CN109777064B - Extrusion-grade polycarbonate alloy material and preparation method and application thereof - Google Patents
Extrusion-grade polycarbonate alloy material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer blending and molding processing, and provides an extrusion-grade polycarbonate alloy material and a preparation method and application thereof; the extrusion-grade polycarbonate alloy material is prepared from the following components in percentage by weight, wherein the following components are calculated by the total weight of 100 wt% in percentage by weight: 30-90 wt% of polycarbonate resin, 5-60 wt% of rubber graft polymer, 1-20 wt% of polyolefin polymer, 0.1-10 wt% of compatilizer and 0-20 wt% of flame retardant. The preparation method comprises the following steps: (1) contacting and mixing the components; (2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder, and stretching and granulating after the materials are melted and extruded. By adding the polyolefin polymer, the melt strength of the obtained polycarbonate alloy material can be obviously improved while the physical and mechanical properties are ensured to be good.
Description
Technical Field
The invention belongs to the technical field of polymer blending and molding processing, and particularly relates to an extrusion-grade polycarbonate alloy material as well as a preparation method and application thereof.
Background
Products such as wire cable grooves, building plates and the like are not suitable for being prepared by adopting an injection molding process due to the characteristics of large thickness, long length and the like, so that the products are generally prepared by adopting an extrusion process. Therefore, the choice of extrusion process requires materials with higher melt strength. Although the melt strength of the PC/ABS alloy is high, the PC/ABS alloy cannot completely meet the requirements of an extrusion process, and quality problems such as unstable size, uneven product surface, bubble and the like often occur.
With the improvement of safety consciousness and national law and regulation requirements of people, the performance requirements of the fields of buildings, electronics and electricity and the like on materials are gradually improved, and flame retardant requirements are provided for partial materials used for electric wire cable grooves and building plates, but the flame retardant property of general-grade polycarbonate alloy cannot meet the requirements, and a certain amount of flame retardant is required to be added.
However, the addition of flame retardants, especially phosphorus-based flame retardants, has a strong plasticizing effect that significantly reduces the melt viscosity of the system. Therefore, during the extrusion process for preparing the plate and the cable groove, the phenomenon can cause the problems of uneven surface, air holes, suspension and the like of the plate.
For PC/ABS systems, much attention is paid to injection-molded grade products, while less consideration is given to extrusion-grade products, in particular their process stability.
The patent document with the publication number CN 102061077A discloses a halogen-free flame-retardant PC/ABS alloy, which comprises the following components in parts by mass: 60-70 parts of PC resin, 10-25 parts of ABS resin, 8-12 parts of phosphate flame retardant, 0.5-3 parts of flame retardant synergist, 3-10 parts of toughening agent, 2-5 parts of compatilizer and 0.2-0.4 part of antioxidant. The modified PC/ABS alloy prepared by blending and extruding the components has high flame retardant efficiency, excellent mechanical property, no halogen and no toxicity, has no pollution to the environment, and can be widely used as automobile and electronic and electric appliance materials. However, the flame-retardant PC/ABS product invented by the patent has low melt strength due to the addition of the phosphorus flame retardant, is only suitable for injection molding and is not suitable for extrusion molding.
The patent document CN102329488 discloses an extrusion-grade low-smoke halogen-free flame-retardant PC/ABS material and a preparation method thereof, wherein the PC/ABS material comprises the following components in parts by weight: 63-72% of PC; 5-12% of ABS; 7-15% of halogen-free flame retardant; 5-16% of an auxiliary agent. The extrusion-grade low-smoke halogen-free flame-retardant PC/ABS material has the characteristics of good flame retardant property, environmental protection and the like. But the added halogen-free flame retardant is concentrated phosphate containing 6-20 percent of phosphorus. The melt viscosity of the concentrated phosphate is low, which inevitably affects the extrusion stability of the product, thereby causing the reduction of the yield.
At present, the main application of polycarbonate alloy materials with flame retardant property is focused in the injection molding field, but the extrusion grade market of related products is rapidly developing, and the extrusion process and the injection molding process have significant difference. Therefore, it is imperative to develop an extrusion-molded polycarbonate alloy product having excellent physical and mechanical properties and also having excellent extrusion characteristics.
Disclosure of Invention
The invention aims to solve the problem that the PC/ABS material prepared by the prior art cannot give consideration to excellent physical and mechanical properties and extrusion stability; providing an extrusion grade polycarbonate alloy material, a preparation method and application thereof; by adding the polyolefin polymer and the corresponding compatible system, the melt strength of the obtained polycarbonate alloy material is obviously improved, the extrusion molding stability of the product is greatly improved, and the product still has excellent physical and mechanical properties.
In order to achieve the above object, the present invention provides an extrusion-grade polycarbonate alloy material, which is prepared from the following components in percentage by weight, wherein the following components are in percentage by weight and the total weight of the components is 100 wt%:
preferably, the extrusion grade polycarbonate alloy material is prepared from the following components in percentage by weight:
according to the extrusion grade polycarbonate alloy material provided by the invention, preferably, the polycarbonate resin is selected from one or more of aromatic polycarbonate, aliphatic polycarbonate and aromatic-aliphatic polycarbonate. In a preferred embodiment of the present invention, the polycarbonate resin is selected from bisphenol a type polycarbonates.
Preferably, the bisphenol A polycarbonate has a melt index of 0.1 to 40g/10min, more preferably 0.2 to 30g/10min, and still more preferably 0.5 to 20g/10min under the test conditions of 300 ℃ and 1.2 kg.
According to the extrusion grade polycarbonate alloy material provided by the invention, preferably, the rubber graft polymer is selected from one or more of acrylonitrile-butadiene-styrene graft copolymer (ABS), methyl methacrylate-butadiene-styrene copolymer (MBS) and acrylonitrile-styrene-acrylate terpolymer (ASA), and is preferably selected from acrylonitrile-butadiene-styrene graft copolymer (ABS). The production method of the acrylonitrile-butadiene-styrene graft copolymer (ABS) can be obtained by a continuous bulk method or an emulsion blending method.
Further preferably, the content of butadiene is 10 to 40 wt%, the content of acrylonitrile is 15 to 30 wt%, and the content of styrene is 45 to 70 wt%, based on 100 wt% of the total weight of the acrylonitrile-butadiene-styrene graft copolymer (ABS).
According to the extrusion grade polycarbonate alloy material provided by the invention, preferably, the polyolefin polymer is selected from polyethylene and/or polypropylene, and more preferably selected from ultrahigh molecular weight polyethylene and/or branched polypropylene.
In a preferred embodiment of the invention, the polyolefin polymer is selected from ultra high molecular weight polyethylene.
Ultra-high molecular weight polyethylene, generally referred to as having a relative number average molecular mass of 150X 104Above, especially at 200X 104The above polyethylene. According to the extrusion grade polycarbonate alloy material provided by the invention, the number average molecular weight of the ultrahigh molecular weight polyethylene is preferably 150 x 104-500×104More preferably 200X 104-400×104。
In a preferred embodiment of the invention, the polyolefin polymer is selected from branched polypropylene.
The branched polypropylene is a long chain branched polypropylene, and the structure of the long chain branched is beneficial to enhancing the melt strength of the polypropylene, so the long chain branched polypropylene generally has higher melt strength and can be called as high melt strength polypropylene. The melt strength of high melt strength polypropylene is generally above 0.1N.
Preferably, the branched polypropylene has a melt strength of 0.1 to 1N, more preferably 0.2 to 0.5N, under test conditions of a temperature of 210 ℃, an initial piston velocity of 0.1mm/s and a traction acceleration of 11.0 mm/s.
According to the extrusion grade polycarbonate alloy material provided by the invention, the compatilizer is preferably selected from polyolefin graft copolymers with active groups, and is preferably selected from one or more of maleic anhydride grafted polyethylene (PE-g-MAH), polyethylene grafted glycidyl methacrylate (PE-g-GMA), maleic anhydride grafted polypropylene (PP-g-MAH), polypropylene grafted glycidyl methacrylate (PP-g-GMA), polyethylene octene copolymer elastomer grafted maleic anhydride POE-g-MAH and polyethylene octene copolymer elastomer grafted glycidyl methacrylate POE-g-GMA. Wherein, MAH is maleic anhydride, and GMA is glycidyl methacrylate.
In a preferred embodiment of the invention, the compatibilizer is POE-g-MAH. The use of the compatilizer can improve the compatibility of the polycarbonate alloy base stock and the polyolefin polymer, and can obviously improve the toughness of the system without adding a toughening agent.
Further preferably, in the POE-g-MAH, the graft ratio of MAH is 0.5 to 1.5 wt%, more preferably 0.9 to 1.1 wt%.
According to the extrusion grade polycarbonate alloy material provided by the invention, the flame retardant is preferably one or more selected from organosilicon flame retardants, organic phosphorus flame retardants and organic sulfonic acid metal salt flame retardants, and is preferably organic phosphorus flame retardant.
Preferably, the organophosphorus flame retardant is selected from one or more of resorcinol bis (diphenyl phosphate), bisphenol a bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], triphenyl phosphate and polyaryl phosphate, more preferably bisphenol a bis (diphenyl phosphate).
According to the extrusion grade polycarbonate alloy material provided by the invention, preferably, the components further comprise a plastic additive.
The plastic additive is used in an amount of 0 to 10 wt%, preferably 0.1 to 5 wt%, based on the total weight of the polycarbonate resin, the rubber graft polymer, the polyolefin polymer, the compatibilizer, and the flame retardant.
Preferably, the plastic additive is selected from one or more of an anti-dripping agent, an antioxidant and a lubricant.
The anti-dripping agent is coated polytetrafluoroethylene or pure powder polytetrafluoroethylene, and is preferably coated polytetrafluoroethylene. The coated polytetrafluoroethylene is preferably styrene-acrylonitrile coated polytetrafluoroethylene.
The anti-dripping agent is used in an amount of 0 wt% to 5 wt%, preferably 0.1 wt% to 3 wt%, based on the total weight of the polycarbonate resin, the rubber graft polymer, the polyolefin polymer, the compatibilizer, and the flame retardant.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant. The primary antioxidant may be selected from, but is not limited to, n-octadecyl beta- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the like, and the secondary antioxidant includes one or more of tris [ 2.4-di-tert-butylphenyl ] phosphite and bis [ 2.4-di-tert-butylphenyl ] pentaerythritol diphosphite.
The lubricant may be selected from, but is not limited to, pentaerythritol stearate (PETS) and/or silicone powder.
The amount of the antioxidant is 0 wt% -2 wt%, preferably 0.2 wt% -1 wt% of the total weight of the polycarbonate resin, the rubber graft polymer, the polyolefin polymer, the compatilizer and the flame retardant.
The lubricant is used in an amount of 0 wt% to 2 wt%, preferably 0.2 wt% to 1 wt%, based on the total weight of the polycarbonate resin, the rubber graft polymer, the polyolefin polymer, the compatibilizer, and the flame retardant.
Another object of the present invention is to provide a method for preparing the extrusion-grade polycarbonate alloy material, which comprises the following steps:
(1) contacting and mixing the components;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder, and stretching and granulating after the materials are melted and extruded.
According to the preparation method provided by the invention, preferably, the mixing process conditions of the step (1) are as follows: the mixing temperature is 10-80 deg.C, and the mixing time is 1-30 min.
Preferably, the extrusion process conditions in step (2) are: the barrel temperature of the double-screw extruder is 230 ℃ and 280 ℃, and the screw rotating speed is 100RPM and 800 RPM.
The invention also provides an application of the extrusion grade polycarbonate alloy material or the extrusion grade polycarbonate alloy material prepared by the preparation method in the field of wire cable grooves or building plates.
The extrusion-grade polycarbonate alloy material prepared by the invention can be used for preparing an electric wire cable groove, is prepared by adopting an extrusion molding process, and has certain flame-retardant requirements on raw materials in order to prevent the electric wire from being ignited by fire.
The extrusion-grade polycarbonate alloy material prepared by the invention can also be used for preparing building boards and the like, and is prepared by adopting an extrusion molding process to prepare hollow boards, multilayer boards, sunlight boards and the like.
The technical scheme of the invention has the following beneficial effects:
(1) the melt strength of the prepared polycarbonate alloy is obviously improved by adding the polyolefin polymer, particularly the polyolefin polymer with high melt content and a corresponding compatible system, so that the extrusion molding stability of the product is greatly improved;
(2) meanwhile, the compatilizer is used, so that the compatibility of the polycarbonate alloy base material and the polyolefin polymer is improved, and the system toughness is obviously improved under the condition of not adding the toughening agent;
(3) the invention is especially suitable for the flame-retardant polycarbonate alloy containing the flame retardant, especially the phosphorus flame retardant, and can obviously improve the melt strength of the obtained polycarbonate alloy material while ensuring good physical and mechanical properties.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below by way of examples. While the preferred embodiments of the present invention are shown in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Firstly, raw material sources are as follows:
1. polycarbonate resin: kashingdi K-1300Y, 300 deg.C, 1.2kg melt index of 3g/10 min;
2. ABS resin: the melt index of Shanghai Gaoqiao 3513 at 220 ℃ under 10kg is 3.9g/10 min;
3. polypropylene polymer:
1) high melt strength PP, Nordic chemical WB180HMS, melt strength 0.17N;
2) high melt strength PP, Nordic chemical WB260HMS, melt strength of 0.2N;
3) general homopolymer grade PP, Exxon Mobil LNR010, melt strength 0.05N.
4. Polyethylene:
1) ultra-high molecular weight polyethylene, Mitsui chemical 240M, molecular weight 200X 104；
2) Ultra-high molecular weight polyethylene, Beijing Oriental petrochemical M2, molecular weight 180X 104；
3) High-molecular polyethylene, Yanshan petrochemical 5000S, molecular weight 14X 104。
5. A compatilizer:
1) exxonmobil 1215HT, grafting rate 1.2%;
2) exxonmobil 0812HT, the grafting yield is 0.8%;
3) the grafting rate of the Guangzhou modest chemical PO-003 is 1 percent;
6. a toughening agent: mitsubishi yang, silicon-based toughener S-2001;
7. organic phosphorus compounds: bisphenol a-bis (diphenyl phosphate) (BDP), available from wan shoji, zhejiang;
8. anti-dripping agent: guangzhou entropy energy polymer technology, Inc., SN3300B3, styrene-acrylonitrile coated polytetrafluoroethylene; wherein the mass ratio of the styrene-acrylonitrile to the polytetrafluoroethylene is 1: 1.
9. Antioxidant: basf B900; wherein the mass ratio of the beta- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionic acid n-octadecyl ester (1076) to the tris [2, 4-di-tert-butylphenyl ] phosphite (168) is 1: 4;
10. lubricant: american dragon sand PETS.
Secondly, a test method comprises the following steps:
1. and (3) observing extrusion stability: and (3) preparing the plate by adopting a single-screw extruder, continuously extruding for 3min, then cutting the plate with the corresponding length, and observing whether the surface of the plate is flat or not, whether pores exist or not and whether size deformation occurs or not. The judgment standard is as follows:
(1) very stable: no air bubble, and the deviation of the two diagonal lines is less than or equal to 1.5 mm;
(2) and (3) stabilizing: 1-3 bubbles are present, and no deformation is visible to naked eyes;
(3) instability: the number of bubbles is more than or equal to 4, and visible deformation occurs.
2. Melt strength testing of the polymers:
the melt strength test was carried out using a German Goettfert melt Strength tester under test conditions of a temperature of 240 ℃, an initial piston speed of 0.1mm/s and a traction acceleration of 11.0 mm/s.
Example 1
(1) Weighing 7.5kg of K-1300Y, 1kg of 3513, 1kg of WB260HMS, 0.5kg of PO-003, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 2
(1) Weighing 6kg of K-1300Y, 3kg of 3513, 0.8kg of WB260HMS, 0.2kg of PO-003, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 3
(1) Weighing 9kg of K-1300Y, 0.5kg of 3513, 0.1kg of WB260HMS, 0.3kg of 1215HT, 0.1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 280 deg.C, 270 deg.C; the temperature of the neck ring mold is 270 ℃, the extrusion rotating speed is 100RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Example 4
(1) Weighing 8kg of K-1300Y, 0.7kg of 3513, 0.8kg of WB260HMS, 0.05kg of PO-003, 0.45kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 5
(1) Weighing 6.5kg of K-1300Y, 1kg of 3513, 1kg of WB260HMS, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 6
(1) Weighing 6kg of K-1300Y, 2kg of 3513, 0.5kg of WB260HMS, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 245 deg.C, 240 deg.C; the temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 200RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 7
(1) Weighing 5kg of K-1300Y, 3kg of 3513, 0.5kg of WB180HMS, 0.5kg of 0812HT, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 245 deg.C, 240 deg.C; the temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 800RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Example 8
(1) Weighing 5kg of K-1300Y, 2kg of 3513, 1.5kg of WB260HMS, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 9
(1) Weighing 5kg of K-1300Y, 2kg of 3513, 1.2kg of WB180HMS, 0.8kg of 0812HT, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 245 deg.C, 240 deg.C; the temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Example 10
(1) Weighing 4.7kg of K-1300Y, 0.3kg of 3513, 2kg of WB180HMS, 1kg of PO-003, 2kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 240 deg.C, 235 deg.C; the temperature of the neck ring mold is 235 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 11
(1) 3kg of K-1300Y, 6kg of 3513, 0.5kg of WB180HMS, 0.2kg of 1215HT, 0.5kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS are weighed;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 230 deg.C, 225 deg.C; the temperature of the neck ring mold is 225 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Example 12
(1) Weighing 5kg of K-1300Y, 2kg of 3513, 1.5kg of 240M, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Example 13
(1) Weighing 5kg of K-1300Y, 2kg of 3513, 1.5kg of M2, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Comparative example 1
(1) Weighing 7.5kg of K-1300Y, 2kg of 3513, 0.5kg of PO-003, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 270 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Comparative example 2
(1) Weighing 7kg of K-1300Y, 1kg of 3513, 0.5kg of S-2001, 1.5kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 245 deg.C, 240 deg.C; the temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Comparative example 3
(1) Weighing 8kg of K-1300Y, 1kg of 3513, 0.2kg of S-2001, 0.8kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 270 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated through water cooling to obtain the alloy material.
Comparative example 4
(1) Weighing 6.5kg of K-1300Y, 1kg of 3513, 1kg of LNR010, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Comparative example 5
(1) Weighing 5kg of K-1300Y, 2kg of 3513, 1.5kg of 5000S, 0.5kg of PO-003, 1kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the materials were added to a twin screw extruder, the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
Comparative example 6
(1) Weighing 8kg of K-1300Y, 0.7kg of 3513, 0.8kg of WB260HMS, 0.05kg of S-2001, 0.45kg of BDP, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the mixed materials were added to a twin-screw extruder, and the temperature settings for each section of the extruder were as follows (in order from the feed port to the head): 80 deg.C, 220 deg.C, 250 deg.C, 245 deg.C; the temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated through water cooling to obtain the alloy material.
The extrusion-grade polycarbonate alloy products prepared in the above examples 1-2, the extrusion-grade flame-retardant polycarbonate alloy products prepared in the examples 3-13, and the polycarbonate alloys prepared in the comparative examples 1-6 have the product performances shown in tables 1 and 2.
Table 1 product Performance test results
Table 2 product Performance test results
The alloy material prepared in example 5 was extruded to prepare a cable trough (single screw plate forming machine), the process was very stable during extrusion, no air holes were found in the cable trough, and each plane of the cable trough was flat and free of depressions.
The thin wall part (1.6mm) of the cable groove is taken, and the requirement of UL941.5mm V0 is met, so that the product has excellent flame retardant property.
As can be seen from the comparative example 1 and the examples 1-2, the addition of the ultra-high molecular weight polyethylene or the high melt strength polypropylene can significantly improve the melt strength of the system without adding a flame retardant, and endow the product with better impact property and flame retardant property.
As can be seen from the above comparative examples 3-5 and examples 3-13, the melt strength of the comparative example formulation was lower after the addition of the flame retardant, and the addition of ordinary polypropylene or high molecular weight polyethylene could not solve the problem. The formula in the embodiment has higher melt strength, can meet the production requirement of an extrusion process, and has more excellent physical properties.
As can be seen from the comparison of the performances of the products obtained in example 4 and comparative example 6, the notched impact strength of the polycarbonate alloy material obtained after the addition of the compatibilizer in the system is much higher than that of the polycarbonate alloy material obtained after the addition of the toughening agent, which indicates that the compatibility of the polycarbonate alloy base material and the polyolefin polymer is improved after the compatibilizer is used, and the toughness of the system is remarkably improved without the addition of the toughening agent.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (20)
1. The extrusion-grade polycarbonate alloy material is characterized by being prepared from the following components in percentage by weight, wherein the following components in percentage by weight are calculated by taking the total weight of the components as 100 wt%:
the extrusion grade polycarbonate alloy material is prepared from the following components in percentage by weight:
the polycarbonate resin is bisphenol A polycarbonate;
the rubber graft polymer is acrylonitrile-butadiene-styrene;
the polyolefin polymer is selected from ultra-high molecular weight polyethylene and/or long-chain branched polypropylene; the melt strength of the long-chain branched polypropylene is 0.1-1N;
the compatilizer is selected from one or more of PE-g-MAH, PE-g-GMA, PP-g-MAH, PP-g-GMA, POE-g-MAH and POE-g-GMA.
2. The extrusion grade polycarbonate alloy material of claim 1,
the melt index of the bisphenol A polycarbonate is 0.1-40g/10 min.
3. The extrusion grade polycarbonate alloy material of claim 2, wherein the bisphenol a polycarbonate has a melt index of 0.2 to 30g/10 min.
4. The extrusion grade polycarbonate alloy material of claim 3, wherein the bisphenol A polycarbonate has a melt index of 0.5-20g/10 min.
5. The extrusion grade polycarbonate alloy material of claim 1,
the total weight of the acrylonitrile-butadiene-styrene graft copolymer is 100 wt%, wherein the content of butadiene is 10-40 wt%, the content of acrylonitrile is 15-30 wt%, and the content of styrene is 45-70 wt%.
6. The extrusion-grade polycarbonate alloy material of claim 1, wherein the ultra-high molecular weight polyethylene has a number average molecular weight of 150 x 104-500×104；
The melt strength of the long-chain branched polypropylene is 0.2-0.5N.
7. The extrusion-grade polycarbonate alloy material of claim 6, wherein the ultra-high molecular weight polyethylene has a number average molecular weight of 200 x 104-400×104。
8. The extrusion grade polycarbonate alloy material of claim 1, wherein the compatibilizer is POE-g-MAH.
9. The extrusion-grade polycarbonate alloy material of claim 8, wherein the POE-g-MAH has a grafting ratio of MAH of 0.5 to 1.5 wt%.
10. The extrusion-grade polycarbonate alloy material of claim 9, wherein the POE-g-MAH has a grafting yield of MAH of 0.9 to 1.1 wt%.
11. The extrusion-grade polycarbonate alloy material of claim 1, wherein the flame retardant is selected from one or more of an organosilicon flame retardant, an organophosphorus flame retardant, and an organic sulfonic acid metal salt flame retardant.
12. The extrusion-grade polycarbonate alloy material of claim 11, wherein the flame retardant is an organophosphorus flame retardant.
13. The extrusion grade polycarbonate alloy material of claim 12, wherein the organophosphorus flame retardant is selected from one or more of resorcinol bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], triphenyl phosphate, and polyaryl phosphate.
14. The extrusion grade polycarbonate alloy material of claim 13, wherein the organophosphorus flame retardant is bisphenol a-bis (diphenyl phosphate).
15. The extrusion grade polycarbonate alloy material of any of claims 1-14, wherein the components further comprise a plastic additive;
the plastic additive is used in an amount of 0 to 10 wt% based on the total weight of the polycarbonate resin, the rubber graft polymer, the polyolefin polymer, the compatibilizer, and the flame retardant.
16. The extrusion-grade polycarbonate alloy material of claim 15, wherein the plastic additive is present in an amount of 0.1 to 5 wt% based on the total weight of the polycarbonate resin, rubber graft polymer, polyolefin polymer, compatibilizer, and flame retardant.
17. The extrusion grade polycarbonate alloy material of claim 15, wherein the plastic additive is selected from one or more of an anti-drip agent, an antioxidant, and a lubricant.
18. A method of making the extrusion grade polycarbonate alloy material of any of claims 1-17, comprising the steps of:
(1) contacting and mixing the components;
(2) adding the mixture obtained in the step (1) into a double-screw extruder, and carrying out melt extrusion on the materials.
19. The method of claim 18, wherein the extrusion process conditions in step (2) include: the barrel temperature of the double-screw extruder is 230 ℃ and 280 ℃, and the screw rotating speed is 100RPM and 800 RPM.
20. Use of the extrusion grade polycarbonate alloy material according to any one of claims 1 to 17 or the extrusion grade polycarbonate alloy material prepared by the preparation method according to any one of claims 18 to 19 in the field of wire cable troughs or building boards.
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