High-fluidity polycarbonate material and high-performance polycarbonate composite material prepared from same

Abstract

The invention provides a high-fluidity polycarbonate material, and every 100 parts by mass of a material finished product comprises: 80-99.9 parts by mass of polycarbonate; and 0.1 to 20 parts of a flow modifier. The invention also provides a high-performance polycarbonate composite material, and every 100 parts by mass of the high-performance polycarbonate composite material product comprises 80-96.9 parts by mass of the high-fluidity polycarbonate; 1 to 10 parts of a toughening agent; 2 to 15 parts of a flame retardant; 0.05 to 2 parts of an anti-dripping agent; and 0.05 to 2 parts of an antioxidant. The preparation method disclosed by the invention has the beneficial effects that the preparation of the high-fluidity polycarbonate is realized, the fluidity of the polycarbonate is obviously improved, and the preparation method is very environment-friendly; compared with a composite material prepared from original CD material polycarbonate, the polycarbonate composite material prepared from the high-fluidity polycarbonate is more excellent and more stable in performance.

Description

[Technical field]

[0001] The invention relates to the technical field of polycarbonate composite materials, in particular to a high-fluidity polycarbonate material and a high-performance polycarbonate composite material prepared therefrom. [Background technology]

[0002] Polycarbonate (PC) contains carbonate groups in its chemical structure. It is an engineering plastic with excellent comprehensive performance, including dimensional stability, strong mechanical properties, good thermal properties and excellent electrical properties. It is widely used in glass assembly, automobile industry, electronics, and electrical industry. The most common polycarbonate applications and products in production and life are mainly divided into two categories: one is high flow and low impact type (MI ≥ 50g / 10min, 300℃ / 1.2Kg), such as CD discs; the other is low flow and high impact type (MI ≤ 8g / 10min, 300℃ / 1.2Kg), such as drinking water bottles. The latter has high melt viscosity and high processing temperature, which greatly restricts the application and development of polycarbonate.

[0003] The preparation methods of high-flow polycarbonate are mainly divided into two categories: one is to add high-flow polycarbonate to low-flow polycarbonate to adjust it, which is similar to the effect of dilution; the other is to obtain high-flow polycarbonate by physical lubrication or chemical chain scission, such as melt blending of lubricants, flow modifiers and other additives with polycarbonate. Regarding the former, with the development of science and technology, the demand for the use of CDs has decreased, resulting in a sharp decline in its production, so this method will aggravate the current situation of increasingly scarce raw materials. Regarding the latter, on the one hand, the use of flow modifiers that can improve or control rheological properties such as viscosity for chain scission degradation may result in incomplete reaction or residue, making it difficult to control the stability of the finished material, affecting the formulation research and production control; on the other hand, with the enhancement of people's awareness of environmental protection, the hygiene requirements for plastic processing additives are getting higher and higher, and the use of traditional flow modifiers and other related additives is not conducive to environmental protection.

[0004] In view of this, the present invention selects a flow modifier of a low molecular weight polymer based on vegetable oil, and the vegetable oil used includes olive oil, rapeseed oil, peanut oil, soybean oil and castor oil, etc., which has excellent properties such as non-toxicity, good biodegradability, good viscosity-temperature characteristics and viscosity index, and good lubricity. The low-flow and high-impact polycarbonate is transformed into a high-flow and low-impact CD-like polycarbonate under mild conditions, and the melt index MI is controllable and unrestricted. It can be directly used to replace the original CD material for experiments and production later. The performance and molecular weight of the finished product are better than the results of experiments and production using the original CD material, and it is more stable. [Summary of the invention]

[0005] In order to solve the problem that the output of high-flow, low-impact CD discs is reduced and cannot meet the needs of industrial production, when using traditional flow modifiers to prepare high-flow, low-impact polycarbonate, the stability of the finished material is difficult to control, resulting in the problem that the formulation research and production control are affected and it is not conducive to environmental protection. The present invention provides a high-flow polycarbonate material and a high-performance polycarbonate composite material prepared therefrom to solve the above problems.

[0006] The solution of the present invention to solve the technical problem is:

[0007] A high-fluidity polycarbonate material, wherein every 100 parts by mass of the high-fluidity polycarbonate material finished product comprises the following components in parts by mass:

[0008] Polycarbonate, 80-99.9 parts;

[0009] Flow modifier, 0.1 to 20 parts.

[0010] As a preferred embodiment of the present invention, the polycarbonate is a compound of one or more of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol A polycarbonate, and high temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of the polycarbonate is between (3 and 49) g / 10min (300°C / 1.2Kg), the weight average molecular weight is between 20000 and 0000, and the molecular weight distribution is between 1 and 2.5.

[0011] As a preference of the present invention, the flow modifier may be a chemical modifier (which will chemically react with polycarbonate) and a physical modifier (which will not chemically react with polycarbonate), and may be a combination of one or more flow modifiers.

[0012] As preferred embodiment of the present invention, the chemical modifier comprises alkaline additives (such as sodium hydroxide, potassium hydroxide, ammonia water, tetrabutyl titanate, etc.), phosphates (such as tetraphenyl bisphenol A diphosphate BDP, tricresyl phosphate TCP, toluene diphenyl phosphate CDP, and fatty alcohol phosphate esters, phenolic phosphate esters, mixed phosphate esters and chlorinated phosphate esters, etc.), and vegetable oil-based (such as polyricinoleate, tributyl citrate (TBC), trioctyl citrate (TOC), acetyl tributyl citrate (ATBC), acetyl trioctyl citrate (ATOC), etc.), and the processing temperature of the chemical modifier is 220-320°C.

[0013] As preferred embodiments of the present invention, the physical modifier includes waxes (such as paraffin wax, PE wax, PP wax, WE4PWD, HI-WAX, etc.), stearates (such as PETS-G748, PETS-G749H, etc.), stearamides (such as ethylene bis stearamide, N, N'-ethylene bis stearamide, etc.), silicones (such as silicone oil, silicone powder, etc.), phosphazenes (such as phenoxy cyclophosphazenes of phosphazene structure, fluorine-containing cyclotriphosphazenes, etc.), hyperbranched polymers (such as HBP-160, HBP-C660, etc.), random copolymers (such as EMI-200), and epoxides (such as epoxidized oils, epoxy fatty acid esters, etc.).

[0014] The present invention also provides a high-performance polycarbonate composite material, which comprises the above-mentioned high-flowability polycarbonate, a toughening agent, a flame retardant, an anti-dripping agent, and an antioxidant, wherein every 100 parts by mass of the high-performance polycarbonate composite product comprises the following components in parts by mass:

[0015] High flow polycarbonate, 80-96.9 parts;

[0016] Toughening agent, 1 to 10 parts;

[0017] Flame retardant, 2 to 15 parts;

[0018] Anti-dripping agent, 0.05-2 parts;

[0019] Antioxidant, 0.05 to 2 parts.

[0020] As preferred embodiments of the present invention, the toughening agent can be an unsaturated rubber (e.g., nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR)), a saturated rubber (e.g., butyl rubber (IIR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), halogenated butyl rubber), a styrene-based thermoplastic elastomer (e.g., methyl methacrylate-butadiene-styrene terpolymer (MBS), styrene-butadiene-styrene copolymer (SBS), hydrogenated SBS (SEBS), styrene-isoprene-styrene (SIS)), a polyurethane-based thermoplastic elastomer (e.g., TPU), a polyolefin-based thermoplastic elastomer (e.g., chlorinated polyethylene (CPE), ethylene-octene copolymer (POE), thermoplastic dynamic vulcanizate (TPV), ethylene-vinyl acetate copolymer (EVA)), a polyamide-based thermoplastic elastomer (e.g., TPAE), a high-rubber powder, an acrylic copolymer (ACR), and the like, and a compound of one or more of their derivatives.

[0021] As a preferred embodiment of the present invention, the flame retardant may include one or more of the following flame retardants in combination: hypophosphite flame retardants, such as vinyl aluminum hypophosphite flame retardant, vinyl hypophosphite; phosphate flame retardants, such as 1,3-phenylene phosphate (2,6-methylphenyl) tetraester, tetraphenyl bisphenol A diphosphate and its derivative flame retardant (BDP), tetraphenyl resorcinol diphosphate and its derivative (RDP) flame retardant, triphenyl phosphate (TPP) flame retardant; sulfonate flame retardants, such as potassium benzenesulfonylbenzenesulfonate (KSS), potassium perfluorobutyl sulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB); silicone flame retardants, such as polysilicon borane and its derivative flame retardants, cross-linked polydimethylsiloxane (PDMS) and its derivatives.

[0022] As a preferred embodiment of the present invention, the anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material or a non-coated PTFE (pure powder type) material.

[0023] As a preferred embodiment of the present invention, the selected antioxidant can be a combination of one or more of hindered phenols (such as (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate), phosphites (such as tris (2,4-di-tert-butylphenyl) phosphite, dioctadecyl alcohol pentaerythritol diphosphite), thio antioxidants, etc.

[0024] The beneficial effects of the present invention are as follows: the preparation of high-fluidity polycarbonate is achieved by adding a vegetable oil-based flow modifier, which can significantly improve the fluidity of plastics, solve the problem that the existing high-fluidity CD disc output is reduced and cannot meet industrial production needs, and is very environmentally friendly; the polycarbonate composite material prepared by using the high-fluidity polycarbonate prepared by adding a vegetable oil-based flow modifier has better performance than the composite material prepared by the original CD material polycarbonate, and the high-fluidity polycarbonate can be directly used to replace the original CD material for experiments and production. The performance and molecular weight of the finished product are better than the results of experiments and production using the original CD material, and are more stable. [Specific implementation method]

[0025] To further illustrate the technical means and effects adopted by the present invention, the following is a detailed description in conjunction with the embodiments of the present invention.

[0026] The present invention provides a high-fluidity polycarbonate material. Every 100 parts by mass of the high-fluidity polycarbonate material finished product comprises the following components in parts by mass:

[0027] Polycarbonate, 80-99.9 parts;

[0028] Flow modifier, 0.1 to 20 parts.

[0029] Specifically, the polycarbonate is a compound of one or more of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer PC, cyclohexane bisphenol A polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of the polycarbonate is between (3 and 49) g / 10min (300°C / 1.2Kg), the weight average molecular weight is between 20,000 and 50,000, and the molecular weight distribution is between 1 and 2.5.

[0030] Specifically, the flow modifier may be a chemical modifier (which will chemically react with polycarbonate) or a physical modifier (which will not chemically react with polycarbonate), and may be a combination of one or more flow modifiers.

[0031] Specifically, the chemical modifier includes alkaline additives (such as sodium hydroxide, potassium hydroxide, ammonia water, tetrabutyl titanate, etc.), phosphates (such as tetraphenyl bisphenol A diphosphate BDP, tricresyl phosphate TCP, toluene diphenyl phosphate CDP, and fatty alcohol phosphate esters, phenolic phosphate esters, mixed phosphate esters and chlorinated phosphate esters, etc.), and plant oil-based (such as polyricinoleate, tributyl citrate (TBC), trioctyl citrate (TOC), acetyl tributyl citrate (ATBC), acetyl trioctyl citrate (ATOC), etc.), and the processing temperature of the chemical modifier is 220-320°C.

[0032] Specifically, the physical modifier includes waxes (such as paraffin wax, PE wax, PP wax, WE4PWD, HI-WAX, etc.), stearates (such as PETS-G748, PETS-G749H, etc.), stearamides (such as ethylene bis stearamide, N, N'-ethylene bis stearamide, etc.), silicones (such as silicone oil, silicone powder, etc.), phosphazenes (such as phenoxy cyclophosphazenes of phosphazene structure, fluorinated cyclotriphosphazenes, etc.), hyperbranched polymers (such as HBP-160, HBP-C660, etc.), random copolymers (such as EMI-200), and epoxides (such as epoxidized oils, epoxy fatty acid esters, etc.).

[0033] The present invention also provides a high-performance polycarbonate composite material, which comprises the above-mentioned high-flowability polycarbonate, a toughening agent, a flame retardant, an anti-dripping agent, and an antioxidant, wherein every 100 parts by mass of the high-performance polycarbonate composite product comprises the following components in parts by mass:

[0034] High flow polycarbonate, 80-96.9 parts;

[0035] Toughening agent, 1 to 10 parts;

[0036] Flame retardant, 2 to 15 parts;

[0037] Anti-dripping agent, 0.05-2 parts;

[0038] Antioxidant, 0.05 to 2 parts.

[0039] Specifically, the toughening agent can be an unsaturated rubber (such as nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR)), a saturated rubber (such as butyl rubber (IIR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), halogenated butyl rubber), a styrene-based thermoplastic elastomer (such as methyl methacrylate-butadiene-styrene terpolymer (MBS), styrene-butadiene-styrene copolymer (SBS), hydrogenated SBS (SEBS), styrene-isoprene-styrene (SIS)), a polyurethane-based thermoplastic elastomer (such as TPU), a polyolefin-based thermoplastic elastomer (such as chlorinated polyethylene (CPE), ethylene-octene copolymer (POE), thermoplastic dynamic vulcanizate (TPV), ethylene-vinyl acetate copolymer (EVA)), a polyamide-based thermoplastic elastomer (such as TPAE), a high-rubber powder, an acrylic copolymer (ACR), and the like, and a compound of one or more of their derivatives.

[0040] Specifically, the flame retardant may include one or more of the following flame retardants in combination: hypophosphite flame retardants, such as vinyl aluminum hypophosphite flame retardant, vinyl hypophosphite; phosphate flame retardants, such as 1,3-phenylene phosphate (2,6-methylphenyl) tetraester, tetraphenyl bisphenol A diphosphate and its derivative flame retardant (BDP), tetraphenyl resorcinol diphosphate and its derivative (RDP) flame retardant, triphenyl phosphate (TPP) flame retardant; sulfonate flame retardants, such as potassium benzenesulfonylbenzenesulfonate (KSS), potassium perfluorobutyl sulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB); silicone flame retardants, such as polysilicon borane and its derivative flame retardants, cross-linked polydimethylsiloxane (PDMS) and its derivatives.

[0041] Specifically, the anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material or a non-coated PTFE (pure powder type) material.

[0042] Specifically, the selected antioxidant can be a combination of one or more of hindered phenols (such as (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate), phosphites (such as tris(2,4-di-tert-butylphenyl) phosphite, distearyl alcohol pentaerythritol diphosphite), thio antioxidants, etc.

[0043] In order to have a further understanding of the purpose, technical effects and technical means of the present invention, the technical solutions of the present invention are further illustrated by specific embodiments below.

[0044] Example 1

[0045] Embodiment 1 provides a high-flow polycarbonate, which is prepared by adding a polyricinoleate flow modifier into polycarbonate. Every 100 parts by weight of the high-flow polycarbonate comprises the following components in parts by weight: 98 parts of polycarbonate and 2 parts of the flow modifier.

[0046] Specifically, the selected polycarbonate is bisphenol A linear polycarbonate, synthesized by phosgene method, MI=6.0g / 10min (300°C / 1.2Kg), weight average molecular weight is between 49000 and 50000, and molecular weight distribution is between 1.6 and 1.7;

[0047] 2 parts of flow improver are vegetable oil based polyricinoleate flow improver.

[0048] When preparing the high-fluidity polycarbonate, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded and granulated using a twin-screw extruder at a processing temperature of 290°C.

[0049] Comparative Example 1

[0050] The polycarbonate in Comparative Example 1 is an original CD material polycarbonate with higher fluidity. The original CD material polycarbonate is a bisphenol A linear polycarbonate synthesized by phosgene method, with MI=60g / 10min (300℃ / 1.2Kg), a weight average molecular weight between 25000 and 30000, and a molecular weight distribution between 1.9 and 2.0.

[0051] When preparing the original CD material polycarbonate, 100 parts by weight of the original CD material polycarbonate was melt-extruded and granulated using a twin-screw extruder at a processing temperature of 290°C.

[0052] According to the above Example 1 and Comparative Example 1, the melt flow index and other related data of the obtained materials were tested according to the standard, and the test results are shown in Table 1:

[0053]

[0054] Table 1 Test results

[0055] It can be seen from the above test results that the present invention achieves the preparation of high-fluidity polycarbonate by adding a vegetable oil-based flow modifier, and the flow modifier used is a polyricinoleic acid ester, which is an ester of polyricinoleic acid, has a strong oil-in-water emulsification effect, and can significantly improve the fluidity of plastics at high temperatures. Since polyricinoleic acid can be obtained from castor oil, it is an environmentally friendly vegetable oil-based flow modifier material, and has the advantages of a small addition amount and obvious improvement in the fluidity of polycarbonate. By adjusting the content of the flow modifier, the required finished product MI (melt flow index) can be easily achieved, which solves the problem that the existing high-fluidity CD disc production is reduced and cannot meet the needs of industrial production.

[0056] Example 2

[0057] Example 2 provides a high-performance polycarbonate composite material, and every 100 parts by mass of the high-performance polycarbonate composite material includes the following components in parts by mass: 86.1 parts of high-flowability polycarbonate, 6 parts of a toughening agent, 7.5 parts of a flame retardant, 0.1 parts of an anti-drip agent, and 0.3 parts of an antioxidant.

[0058] Specifically, 86.1 parts of the high-fluidity polycarbonate selected was prepared from Example 1.

[0059] The 6 parts of toughening agent selected are styrene-based thermoplastic elastomer MBS, which can significantly improve the impact resistance of resins and engineering plastics, and also has excellent heat aging resistance and hydrolysis resistance.

[0060] The flame retardant selected in an amount of 7.5 parts is a phosphate flame retardant, which is a light yellow liquid with a high viscosity at room temperature (25° C.) and a P element content of ≥8.9%.

[0061] The 0.1 part anti-drip agent selected is non-coated PTFE (pure powder type), which has a small addition amount and a significant anti-drip effect.

[0062] The 0.3 parts of antioxidant selected is a compound of hindered phenols and phosphites, which has a significant synergistic effect, and has the characteristics of small addition amount, significant antioxidant and anti-yellowing effects.

[0063] When preparing the high-performance polycarbonate composite material, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded and granulated using a twin-screw extruder at a processing temperature of 220°C.

[0064] Comparative Example 2

[0065] Comparative Example 2 provides an original CD material polycarbonate composite material, which is obtained by replacing the high-flowability polycarbonate in Example 2 with the same mass portion of original CD material polycarbonate, while keeping the material selection and mass portions of the other components unchanged. Every 100 mass portions of the original CD material polycarbonate composite material includes the following components in mass portions: 86.1 parts of original CD material polycarbonate (MI=60), 6 parts of a toughening agent, 7.5 parts of a flame retardant, 0.1 parts of an anti-dripping agent, and 0.3 parts of an antioxidant.

[0066] Specifically, 86.1 parts of the original CD material polycarbonate selected are the original CD material polycarbonate described in Comparative Example 1 (MI=60).

[0067] The toughening agent used in the amount of 6 parts is styrene-based thermoplastic elastomer MBS.

[0068] The flame retardant selected in an amount of 7.5 parts is a phosphate flame retardant.

[0069] The anti-dripping agent selected in an amount of 0.1 parts is non-coated PTFE (pure powder type).

[0070] The selected antioxidant of 0.3 parts is a compound of hindered phenols and phosphites.

[0071] When preparing the original CD material polycarbonate composite material, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded and granulated using a twin-screw extruder at a processing temperature of 220°C.

[0072] According to the above Example 2 and Comparative Example 2, the melt flow index and other related data of the obtained materials were tested according to the standard, and the test results are shown in Table 2:

[0073]

[0074] Table 2 Test results

[0075] From the test results of Example 2 and Comparative Example 2, it can be seen that the polycarbonate composite material prepared by using high-fluidity polycarbonate obtained by adding a vegetable oil-based flow modifier has better performance than the composite material prepared from the original CD material polycarbonate. The performance and molecular weight of the finished product are better than the results of experiments and production using the original CD material, and it is more stable and environmentally friendly.

[0076] It should be pointed out that the present invention is not limited to the above-mentioned implementation modes, and any simple modifications, equivalent changes and modifications made to the above-mentioned embodiments by any technician familiar with the profession based on the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A high-flow polycarbonate material, characterized in that: Every 100 parts by mass of the finished material includes the following components by mass: Polycarbonate, 80-99.9 parts; Flow modifier, 0.1 to 20 parts.

2. A high-flowability polycarbonate material as claimed in claim 1, characterized in that: The polycarbonate is a compound of one or more of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol A polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of the polycarbonate is between (3 and 49) g / 10 min (300° C. / 1.2 kg), the weight average molecular weight is between 20,000 and 0,000, and the molecular weight distribution is between 1 and 2.

5.

3. A high-flowability polycarbonate material as claimed in claim 1, characterized in that: The flow modifier may be a chemical modifier or a physical modifier, and may be a combination of one or more flow modifiers.

4. A high-flowability polycarbonate material as claimed in claim 3, characterized in that: The chemical modifier comprises alkali additives, phosphates, vegetable oil-based, and acetyl trioctyl citrate (ATOC) chemical modifiers, and the processing temperature of the chemical modifier is 220-320°C.

5. A high-flowability polycarbonate material as claimed in claim 3, characterized in that: The physical modifiers include waxes, stearamides, silicones, phosphazenes, hyperbranched polymers, random copolymers, and epoxy physical modifiers.

6. A high-performance polycarbonate composite material, comprising the high-flow polycarbonate, a toughening agent, a flame retardant, an anti-drip agent, and an antioxidant, wherein: The polycarbonate composite material product comprises the following components in parts by weight per 100 parts by weight: High flow polycarbonate, 80-96.9 parts; Toughening agent, 1 to 10 parts; Flame retardant, 2 to 15 parts; Anti-dripping agent, 0.05-2 parts; Antioxidant, 0.05 to 2 parts.

7. A high performance polycarbonate composite material according to claim 6, characterized in that: The toughening agent can be one or a combination of unsaturated rubber, saturated rubber, styrene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer, polyamide thermoplastic elastomer, high rubber powder, acrylic copolymer (ACR) and their derivatives.

8. The high performance polycarbonate composite material according to claim 6, characterized in that: The flame retardant may be a combination of one or more of a hypophosphite flame retardant, a phosphate ester flame retardant, a sulfonate flame retardant, and an organosilicon flame retardant.

9. A high performance polycarbonate composite material according to claim 6, characterized in that: The anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

10. The high performance polycarbonate composite material according to claim 6, characterized in that: The antioxidant can be a combination of one or more of hindered phenols, phosphites, and thio antioxidants.

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