C ₄ F ₉ CH One or more of ₂ CH ₂ OH, C ₇ F ₁₅ COOHNH ₃ ; more preferably C ₄ F ₉ I, C ₄ F ₉ CH ₂ CH ₂ OH, C ₆ F ₁₃ CH ₂ CH ₂ OOCCH=CH ₂ One or more of C ₇ F ₁₅ CF=CHCOOH, C ₄ F ₉ SO ₂ OH, C ₈ F ₁₇ I, C ₈ F ₁₇ SO ₂ ONH ₃ , C ₇ F ₁₅ COOH, C ₇ F ₁₅ COOHNH ₃ Kind.
6. The polycarbonate composition according to claim 1 or 2, wherein the polycarbonate is selected from the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, and a branched poly Carbonate, One or one of siloxane copolycarbonates; preferably an aromatic polycarbonate.
7. The polycarbonate composition according to claim 6, wherein the aromatic polycarbonate is selected from aromatic polycarbonates having a viscosity average molecular weight of from 13,000 to 40,000, more preferably aromatic having a viscosity average molecular weight of from 16,000 to 28,000. Family polycarbonate.
8. The polycarbonate composition according to claim 1 or 2, wherein the flame retardant is selected from a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant; The flammable agent is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, One or more of decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromotricyclopentadecane or brominated aromatic crosslinked polymer; the halogen-free flame retardant is selected from One or more of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant, a flame retardant containing nitrogen and phosphorus, a silicon-containing flame retardant, a boron-containing flame retardant, and a sulfonate flame retardant.
9. The polycarbonate composition according to claim 1 or 2, which further comprises 0 to 4.9 parts of rubber and 0 to 3 parts of other auxiliary agents selected from the group consisting of antioxidants and light stabilizers. One or more of a dose, an anti-drip agent, a lubricant, and a colorant.
10. A method of preparing a polycarbonate composition according to any one of claims 1 to 9, comprising the steps of:

    The polycarbonate, the flame retardant, the perfluoro-substituted alkyl acid and the derivative thereof are uniformly mixed in a high-mixer, and the speed of the mixer is 450 rpm to 500 rpm, and is added to the twin-screw extrusion. In the machine, melt mixing is carried out at a temperature of from 240 ° C to 260 ° C, followed by granulation, cooling, and drying to obtain a polycarbonate composition.
11. Use of a polycarbonate composition according to any of claims 1-9 in a shaped charger and battery.