CN111057358B

CN111057358B - High-heat-resistance impact-resistance polycarbonate composition and preparation method thereof

Info

Publication number: CN111057358B
Application number: CN201911257777.5A
Authority: CN
Inventors: 徐禄波; 麻一明; 吴剑波; 王旭; 孙剑; 范方虹; 蒋祥鸳
Original assignee: Ningbo Dopda Polymer Co ltd
Current assignee: Ningbo Jianfeng New Material Co ltd
Priority date: 2019-12-10
Filing date: 2019-12-10
Publication date: 2022-03-04
Anticipated expiration: 2039-12-10
Also published as: CN111057358A

Abstract

The invention relates to a high heat-resistant impact-resistant polycarbonate composition, which comprises the following components in percentage by mass: 40-70% of polycarbonate, 1-10% of polyether-ether-ketone, 5-20% of polyetherimide, 5-20% of superfine fully vulcanized powdered rubber, 1-10% of bismaleimide, 10-30% of glass fiber, 5-15% of a flame retardant and 0.1-1.0% of a processing aid; wherein, the polyether-ether-ketone is fine powder with the average grain diameter less than or equal to 30 μm. According to the invention, PEEK, PEI and glass fiber are added into PC to improve the high temperature resistance and mechanical strength of PC, the compatibility among all components is improved through bismaleimide, and the superfine fully vulcanized powder rubber is filled to effectively improve the impact resistance, so that the high heat-resistant and impact-resistant polycarbonate composite material with good comprehensive performance is finally obtained.

Description

High-heat-resistance impact-resistance polycarbonate composition and preparation method thereof

Technical Field

The invention belongs to the technical field of polymer composite materials, and particularly relates to a high-heat-resistance impact-resistance polycarbonate composition and a preparation method thereof.

Background

Polycarbonate (PC) is a high molecular polymer containing a carbonate group in a molecular chain, and is classified into aliphatic polycarbonate, alicyclic polycarbonate, and aromatic polycarbonate according to the molecular structure. Among them, bisphenol A type aromatic polycarbonates are the most widely used ones with the highest productivity. PC has the advantages of excellent impact toughness, creep resistance, dimensional stability, electrical insulation, weather resistance, transparency, nontoxicity and the like, and is widely applied to the fields of mechanical equipment, constructional engineering, transportation, instruments, electrical appliance illumination and the like. In some specific fields, such as the field of automobile instruments, higher requirements are put on the heat resistance of PC, and the pure PC material cannot meet the requirements. In the hottest summer of tropical countries, the highest temperature of the surface of the instrument can reach 120 ℃ when the automobile is exposed to the sun at noon, and the heat-resistant temperature of the conventional PC/ABS instrument is 110-135 ℃, so that the instrument is easy to deform under long-time high-temperature roasting. In addition, the light pollution reflected by the glass curtain wall of the high-rise building, which is more and more appeared in the urban building, can also cause the severe rise of the internal temperature of the automobile, thereby seriously affecting the safety of the automobile. Therefore, the high heat-resistant impact-resistant PC material is developed and has important application value in the fields of automobile instruments, aerospace and the like.

Polyetherimide (PEI) is a special engineering plastic with a main chain made of a special high polymer material containing imide rings and good heat resistance, mechanical property, high temperature resistance and chemical corrosion resistance, is widely applied to the fields of aerospace, machinery, automobiles, electronics and the like, and has a long-term use temperature of-200-170 ℃. Polyether ether ketone (PEEK) is a special high polymer material which is composed of a repeating unit containing one ketone bond and two ether bonds in a main chain structure, has physicochemical properties of high temperature resistance, chemical corrosion resistance and the like, is a semi-crystalline high polymer material, has a melting point of about 334 ℃, and has a long-term use temperature of up to 250 ℃. PEI and PEEK have higher heat resistance temperature and mechanical strength than PC, but have high processing temperature and poor fluidity, and PC has better processing fluidity, and the PC is blended with PEI and PEEK to hopefully obtain the resin composition with good heat resistance and processing performance.

Chinese patent CN105637032 discloses a polyethylene terephthalate/polycarbonate (PET/PC) composition modified by polyetherimide and Glass Fiber (GF), which is filled with 5% of polyetherimide and 33% of glass fiber, and matched with a proper flame retardant, so that the heat deformation temperature of the composition can be controlled between 100 ℃ and 140 ℃. Chinese patent CN104204095 discloses a PEI/PC blend, which greatly increases the heat distortion temperature of PC composite material by introducing polyetherimide (Ultem 1010) with excellent heat resistance and siloxane polyetherimide (Ultem 9000) into polycarbonate, and the maximum can approach 160 ℃. However, poor compatibility of PEI with PC results in a reduction of the impact toughness of the material. In order to overcome the decrease in impact strength caused by material incompatibility, the prior art has been addressed mainly by improving material compatibility or filling impact modifiers. Chinese patent CN108137927 adopts poly (carbonate-arylate ester) as a compatibilizer to improve the compatibility of PEI with PC; chinese patent CN109952346 adopts an impact modifier with a siloxane-acrylic core-shell structure to improve the impact toughness of PEI/PC composite material; chinese patent CN107429053 adopts poly (carbonate-arylate ester) as compatibilizer, and introduces core-shell acrylic rubber and styrene-ethylene-butylene-styrene rubber as impact modifier to improve the comprehensive properties of the material.

The problem of poor heat resistance of PC is solved to a certain extent by adopting blending of PEI and the like, and the defects of poor compatibility and impact resistance caused by blending are mostly solved by adding a compatibilizer or an impact modifier, but the compatibilizer adopted in the prior art mainly depends on physical action (similar compatibility principle) to increase the compatibility of PEI and PC, and the effect of the compatibilizer is greatly influenced by the molecular structures of PEI and PC and a melt blending process, so that the heat resistance and the impact strength of the prepared PC composite material are unstable in the actual operation process.

Disclosure of Invention

Aiming at the problems in the prior art, the high heat-resistant and impact-resistant polycarbonate composite material with good comprehensive performance is finally obtained by adding components such as PEEK, PEI, glass fiber, bismaleimide, superfine fully vulcanized powdered rubber and the like into PC and reasonably proportioning.

The above object of the present invention is achieved by the following technical solutions:

a high heat-resistant impact-resistant polycarbonate composition comprises the following components in percentage by mass:

40 to 70 percent of polycarbonate,

1-10% of polyether-ether-ketone,

5 to 20 percent of polyetherimide,

5 to 20 percent of superfine fully vulcanized powdered rubber,

1 to 10 percent of bismaleimide,

10 to 30 percent of glass fiber,

5 to 15 percent of flame retardant,

0.1-1.0% of processing aid;

wherein, the polyether-ether-ketone is fine powder with the average grain diameter less than or equal to 30 μm.

Polyetheretherketone (PEEK) is a semi-crystalline polymer with a melting point of up to 334 c, above the normal processing temperature of PC (250-. If the PEEK is allowed to melt completely, the processing temperature needs to be raised above 350 ℃, but such high processing temperature can cause degradation of the PC, severely affecting the properties of the composite. Therefore, it is necessary to process under the condition of less than 350 ℃. In the invention, the PEEK is added in a small amount and has small particle size (micron order), and can be taken as a filler, so that the influence on the melt processing performance of PC is small; and the PEEK is a semi-crystalline polymer, the crystallization degree is low, most molecular chains are in an amorphous state, and the PEEK has certain molecular motion capability under the condition that the temperature is higher than the glass transition temperature (143 ℃), so that the PEEK addition of the invention has very limited influence on the processing temperature of PC, and the normal processing can be carried out at the temperature of about 300 ℃.

The PEEK adopted by the invention is fine powder, and the average grain diameter is less than or equal to 30 mu m. Under proper processing temperature, PEEK molecular chains in an amorphous region are in a viscous state, and PEEK molecular chain segments in a crystalline region are still in a crystalline state and cannot move freely; a PEEK molecule possibly passes through the crystal region for many times and is divided into a plurality of free motion regions and motion limiting regions, molecular chains in the free motion regions can be intertwined with molecular chains of polycarbonate, polyetherimide and bismaleimide, and finally a net-shaped structure taking the PEEK crystal region as a physical cross-linking point is formed, so that the mechanical property of the composite material is greatly improved. It is to be noted that the use of ordinary PEEK pellets instead of PEEK fine powder did not achieve a similar effect. The PEEK fine powder adopted by the invention has the characteristics of small particle size and large specific surface area, and is one of the main direct reasons for forming physical crosslinking points in the composite material.

PEEK of the present invention is a fine powder of the type available from Solvay, Belgium

Series of micro-powders or Wegges

Series of micro powders. More preferably, the polyether ether ketone fine powder has an average particle diameter of 20 μm or less, and is selected from

KT-820UFP、

150UF 10。

Polyetherimide (PEI) is amorphous special engineering plastic, the glass transition temperature of the PEI is about 215 ℃, the thermal deformation temperature of the PEI is 198-208 ℃, the PEI can be used for a long time at 160-180 ℃, and the maximum allowable intermittent use temperature is 200 ℃. PEI also has good flame retardancy, with an oxygen index of 47% and a flame rating of UL 94-V-0. By introducing PEI into PC, the heat resistance and flame retardant property of PC can be improved to a certain extent. The polyetherimide used in the present invention may be selected from Ultem resins available from Sauter basic Innovation industries, Inc., and Ultem 1010 is more preferable.

The fully vulcanized superfine powder rubber is powder rubber formed by radiating vulcanization and spray drying of rubber emulsion, has an average particle size of 50-200nm, is of a highly crosslinked structure, has the characteristics of large surface crosslinking degree and small internal crosslinking degree, is not coagulated in the blending process with a polymer material, is highly dispersed, and can simultaneously improve the toughness and heat resistance of a polymer. The ultra-fine fully vulcanized powdered rubber is selected from one or more of the following: superfine fully-vulcanized powdered nitrile rubber, superfine fully-vulcanized powdered silicone rubber, superfine fully-vulcanized powdered carboxylated nitrile rubber, superfine fully-vulcanized powdered acrylate rubber, superfine fully-vulcanized powdered carboxylated styrene-butadiene rubber and superfine fully-vulcanized powdered styrene-butadiene rubber.

More preferably, the superfine fully vulcanized powdered rubber is superfine fully vulcanized powdered acrylate rubber, and the average particle size is 50-150 nm. VP-301 of the chemical research institute of Beijing, petrochemical China can be selected.

Although the addition of the components such as polyether-ether-ketone, polyetherimide and superfine fully vulcanized powdered rubber is theoretically for greatly improving the performance of the polycarbonate composite material, the polycarbonate composite material is not ideal in performance improvement effect due to the fact that the polymers are different in polarity and poor in compatibility. In the prior art, the compatibility among the components is improved by using a compatibilizer mostly according to the principle of similar compatibility, and the compatibility among the components is improved by physical action, so that the effect of the compatibilizer is greatly influenced by the molecular structure of a polymer and a melt blending process. In the actual operation process, the heat resistance and the impact strength of the prepared composite material often fluctuate greatly, and the product quality is influenced. The invention adopts bismaleimide to improve the compatibility between polymers, the bismaleimide forms a Polymer Interpenetrating Network (IPN) in the process of melting and blending Polymer fillers such as PC, PEEK, PEI, fully-vulcanized ultrafine powder acrylate rubber and the like, PC molecules and other Polymer molecules are confined in the IPN to a certain extent, the distribution state of the IPN can be controlled to a certain extent by controlling the molecular structure and the dosage of the bismaleimide, and the compatibility between the PC and the Polymer filler molecules is improved on the premise of not influencing the thermoplastic processability of the composite material.

The bismaleimide comprises the following structure:

wherein R is selected from one or more of the following structural groups:

further preferably, R is the following structural group:

the bismaleimide is preferably 2,2' -bis [4- (4-maleimidophenoxy) phenyl ] propane (BMP-BMI). The BMP-BMI has a bisphenol A structure similar to the molecular structure of PEI, and has good intermolecular interaction force with PEI. The double bond of the end group of BMP-BMI can carry out free radical reaction under the condition of high temperature to form a self-crosslinking structure. PC may also generate molecular chain breakage during high-temperature processing to form free radicals, so as to perform chemical crosslinking reaction with BMP-BMI. In the processing process of the PEEK fine powder, free molecular chains in an amorphous region and bismaleimide molecular chains are mutually entangled to form a net structure taking a PEEK crystal region as a physical crosslinking point. In the process of processing the PC composite material, the BMP-BMI has good fluidity and slowly generates self-crosslinking reaction and is crosslinked with the PC and the PEEK to form the IPN, so that the compatibility of the PC and the polymer fillers such as the PEEK, the PEI and the superfine fully vulcanized powdered rubber can be improved on the basis of not influencing the thermoplastic processability of the composite material.

The Glass Fiber (GF) of the present invention is preferably a chopped glass fiber having a length of 0.1 to 10mm and a diameter of 1 to 100 μm; more preferably, the length is 1 to 5mm and the diameter is 5 to 30 μm.

The flame retardant of the present invention is preferably a nitrogen-containing flame retardant and/or an organic phosphorus oxide; further preferred are a combination of a nitrogen-containing flame retardant and an organic phosphorus oxide. The nitrogen-containing flame retardant can be selected from melamine, melamine polyphosphate, melamine cyanurate, melamine pyrophosphate and melamine phosphate; the organophosphorus oxide may be selected from triphenylphosphine oxide, tris (4-nonylphenyl) phosphine oxide, tricyclohexylphosphine oxide, tri-p-tolyl-phosphine oxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, phenylbis (n-hexyl) phosphine oxide, benzylbis (cyclohexyl) phosphine oxide, benzylbis (phenyl) phosphine oxide, and the like. The flame retardant of the present invention is further preferably used in combination with melamine cyanurate and triphenylphosphine oxide.

The processing aid comprises antioxidant, lubricant and the like, which can improve the technological properties of the plastic raw material, influence the processing conditions and improve the performance of the composite material.

The antioxidant is preferably a hindered phenol-based and/or phosphite-based antioxidant, such as triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ], octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-4-methylphenol, octadecyl beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate, isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxybenzamide), N, N '-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 2,2' -oxamido-bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) ] propionate, 2, 4-di (N-octylthiomethylene) -6-methylphenol, 4- [ (4, 6-dioctylthio-1, 3, 5-triazin-2-yl) ] -2, 6-di-tert-butylphenol, 4, 4' -methylenebis (2, 6-di-tert-butylphenol) 2, 6-di-tert-butyl-4-methylphenol, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecylpentaerythritol diphosphite and the like.

The antioxidant is preferably a compound of hindered phenol antioxidant and phosphite antioxidant. Further preferred is a combination of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite.

The lubricant can be one or more selected from stearic acid, calcium stearate, paraffin, polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate, N '-ethylene bis stearamide and silicone powder, and is preferably a compound of N, N' -ethylene bis stearamide and silicone powder.

According to the invention, PEEK, PEI and glass fiber are added into PC to improve the high temperature resistance and mechanical strength of PC, and a network structure is formed by cross-linking bismaleimide with PC, PEI and PEEK fine powder molecular chains to improve the compatibility among the components, and the superfine fully vulcanized powder rubber is filled to effectively improve the impact resistance, so that the high heat-resistant impact-resistant polycarbonate composite material with good comprehensive performance is finally obtained. The polycarbonate composition has a heat softening point of not less than 150 ℃ according to GB/T1634-2004 test and a heat softening point of not less than 40KJ/m at room temperature according to GB/T1843-2008 test²The unnotched impact strength of (2).

The other purpose of the invention is realized by the following technical scheme:

a preparation method of a high heat-resistant impact-resistant polycarbonate composition comprises the following steps:

s1, weighing the components according to the mass fraction;

s2, dissolving polyetherimide in an organic solvent, sequentially adding polyether-ether-ketone, glass fiber and superfine fully vulcanized powdered rubber into the solution, uniformly stirring, slowly adding the mixed solution into water to separate out, boiling and washing with water, and drying to obtain mixed powder containing the polyetherimide, the polyether-ether-ketone, the glass fiber and the superfine fully vulcanized powdered rubber;

s3, uniformly mixing the mixed powder with polycarbonate, bismaleimide, a flame retardant and a processing aid to obtain a premix;

and S4, carrying out melt blending on the premix in a screw extruder, carrying out grain cutting to obtain composite granules, and carrying out injection molding to obtain the composite material.

In step S2, dissolving polyetherimide in organic solvent to form polyetherimide solution with solid content of 6-15 m/v%, adding water, and boiling at 80-100 deg.C for 2-5 times.

In the composite material filled with the glass fibers, the interface bonding capability of the glass fibers and the polymer resin matrix directly influences the dispersion effect of the glass fibers and the stress transfer between the glass fibers and the polymer resin matrix. If the glass fibers have poor interfacial bonding with the polymer resin matrix, it can easily lead to "floating fibers" in the composite during processing. In order to improve the "fiber floating" phenomenon of glass fiber, common technical means include adding auxiliary agents such as compatilizer, dispersant, lubricant and the like, and improving processing techniques such as increasing injection temperature, increasing injection speed and the like. However, the addition of a large amount of the auxiliary agent not only increases the material cost, but also has a negative effect on the mechanical properties of the material. The inventor finds that the phenomenon of fiber floating can be improved to a certain extent by premixing the raw materials to a certain extent in the actual operation process. Particularly, in certain specific embodiments, the polyetherimide, the polyetheretherketone, the glass fiber and other fillers are uniformly mixed in an organic solvent, then the mixture is precipitated, boiled and dried to obtain premixed powder, and then the premixed powder is subjected to melt mechanical blending with other residual fillers, so that the dispersibility of the fillers such as the polyetherimide, the polyetheretherketone, the glass fiber and the like in the composite material can be improved, and the occurrence of 'floating fiber' is effectively avoided. And the premixing of the fine powder of the polyether-ether-ketone can exert the function of the physical crosslinking point of the fine powder of the polyether-ether-ketone to the maximum extent, and is favorable for obtaining a stable and complex crosslinking network.

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

the polyether-ether-ketone, the polyetherimide and the glass fiber are simultaneously filled in the polycarbonate, so that the heat resistance and the mechanical strength of the polycarbonate can be improved to the maximum extent; the bismaleimide is used as a modifier to form a polymer interpenetrating network with the PC, PEI and PEEK fine powder molecular chains through mutual crosslinking, so that the compatibility between the PC, the PEEK and the PEI is improved, and the negative influence on the mechanical property of the polycarbonate composition caused by phase separation is avoided; the filling of the superfine fully vulcanized acrylate rubber effectively improves the shock resistance of the polycarbonate, and simultaneously avoids the reduction of the heat resistance of the polycarbonate caused by the addition of a large amount of the acrylate rubber; the processing route of solution premixing and melt blending is adopted, the function of physical crosslinking points of the fine polyether-ether-ketone powder is exerted to the maximum extent, and the dispersibility of fillers such as polyetherimide, glass fiber and the like in the composite material is improved.

The high heat-resistant impact-resistant polycarbonate composition obtained by the invention has a heat softening point of not less than 150 ℃ according to GB/T1634-²The impact strength of (2).

Detailed Description

Hereinafter, the technical solutions of the present invention will be further described and illustrated by specific examples, however, these embodiments are exemplary, and the present disclosure is not limited thereto. Unless otherwise specified, the raw materials used in the following specific examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art.

Example 1

Weighing raw materials according to the mass fractions of the components in the example 1 in the table 1; first, PEI Ultem 1000 was dissolved in a dimethylacetamide (DMAc) organic solvent to prepare a PEI solution having a solid content of 10 wt%, and then PEEK fine powder was pulverized

150UF10, glass fiber and superfine fully vulcanized powder acrylate rubber VP-301 are added into the solution in sequence and stirred uniformly. And then slowly adding the mixed solution into deionized water for precipitation, boiling and washing the mixed solution for 3 times at 90 ℃ by using the deionized water, and then placing the boiled mixed solution into a common oven for drying to obtain mixed powder containing PEI, PEEK, glass fiber and superfine fully vulcanized acrylate rubber. Then theMixing the mixed powder with PC, BMP-BMI, melamine polyphosphate, tricyclohexylphosphine oxide, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2' -oxamido-bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl)]And adding the propionate, the stearic acid and the pentaerythritol stearate into a high-speed mechanical blender, and uniformly stirring to obtain the premix. And carrying out melt blending on the premix in a single-screw extruder, granulating to obtain composite granules, and finally carrying out injection molding on the composite granules to obtain the composite material.

Example 2

Weighing raw materials according to the mass fractions of the components in the example 2 in the table 1; first, PEI Ultem 1010 was dissolved in DMAc organic solvent to prepare a PEI solution having a solid content of 12 wt%, and then PEEK fine powder was pulverized

KT-820UFP, glass fiber and superfine fully-vulcanized powder acrylate rubber are sequentially added into the solution and stirred uniformly. And then slowly adding the mixed solution into deionized water for precipitation, boiling and washing the mixed solution for 4 times at 85 ℃ by using the deionized water, and then placing the boiled mixed solution into a common oven for drying to obtain mixed powder containing PEI, PEEK, glass fiber and superfine fully vulcanized acrylate rubber. Then mixing the mixed powder with PC, BMP-BMI, melamine cyanurate, triphenylphosphine oxide and tetra [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, tris (2, 4-di-tert-butylphenyl) phosphite, N' -ethylene bis stearamide and silicone powder are added into a high-speed mechanical blender and stirred uniformly to obtain the premix. And carrying out melt blending on the premix in a double-screw extruder, granulating to obtain composite granules, and finally carrying out injection molding on the composite granules to obtain the composite material.

Example 3

Weighing raw materials according to the mass fractions of the components in the example 3 in the table 1; firstly, PEI Ultem 1010 is dissolved in DMAc organic solvent to prepare PEI solution with the solid content of 9 wt%, and then PEEK fine powder is mixed

KT-820UFP, glass fiber and superfine fully-vulcanized powder acrylate rubber are sequentially added into the solution and stirred uniformly. And then slowly adding the mixed solution into deionized water for precipitation, boiling and washing the mixed solution for 3 times at 95 ℃ by using the deionized water, and then placing the boiled mixed solution into a common oven for drying to obtain mixed powder containing PEI, PEEK, glass fiber and superfine fully vulcanized acrylate rubber. Then mixing the mixed powder with PC, BMP-BMI, melamine cyanurate, triphenylphosphine oxide and tetra [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, tris (2, 4-di-tert-butylphenyl) phosphite, N' -ethylene bis stearamide and silicone powder are added into a high-speed mechanical blender and stirred uniformly to obtain the premix. And carrying out melt blending on the premix in a double-screw extruder, granulating to obtain composite granules, and finally carrying out injection molding on the composite granules to obtain the composite material.

Comparative example 1

Weighing raw materials according to the mass fractions of the components in comparative example 1 in the table 1; the preparation process was the same as in example 2 to obtain a composite material.

Comparative example 2

Weighing raw materials according to the mass fractions of the components in comparative example 2 in the table 1; the preparation process was the same as in example 2 to obtain a composite material.

Comparative example 3

Weighing raw materials according to the mass fractions of the components in comparative example 3 in the table 1; the preparation process was the same as in example 2 to obtain a composite material.

Comparative example 4

Weighing raw materials according to the mass fraction of each component of comparative example 4 in the table 1; the preparation process was the same as in example 3 to obtain a composite material.

Comparative example 5

Weighing the raw materials according to the mass fractions of the components of comparative example 5 in the table 1, wherein the PEEK of the comparative example 5 is

450PF, the grain size is about 50 μm; the preparation process was the same as in example 3 to obtain a composite material.

Comparative example 6

Weighing raw materials according to the mass fractions of the components in the example 2 in the table 1; adding PEI, PEEK, glass fiber, superfine fully vulcanized acrylate rubber, PC, BMP-BMI, melamine cyanurate, triphenylphosphine oxide, tetra [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid ] pentaerythritol, tris (2, 4-di-tert-butylphenyl) phosphite, N' -ethylene bis stearamide and silicone powder into a high-speed mechanical blender, and uniformly stirring to obtain the premix. And carrying out melt blending on the premix in a double-screw extruder, granulating to obtain composite granules, and finally carrying out injection molding on the composite granules to obtain the composite material.

TABLE 1 formulation tables of high heat-resistant impact-resistant polycarbonate compositions of examples 1 to 3 and comparative examples 1 to 5

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

PC

67％

49％

40％

54％

49％

50％

40％

PEEK

1％

5％

10％

5％

-

10％

PEI

6％

5％

-

5％

VP-301

4％

5％

10％

5％

-

10％

BMP-BMI

1％

5％

-

5％

-

5％

GF

10％

20％

30％

20％

Flame retardant A

3％

Flame retardant B

7％

6％

7％

6％

Antioxidant A

0.3％

Antioxidant B

0.3％

Lubricant A

0.2％

Lubricant B

0.2％

Remarking: in the compositions of examples 1-3 and comparative examples 1-5, PC is a Saber-based LEXAN^TM233R, BMP-BMI is a general product sold in the market, purchased from Kalimeris Henan, New Material science and technology GmbH; in example 1, PEEK is

150UF10, PEI is Ultem 1000; in examples 2 to 3 and comparative examples 1 to 4, PEEK was

KT-820UFP, PEI is Ultem 1010; in comparative example 5, PEEK is

450PF, the grain size is about 50 μm, and PEI is Ultem 1010. In example 1, flame retardant a was melamine polyphosphate and flame retardant B was tricyclohexylphosphine oxide; antioxidant A is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and antioxidant B is 2,2' -oxamido-bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl)]Propionate esters; lubricant A is stearic acid and lubricant B is pentaerythritol stearate. In examples 2 to 3 and comparative examples 1 to 5, flame retardant A was melamine cyanurate and flame retardant B was triphenylphosphine oxide; the antioxidant A is tetra [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol tetraester alcohol, antioxidant B is phosphorous acid tri (2, 4-di-tert-butylphenyl) ester; lubricant A is N, N' -ethylene bis stearamide, and lubricant B is silicone powder。

The polycarbonate composites obtained in examples 1 to 3 and comparative examples 1 to 6 were subjected to a performance test. The mechanical tensile property of the material is tested according to GB/T1040.2-2006, the bending property of the material is tested according to GB/T9341-2008, the softening point of the material is tested according to GB/T1634.2-2004, the unnotched impact strength of the material is tested according to GB/T1843-2008, the flame retardant property of the material is tested according to UL-94 standard, and meanwhile, the floating fiber and the glossiness of the surface of a sample are observed visually. The test results are shown in table 2.

TABLE 2 Performance data for composites of examples 1-3 and comparative examples 1-6

As shown in Table 2, the composites of examples 1-3 have an excellent combination of properties, including good mechanical strength, impact toughness, and high temperature resistance. The composite material of comparative example 1 does not contain BMP-BMI, the elongation at break is increased, but the mechanical strength, the high temperature resistance and the impact toughness are reduced compared with example 2, and the composite material of comparative example 1 lacking BMP-BMI cannot form a complex network structure in the processing process, and the compatibility among the components is poor, thereby influencing the performance of the components. The composite of comparative example 2, which does not contain VP-301, has a greatly reduced impact toughness. The composite material of comparative example 3 does not include PEEK, PEI, BMP-BMI, the heat resistance of the composite material is greatly reduced, the compatibility among the components is poor, a small amount of floating fibers are present in the composite material, and the glossiness is poor. The composite material of comparative example 4, which does not include PEEK, is inferior in performance to that of example 3, whereas the composite material of comparative example 5, which has a PEEK particle size of 50 μm and a PEEK particle size larger than that, has a relatively poor effect of forming physical cross-linking points inside the composite material, thus exhibiting performance inferior to that of example 3 even though PEEK is added to comparative example 5. The composite material of comparative example 6 is prepared without a premixing process, but by directly blending and melting the components, the compatibility between the glass fiber and the polymer is greatly reduced, the composite material presents a small amount of floating fibers and has poor glossiness, the dispersion uniformity of the components in the matrix is also reduced without the premixing process, and the performance of the composite material is also reduced.

According to the invention, the heat softening point of not less than 150 ℃ according to GB/T1634-²The polycarbonate composite material has good comprehensive performance and no notch impact strength.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims

1. The polycarbonate composition with high heat resistance and impact resistance is characterized by comprising the following components in percentage by mass:

40 to 70 percent of polycarbonate,

1-10% of polyether-ether-ketone,

5 to 20 percent of polyetherimide,

5 to 20 percent of superfine fully vulcanized powdered rubber,

1 to 10 percent of bismaleimide,

10 to 30 percent of glass fiber,

5 to 15 percent of flame retardant,

0.1-1.0% of processing aid;

wherein, the polyether-ether-ketone is fine powder with the average grain diameter less than or equal to 20 μm;

the bismaleimide comprises the following structure:

wherein R is selected from one or more of the following structural groups:

。

2. the highly heat and impact resistant polycarbonate composition as claimed in claim 1, wherein the polycarbonate composition has a heat softening point of not less than 150 ℃ as measured by GB/T1634-²The unnotched impact strength of (2).

3. The high heat and impact resistant polycarbonate composition of claim 1, wherein the ultra-fine fully vulcanized powder rubber is selected from one or more of the following: superfine fully-vulcanized powdered nitrile rubber, superfine fully-vulcanized powdered silicon rubber, superfine fully-vulcanized powdered carboxylated nitrile rubber, superfine fully-vulcanized powdered acrylate rubber, superfine fully-vulcanized powdered carboxylated styrene butadiene rubber and superfine fully-vulcanized powdered styrene butadiene rubber, wherein the average particle size is 50-200 nm.

4. The highly heat and impact resistant polycarbonate composition according to claim 1 or 3, wherein the ultra-fine fully vulcanized powder rubber is an ultra-fine fully vulcanized powder acrylate rubber having an average particle diameter of 50 to 150 nm.

5. The highly heat and impact resistant polycarbonate composition according to claim 1, wherein R is the following structural group:

。

6. the highly heat and impact resistant polycarbonate composition according to claim 1, wherein the glass fiber is a chopped glass fiber having a length of 0.1 to 10mm and a diameter of 1 to 100 μm.

7. The high heat and impact resistant polycarbonate composition of claim 1, wherein the flame retardant is a nitrogen-containing flame retardant and/or an organic phosphorus oxide.

8. A method for preparing a high heat and impact resistant polycarbonate composition according to claim 1, comprising the steps of:

s1, weighing the components according to the mass fraction of claim 1;

s2, dissolving polyetherimide in an organic solvent, adding polyether-ether-ketone, glass fiber and superfine fully vulcanized powder rubber, stirring uniformly, slowly adding the mixed solution into water to separate out, boiling and washing with water, and drying to obtain mixed powder containing the polyetherimide, the polyether-ether-ketone, the glass fiber and the superfine fully vulcanized powder rubber;