CN101469115A - High flowability and high tenacity polycarbonate composition - Google Patents

Abstract

The invention discloses a polycarbonate composition with high fluidity and high toughness, which comprises the following components by weight portion: 40 to 85 portions of polycarbonate, 10 to 55 portions of two acrylonitrile-butadiene-phenethylene graft copolymer ABS mixtures with different rubber particle diameters, and 2 to 5 portions of thermoplastic polyester. The PC composition has the advantages of high toughness, good low-temperature impact resisting property in particular and good fluidity, and is easy to fill and form large-sized moulds. The polycarbonate composition with the high fluidity and the high toughness can be used for manufacturing various large-scale plastic products such as automobile instrument board and the like.

Description

A kind of high mobile, high tenacity polycarbonate composite

Technical field

The present invention relates to polycarbonate compositions, especially a kind of high mobile, high tenacity polycarbonate composite belongs to the polymer composite field.

Background technology

Polycarbonate (PC) plastics have the thermotolerance height, and transparency is good, the gloss height, and advantages such as good toughness, but it is mobile poor, difficult forming; Goods are easy to generate stress cracking to the breach sensitivity; Not anti-solvent, and cost an arm and a leg.

Have and manyly knownly improve these shortcomings by the method for preparing the PC polyblend, wherein the PC/ABS polyblend is modal method, for example U.S. Pat 3130177, US4624986 etc. have obtained high impact toughness and have improved mobile low-cost PC/ABS polyblend composition by the blending technology with ABS and PC.

When the PC/ABS blend composition being applied to as various large-scale plastic items such as fascia and electronic apparatus shell, often require this material to have more low melt viscosity, in the time of better processing characteristics, still keep good comprehensive performances such as shock strength height.Yet, the serious consequence that the effort of the various further PC/ABS of improvement flowabilities all may cause resistance to impact shock and heat-resistant deforming temperature (HDT) to reduce.

Summary of the invention

The object of the invention provides a kind of high mobile, high tenacity polycarbonate composite.To solve the problems referred to above of prior art.

Purpose of the present invention can be achieved through the following technical solutions:

A kind of high mobile, high tenacity polycarbonate composite, the mixture and the thermoplastic polyester that comprise the acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) that polycarbonate, two kinds of rubber sizes are different, described polycarbonate is 40～85 weight parts, acrylonitrile-butadiene-phenylethene grafted copolymer ABS mixture is 10～55 weight parts, and thermoplastic polyester is 2～5 weight parts.

Described polycarbonate is the bisphenol A-type aromatic copolycarbonate.

In preferred embodiments, polycarbonate resin component of the present invention is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.

In preferred embodiments, the weight-average molecular weight of polycarbonate resin of the present invention is 20000-40000g/mol, and polycarbonate resin of the present invention is known and can obtains by a plurality of commercial source.

The mixture of described acrylonitrile-butadiene-phenylethene grafted copolymer comprises that ABS-1 that rubber size is respectively 0.5～1 μ m and rubber size are the mixing of two kinds of ABS of the ABS-2 of 0.1～0.4 μ m.Its blending ratio be ABS-1 account for whole ABS mixtures 50%～90%.

Described thermoplastic polyester is polybutylene terephthalate resin (PBT), one of pet resin (PET), or their mixture.

Described composition also can comprise tinting material, filler, thermo-stabilizer, static inhibitor, lubricant etc.

PC composition of the present invention has high tenacity, particularly good low-temperature impact performance; Mobile good, be easy to filling shaping large size mould; Heat-drawn wire remains unchanged simultaneously.Height of the present invention flows, high tenacity polycarbonate composite can be used for various large-scale plastic parts such as fascia.

Embodiment

Below in conjunction with specific embodiment, the present invention will be further described, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.

Embodiments of the invention adopt following material:

Polycarbonate, U.S. Dow chemical company, weight-average molecular weight is about 27,000, trade mark Calibre201-10;

Polycarbonate-2, U.S. Dow chemical company, weight-average molecular weight is about 30,000, trade mark Calibre301-5

ABS-1, U.S. Dow chemical company, average rubber particle size is 0.61 μ m, trade mark Magnum 3904;

ABS-2-1, Lanzhou general petrochemicals factory produces, and average rubber particle size is 0.26 μ m, and divinyl rubber content is 60%;

ABS-2-2 extrudes preparation by the SAN of 40%ABS-2-1 and 60% (weight) by twin screw, and average rubber particle size is 0.34 μ m, and divinyl rubber content is 24%;

Acrylonitritrile-styrene resin SAN, Taiwan Qi Mei company, trade mark PN-127H;

Polybutylene terephthalate resin PBT, BASF AG, trade mark B4500;

Pet resin PET far spins industrial (Shanghai) Co., Ltd., trade mark CB-608S;

Processing aid OP wax, Clariant company;

Oxidation inhibitor, tetramethylolmethane stearic bicine diester bis-phosphite, GE plastics fine chemicals, Weston 619F.

The product performance testing method:

Melting index: press ASTM D1238 method, 260 ℃, test under 5 kilograms of load

Tensile property: press ASTM D638 method, draw speed 50 mm/min.

Bending property: press ASTM D790 method, trial speed 2 mm/min.

IZOD notched Izod impact strength: press ASTM D256 method, the sample of 3.2 mm thick.

The low temperature multiaxis impacts: press ASTM D3763 method, trial speed 6.6 meter per seconds are tested 10 100 * 100 millimeters, the print of 3.2 mm thick, and the ratio of calculating toughness failure mode print.The test environment temperature is-30 ℃.

Heat-drawn wire: press ASTM D648 method, 120 ℃/hour of temperature rise rates are tested under the 1.82MPa load.

Embodiment 1-3 and comparative example 1-2:

After mixing by proportion of composing in the table 1, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, styrene copolymer resin ABS, PBT and other auxiliary agent.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.The said products is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result sees Table 1.

Table 1:

Form	Comparative example 1	Comparative example 2	Embodiment 1	Embodiment 2	Embodiment 3
						PC-1	65	65	65	65	65
ABS-1		35	28	22	16
						ABS-2-1			4	10
ABS-2-2	35				16
						PBT			3	3	3

OP wax	0.2	0.2	0.2	0.2	0.2
						Stablizer 619F	0.2	0.2	0.2	0.2	0.2
Test result	Comparative example 1	Comparative example 2	Embodiment 1	Embodiment 2	Embodiment 3
						Melting index	16.6	12.7	23.5	26.6	25.7
Tensile strength (MPa)	54.6	53.2	52.3	50.6	54.6
						Modulus in flexure (MPa)	2360	2170	2180	2020	2380
Notched Izod impact strength	520	636	537	656	517
						Heat-drawn wire (℃)	103.4	103.8	104.2	102.2	103.3
The multiaxis shock strength,
						The ultimate load energy, J	54	70	68	82	71
Toughness failure mode ratio	0/10	2/10	7/10	9/10	7/10

By table 1 as seen, with disclosed technology, promptly directly compare (comparative example 1 and comparative example 2) with the PC/ABS alloy material that independent a kind of ABS resin is produced by PC, PC/ABS composition by the present invention's preparation has bigger low temperature multiaxis impact value, and the ratio of exemplar toughness failure mode increases greatly simultaneously; In addition, the PC/ABS composition that is prepared by the present invention also has bigger melting index, shows that this composition material has more excellent processing characteristics; Simultaneously, the material of mechanics such as tensile strength, heat-drawn wire and resistance toheat and prior art production is suitable.

Embodiment 4-7 and comparative example 3:

After mixing by proportion of composing in the table 2, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, styrene copolymer resin ABS, PBT, PET and other auxiliary agent.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.The said products is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result sees Table 2.

Table 2:

Form	Comparative example 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7
						PC-2	70	40	55	70	85
ABS-1	25	50	40	22	5
						ABS-2-1	5		5	5	5
ABS-2-2		8
						PBT		2	3	3
PET					5
						OP wax	0.2	0.2	0.2	0.2	0.2
Stablizer 619F	0.2	0.2	0.2	0.2	0.2
						Test result	Comparative example 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7
Melting index	8.3	22.7	22.8	20.6	22.7
						Tensile strength (MPa)	57.6	53.5	52.2	57.6	60.6
Modulus in flexure (MPa)	2360	2270	2160	2220	2380
						Notched Izod impact strength	520	426	667	626	627
Heat-drawn wire (℃)	107.6	93.1	98.7	108.2	123.2
						The multiaxis shock strength,
The ultimate load energy, J	75	54	76	78	78
						Toughness failure mode ratio	9/10	5/10	8/10	9/10	7/10

By table 2 as seen, when various different PC content, kept the exemplar toughness failure mode of excellent low temperature multiaxis impact value, particularly vast scale by the PC/ABS composition of the present invention's preparation; Simultaneously, the material of mechanics such as tensile strength, heat-drawn wire and resistance toheat and prior art production is suitable.Yet, have bigger melting index by the PC/ABS composition of the present invention's preparation, show that this composition material has more excellent processing characteristics; (comparative examples 3 and embodiment 6).

The object of the invention provides a kind of high mobile, high tenacity polycarbonate composite.PC composition of the present invention has high tenacity, particularly good low-temperature impact performance; Mobile good, be easy to filling shaping large size mould; Heat-drawn wire remains unchanged simultaneously.Height of the present invention flows, high tenacity polycarbonate composite can be used for various large-scale plastic parts such as fascia.

Claims (7)

1, a kind of high mobile, high tenacity polycarbonate composite, the mixture and the thermoplastic polyester that comprise the acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) that polycarbonate, two kinds of rubber sizes are different, described polycarbonate is 40～85 weight parts, acrylonitrile-butadiene-phenylethene grafted copolymer ABS mixture is 10～55 weight parts, and thermoplastic polyester is 2～5 weight parts.

2, a kind of high mobile, high tenacity polycarbonate composite according to claim 1, it is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate.

3, a kind of high mobile, high tenacity polycarbonate composite according to claim 2, it is characterized in that: polycarbonate resin component of the present invention is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.

4, a kind of high mobile, high tenacity polycarbonate composite according to claim 1, it is characterized in that: the weight-average molecular weight of described polycarbonate resin is 20000-40000g/mol.

5, according to claim 1ly a kind ofly highly flow, high tenacity polycarbonate composite, it is characterized in that: the mixture of described acrylonitrile-butadiene-phenylethene grafted copolymer comprises that ABS-1 that rubber size is respectively 0.5～1 μ m and rubber size are the mixing of two kinds of ABS of the ABS-2 of 0.1～0.4 μ m.

6, according to claim 5ly a kind ofly highly flow, high tenacity polycarbonate composite, it is characterized in that: two kinds of ABS of described ABS-1 and ABS-2, its blending ratio be ABS-1 account for whole ABS mixtures 50%～90%.

7, a kind of high mobile, high tenacity polycarbonate composite according to claim 1, it is characterized in that: described thermoplastic polyester is one or both mixtures in polybutylene terephthalate resin, the pet resin.