CN105482425B - Polycarbonate composite material - Google Patents

Abstract

The invention discloses a polycarbonate composite material, comprising 30-80 parts by weight of polycarbonate; 5-40 parts by weight of ABS; 5-80 parts by weight of filler; wherein, based on the total weight of the polycarbonate composite material , the weight content of iron element is 0.1-50ppm. It has been surprisingly found that the present invention can make polycarbonate composites with improved bending by adding iron-containing elements or iron-containing compounds with lower soluble iron content and reducing or avoiding the addition of other iron-containing compounds in the composite materials Modulus and impact strength, and has excellent molding stability and color stability.

Description

A polycarbonate composite material

technical field

The invention belongs to the field of polymer material modification, in particular to a polycarbonate composite material with improved flexural modulus and impact strength and stable long-term performance.

Background technique

Polycarbonate PC has excellent heat resistance and high impact resistance, and is widely used in the field of exterior materials such as electrical/electronic products and automotive parts. In recent years, the thinning of molded articles molded from resin compositions has progressed, and demands for improvement in various physical properties of molded articles have been increasing.

Better rigidity can be obtained by adding fillers in polycarbonate, but the ductility will be greatly reduced. In order to improve the impact strength of materials, there is currently a technology to improve the impact strength of the composition by adding an impact modifier, but it will affect the heat distortion temperature and flow properties of the product, and there are also technologies through the selection of filler size or surface treatment To improve the impact strength, but the increase is not large, the effect is not obvious.

The inventors have surprisingly found that in polycarbonate composites containing fillers, the polycarbonate composites produced can have improved Excellent flexural modulus and impact strength, and has excellent molding stability and color stability.

Contents of the invention

The object of the present invention is to provide a kind of polycarbonate composite material, by adding trace iron element in polycarbonate composite material, can make the polycarbonate composite material obtained have improved flexural modulus and impact strength, and have Excellent forming stability and color stability.

The present invention is achieved through the following technical solutions:

A polycarbonate composite material comprising the following components:

30-80 parts by weight of polycarbonate;

5-40 parts by weight of ABS;

5-80 parts by weight of filler;

Wherein, based on the total weight of the polycarbonate composite material, the weight content of the iron element is 0.1 ppm-50 ppm.

The present invention adds iron-containing elemental substance or iron-containing compound with lower soluble iron content in the composite material, and reduces or avoids the damage caused in the composite material and other foreign metal-containing compounds, especially the presence of traces of active alkali metals , the content of iron in the composite material is controlled within the range of 0.1ppm-50ppm, which can not only avoid the pretreatment of the filler powder, but also stabilize the alkaline ions in the system. Iron element will reduce the color darkening and performance damage caused by the introduction of screw or other metals, so that the prepared polycarbonate composite material has significantly improved flexural modulus and impact strength, and has excellent molding stability and color stability.

Preferably, based on the total weight of the polycarbonate composite material, the weight content of the iron element is 5 ppm-40 ppm, more preferably 10 ppm-30 ppm.

Wherein, the iron element is derived from an iron-containing element or an iron-containing compound, and the iron-containing compound is selected from ferric chloride, ferrous chloride, ferric nitrate, ferric sulfate, ferrous sulfate or iron complexes species or several.

The polycarbonate is selected from homopolycarbonates or copolycarbonates comprising repeating structural carbonate units.

The polycarbonate may have a weight-average molecular weight of about 15000-40000, and the weight-average molecular weight can be measured by methods known in the art. Using polycarbonate within this weight-average molecular weight range as a modified component can take into account processing fluidity and mechanical properties. If the weight-average molecular weight is lower than 15,000, the modified composition will lose toughness and cannot meet the requirements of the product. Requirements, if the weight-average molecular weight is higher than 40,000, it will be difficult to process, which will increase the scrap rate and energy consumption.

The polycarbonate has a PDI coefficient of 2.0-4.0 at the same time, and the PDI coefficient is a polydispersity index, which is determined based on BPA polycarbonate standard gel chromatography. The PDI value is greater than or equal to 1, and the PDI value indicates the uniformity of the polymer molecular chain.

According to ASTM D1238 300°C, the melt flow rate of polycarbonate measured under a load of 1.2kg is 3g/10min-30g/10min; the general molding temperature of the composition is 300°C, at this processing temperature, if the flow of polycarbonate If the rate is too low, the viscosity will be too high, and the compatibility with other components in the composition will be poor, which will eventually lead to an increase in the instability of product performance. If the flow rate of polycarbonate is greater than 30g/10min, it indicates that the molecular segment ends The base content is high, the activity is high, the mechanical properties and color stability of the product are vulnerable to heat and oxygen intrusion during processing, resulting in failure.

The ABS refers to an acrylonitrile-butadiene-styrene graft copolymer, which is prepared by a method well known in the art, and can be prepared by an emulsion method or a solution method, specifically, first by conjugated diene, such as Butadiene or other copolymerizable monomers, such as styrene, are polymerized to provide a polymer backbone to prepare a graft copolymer. After forming the polymer backbone, at least one graft monomer, and specifically two Polymerization is carried out in the presence of a polymer backbone to obtain graft copolymers.

ABS can be obtained by emulsion method or bulk method polymerization.

The ABS copolymer has an average particle size of 500 nm to 2000 nm, preferably has an average particle size of 750 nm to 1250 nm, more preferably has an average particle size of 900 nm to 1100 nm. If the average particle size is greater than 2000nm, the dispersibility of ABS in the matrix will be greatly reduced. If the average particle size is less than 500nm, the synthesis process requirements are relatively harsh, and the yield is low, which cannot meet the requirements of industrialization.

The glass transition temperature of the ABS copolymer is greater than 25°C, preferably greater than 70°C, more preferably greater than 100°C. If the glass transition temperature is too low and the rubber content is too high, the compatibility will be affected. If the glass transition temperature is too high, the polarity of ABS will be high, and the surface energy will be large, which will increase the difficulty of dispersion.

The filler is a mineral filler, specifically talcum powder, wollastonite, kaolin, clay, whiskers, diatomaceous earth, etc., and its volume surface area value is 20um to 90um.

The filler can be without any surface treatment or coating treatment, such as alkyl surface coating, epoxy surface treatment, amide surface treatment, hydroxyl silicone oil, alkyl silane, methoxy silane, sulfonic acid base treatment.

According to different application requirements, the polycarbonate composite material of the present invention can further include 0-20 parts by weight of antioxidants, light stabilizers, impact modifiers, flame retardants, fluorescent whitening agents, lubricants, brighteners, etc. Plasticizers, tougheners, antistatic agents, release agents, pigments, etc.

The antioxidant is selected from one or more of hindered amine antioxidants, hindered phenolic antioxidants, or phosphite antioxidants, specifically 1010, 168, 1076, 445, 1098 One or a mixture of two or more;

Described toughening agent is EVA type toughening agent, EMA type toughening agent, ASA type toughening agent, AES type toughening agent, SAS type toughening agent, acrylate toughening agent, organosilicon toughening agent One or more mixtures.

The light stabilizer is a mixture of one or more of hindered amines or ultraviolet absorbers, specifically one or two of UV-944, UV-234, 770DF, 328, 531, 3896 and a mixture of the above;

The impact modifier is one or a mixture of PTW, styrene-ethylene/butylene-styrene block copolymer SEBS;

The flame retardant is a phosphorus-based flame retardant, specifically bisphenol A bis(diphenyl phosphate) BDP, red phosphorus, OP1240, OP1230, or a mixture of two or more;

The fluorescent whitening agent is one of bistriazine aminostilbene, titanium dioxide or a mixture of both;

The lubricant is one or a mixture of two or more of talcum powder, ethylene bisstearamide EBS, erucamide, zinc stearate, silicone oil;

The plasticizer is one or a mixture of two or more of glycerin, citric acid, butyl citrate, epoxidized soybean oil, etc.;

The antistatic agent is a permanent antistatic agent, specifically PELESTAT-230, PELESTAT-6500, SUNNICO ASA-2500 or a mixture of two or more;

The release agent is one or a mixture of two or more of silicone oil, paraffin, white mineral oil, and vaseline;

The pigment is one or a mixture of two or more of carbon black, black seed, titanium dioxide, zinc sulfide, phthalocyanine blue, and fluorescent orange.

The way to obtain the iron element of the present invention can be by directly adding iron-containing element or iron-containing compound in the polycarbonate composite material processing process, and the addition of iron-containing element or iron-containing compound makes the content of iron element in the composite material reach 0.1ppm-50ppm is suitable.

The polycarbonate composite material of the present invention has a spline size of 12.6mm*3.2mm, a length of more than 100mm, and a flexural modulus of more than 5700MPa at a temperature of 23°C.

The polycarbonate composite material of the present invention has a spline size of 12.6mm*3.2m*67mm, uses a 2.75J pendulum, and has a notched impact strength greater than 70 J/m at a temperature of 23°C.

Due to its excellent flexural modulus and impact strength, the polycarbonate composite material of the present invention can be applied to thin-walled products with enhanced characteristics, such as notebook computer casings, household appliance casings and other fields that require relatively high rigidity.

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

Experiment finds surprisingly, the present invention controls the content of iron element in the composite material by adding iron-containing simple substance or iron-containing compound with lower soluble iron content and reducing or avoiding the addition of other iron-containing compounds in the polycarbonate composite material In the range of 0.1-50ppm, the prepared polycarbonate composite material can have improved flexural modulus and impact strength, and have excellent molding stability and color stability.

detailed description

The present invention will be further described below through specific embodiments. The following examples are preferred implementation forms of the present invention, but the implementation manners of the present invention are not limited by the following examples.

PC: Homopolymer, weight average molecular weight 22000, PDI coefficient 2.0, melt flow rate 10g/10min Nippon Idemitsu;

ABS1: SAN grafted butadiene, with an average particle size of 1000nm and a glass transition temperature of 110°C;

ABS2: SAN grafted butadiene, with an average particle size of 750nm and a glass transition temperature of 80°C;

ABS3: SAN grafted butadiene, with an average particle size of 1500nm and a glass transition temperature of 60°C;

Flame retardant: bisphenol A bis (diphenyl phosphate) BDP, Adeka;

Iron-containing element and iron-containing compound: both are commercially available;

Filler 1: Talc powder, uncoated Imery, with a volume surface area of 29um;

Filler 2: Talc powder, Imery coated on the surface of the alkyl group, with a volume surface area of 32um;

Filler 3; Talc powder, epoxy surface treatment Imery, volume surface area is 40um;

Filler 4; Talc powder, amide surface treatment Imery, volume surface area is 25um;

Other additives: Toughener: HR-181

Antioxidant 1076, CIBA

Antioxidant 168, CIBA

Release agent PETS, Lonza

Light stabilizer 3896, Cytec

Embodiment 1-12 and comparative example 1-2: the preparation of polycarbonate composite material

According to the formula in Table 1, blend polycarbonate, ABS resin, iron-containing compounds, fillers, and flame retardants in a high-speed mixer to obtain a pretreated resin matrix; pretreated resin matrix and other additives in proportion After weighing, blending is completed by a high-speed mixer or a mixer, the extrusion temperature is 240 ° C, cooled by water, and pelletized to obtain a polycarbonate composite material with columnar particles. The ratio of each component and performance test results are shown in Table 1.

Various performance evaluation methods:

(1) Flexural modulus:

The polycarbonate composite material is injection molded at an injection temperature of 260°C, the mold temperature is 100°C, and the test piece with a sample size of 12.6mm*3.2mm and a length greater than 100mm is used to measure At a flexural modulus of 23°C, the speed of the sensor bar is 1 mm/min.

(2) Impact strength

The polycarbonate composite material was injection molded at an injection temperature of 260°C, the mold temperature was 100°C, the sample size was 12.6mm*3.2m*67mm, and a 2.75J pendulum was used to measure the notched impact strength at 23°C.

(3) Molding stability

Using an 80-ton injection molding machine manufactured by Nissei Plastic Industry Co., Ltd., stay at a barrel temperature of 300°C for 20

Minutes, then inject the polycarbonate composite material, measure the weight-average molecular weight before and after injection, and evaluate the molding stability. The smaller the absolute value of the difference between the "weight average molecular weight after injection" and the "weight average molecular weight before injection", the more preferable. Here, when the absolute value of the difference is less than 2000, the evaluation is "good (G)", when the absolute value of the difference is 2000 or more and less than 5000, the evaluation is "medium (M)", and when the absolute value of the difference is 5000 or more , evaluated as "Bad (NG)".

(4) Determination method of iron content

Accurately weigh 2g of polycarbonate composite particles in an analytical balance, pour them into a 100ml digestion bottle, then add 5ml of 97% concentrated sulfuric acid, heat in an iron plate heating instrument at a preset temperature of 300°C for 10 minutes, and then add 5ml of 68% nitric acid, keep heating for another 20 minutes to completely decompose the particles, then cool to room temperature, add 20ml of hydrogen peroxide to neutralize the acidity until the pH value is 7, dilute the above liquid with deionized water, and introduce the liquid through the sampling tube The concentration of iron element is determined in the ICP detection instrument.

(5) Color stability

The polycarbonate composite material is injection molded to produce a plate with a thickness of 2 mm, a width of 40 mm, and a length of 100 mm. The mold temperature is set at 80 °C, and the injection molded plate is adjusted for 48 hours at a room temperature of 23 °C and a humidity of 50%. Test, and according to the injection molding conditions of (3), produce a plate with a thickness of 2 mm, a width of 40 mm, and a length of 100 mm, wherein the mold temperature is set at 80 °C. After the injection molded board is adjusted for 48 hours at a room temperature of 23°C and a humidity of 50%, the color difference test is carried out, and the difference (ΔE) between the two test boards is calculated. The smaller this difference, the smaller the hue change.

(6) Flame retardancy: standard UL94

Table 1 The proportions (parts by weight) and performance test results of each component in Examples 1-12 and Comparative Examples 1-2

As can be seen from Examples 1-12 of Table 1, the iron element content in the polycarbonate composite material is in the range of 0.1-50ppm, the flexural modulus of the polycarbonate composite material is greater than 5700MPa, and the notched impact strength is greater than 70 J/m; These polycarbonate composites have excellent molding stability and color stability. In Comparative Example 1-2, when the iron content in the polycarbonate composite material is less than 0.1ppm or greater than 50ppm, the flexural modulus, notched impact strength, molding stability, color stability and flame retardancy of the polycarbonate composite material significantly worse than the examples. It can be seen from this that by controlling the content of iron in the polycarbonate composite material, the prepared polycarbonate composite material has significantly improved flexural modulus and impact strength, and has excellent molding stability and color stability, Excellent overall performance.

Claims (13)

1. a kind of polycarbonate composite material, it is characterised in that including following component：

The Merlon of 30-80 weight portions；

The ABS of 5-40 weight portions；

The filler of 5-80 weight portions；

Wherein, the gross weight based on polycarbonate composite material, the weight content of ferrum element is 0.1ppm-50ppm.

2. polycarbonate composite material according to claim 1, it is characterised in that the weight content of the ferrum element is adopted Following method is determined：The granule 2g of accurate weighing polycarbonate composite material in analytical balance, pours 100ml into and clears up in bottle, 97% concentrated sulphuric acid 5ml is subsequently adding, is heated 10 minutes in 300 DEG C of iron plate heating instruments of preset temperature, is then added 68% Nitric acid 5ml, then keep heating 20 minutes, make particulate matter after decomposing completely, be cooled to room temperature, add the hydrogen peroxide neutralization of 20ml After acidity is 7 to pH value, liquid is imported in ICP detecting instruments by sample feeding pipe and is determined by deionized water dilution aforesaid liquid The concentration of ferrum element.

3. polycarbonate composite material according to claim 1, it is characterised in that based on the total of polycarbonate composite material Weight, the weight content of ferrum element is 5ppm-40ppm.

4. polycarbonate composite material according to claim 3, it is characterised in that based on the total of polycarbonate composite material Weight, the weight content of ferrum element is 10ppm-30ppm.

5. polycarbonate composite material according to claim 1, it is characterised in that the Merlon is homo-polycarbonate Or Copolycarbonate, the weight average molecular weight of the Merlon is 15000-40000, and PDI coefficients are based on BPA polycarbonate standard Gel chromatography is 2.0-4.0, and melt flow rate (MFR) is measured as under 1.2kg loads for 300 DEG C according to ASTM D1238 3g/10min-30g/10min。

6. polycarbonate composite material according to claim 1, it is characterised in that the ABS is emulsion method or solution Prepared by method, particle mean size is 500nm to 2000nm, and glass transition temperature is more than 25 DEG C.

7. polycarbonate composite material according to claim 6, it is characterised in that the ABS particle mean sizes are 750nm- 1250nm, glass transition temperature are more than 70 DEG C.

8. polycarbonate composite material according to claim 7, it is characterised in that the ABS particle mean sizes are 900nm- 1100nm, glass transition temperature are more than 100 DEG C.

9. polycarbonate composite material according to claim 1, it is characterised in that described filler is mineral filler, volume Surface area is 20um to 90um.

10. polycarbonate composite material according to claim 1, it is characterised in that the ferrum element derives from iron content list Matter or iron containing compoundses, the iron containing compoundses are selected from iron chloride, ferrous chloride, ferric nitrate, iron sulfate, ferrous sulfate or ferrum One or more in complex.

11. polycarbonate composite materials according to claim 1, it is characterised in that the polycarbonate composite material is also Antioxidant, light stabilizer, impact modifier, fire retardant, fluorescent whitening agent, lubricant, plasticizer including 0-20 weight portions, One or more in toughener, antistatic additive, releasing agent, pigment.

12. polycarbonate composite materials according to any one of claim 1-11, it is characterised in that the Merlon is multiple Condensation material is 12.6mm*3.2mm in batten size, and more than 100mm, temperature is that 23 DEG C of bending moduluses are more than 5700MPa to length.

13. polycarbonate composite materials according to any one of claim 1-11, it is characterised in that the Merlon is multiple Condensation material is 12.6mm*3.2m*67mm in batten size, and using the pendulum of 2.75J, temperature is that 23 DEG C of notch impact strength is big In 70 J/m.