CN101717568B - Polycarbonate/nylon 6 alloy material and preparation method thereof - Google Patents
Polycarbonate/nylon 6 alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polycarbonate/nylon 6 alloy material and a preparation method thereof. The alloy consists of the following components in percentage by weight: 22 to 70 percent of polycarbonate, 22 to 70 percent of nylon 6, 0.5 to 1 percent of antioxidant, 5 to 20 percent of compatibilizer, 0 to 15 percent of flame retardant, and 2 to 6 percent of processing aids, wherein the compatibilizer is ethylene-acrylic ester-maleic anhydride copolymer or propylene ester-maleic anhydride copolymer. The preparation method comprises the steps of drying raw materials, proportioning and premixing the dried raw materials, extruding and granulating the obtained product. The alloy is stable in tensile and bending properties, and the impact and temperature-resisting properties of the alloy change with the difference of the PC/PA6 proportion. Different mixture ratio can be chosen according to need, so the application fields of the alloy are broadened.
Description
Technical field
The invention belongs to the thermoplastic macromolecule material technical field, relate to a kind of polycarbonate/nylon 6 alloy material and preparation method thereof.
Background technology
Polycarbonate (PC) and nylon 6 (PA6) all belong to thermoplastic engineering plastic, and its performance respectively has relative merits.Wherein polycarbonate (PC) has thermotolerance, and decomposition temperature is more than 300 ℃, 130～135 ℃ of heat-drawn wires (1.82MPa), and the long term operation temperature can be up to 120 ℃; Winter hardiness is good simultaneously, and embrittlement temperature is low to reach-100 ℃, and its life-time service temperature range is at-60～120 ℃; Also have plurality of advantages such as mechanical property is good, light stability is good simultaneously.But PC molecular rigidity and sterically hindered bigger, melt temperature is higher, and mobile relatively poor, processing is difficulty, and goods are easy to generate internal stress; Simultaneously the PC solvent resistance is bad, and wear resistance and fatigue resistance are relatively poor, these drawbacks limit the application of PC.Nylon 6 (PA6) has excellent mechanical property, physical strength height, good toughness.Its outstanding advantage is to have self lubricity, and wear resistance is outstanding.But it also has shortcoming: heat-drawn wire (1.86MPa) has only 63 ℃.
After PC and PA6 made alloy, its merits and demerits can be complementary, and promptly the various advantages of PC and PA6 are further brought into play, and shortcoming improves, and so just can enlarge the Application Areas of alloy.Yet the solubility parameter of PC and PA6 differs bigger, and the thermodynamics of the two is incompatible, when PC and PA6 blend, can significantly produce demixing phenomenon, and amide exchange reaction takes place easily, causes the molecular weight of the two to reduce, thereby influences the performance of alloy material.And after in system, adding the compatilizer of some amount, can significantly improve two alternate consistencies, can avoid demixing phenomenon, reduce simultaneously and eliminate transamination and reflect, improve the alternate bonding force of PC/PA6, the performance of PC/PA6 alloy material is optimized and improves.Therefore, selecting appropriate compatilizer is the key of this alloy material preparation.
Secondly, for the consideration of aspect safe in utilization, the PC/PA6 alloy material is proposed the requirement of anti-fire-retardant aspect.Polycarbonate (PC) makes combustible, and its oxygen index is 25, leaves burning things which may cause a fire disaster and can put out certainly; The oxygen index of nylon 6 (PA6) is 26.4, also belongs to the self-extinguishing type resin, and by U.S. UL standard, they are equivalent to the UV-94V2 level, but still are combustiblematerials.
At present, the nylon alloy kind is many, but the alloy that relates to polycarbonate/nylon 6 rarely has discovery, and therefore necessity of further research and development arranged.
Summary of the invention
The present invention proposes a kind of Alloy And Preparation Method of being made by polycarbonate (PC) and two kinds of engineering plastics of nylon (PA6) in order to address the above problem, and can bring into play the advantage separately of PC and PA6, overcomes its shortcoming separately, to widen its Application Areas.
Above-mentioned polycarbonate/nylon 6 alloy material is made of following components in percentage by weight:
Polycarbonate 22～58.5%;
Nylon 622～70%;
Oxidation inhibitor 0.5～1%;
Compatilizer 5～20%;
Fire retardant 0～15%;
Processing aid 2～6%;
Described compatilizer is ethylene-acrylate-copolymer-maleic anhydride or propylene ester-copolymer-maleic anhydride.
Described polycarbonate is meant aromatic bisphenol A polycarbonate.
Described oxidation inhibitor is β (3; 5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester, N; N '-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl] mixing arbitrarily in four of hexanediamine, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, tricresyl phosphite (24-di-tert-butyl-phenyl) ester.
Described processing aid comprises lubricant, toughner.
The preparation method of above-mentioned polycarbonate/nylon 6 alloy material is:
A, to polycarbonate and nylon 6 drying treatment, temperature is controlled at 100～120 ℃, the time is more than 6 hours, to water-content below 0.02%; Nylon 6 is dry under vacuum condition;
B, batching and premix: put in the high-speed mixer together by load weighted dried raw material of formula rate requirement and auxiliary agent and to mix, stir 5～15min at normal temperatures;
C, blender extruding pelletization:
A, employing parallel double-screw extruder, screw diameter 35-75MM;
The temperature of b, forcing machine is set to: a district: 200～210 ℃; Two districts: 210～220 ℃; Three districts: 220～230 ℃ of four district: 230～240 ℃; Five districts: 240～250 ℃; Six districts: 250～260 ℃; Seven districts: 260～270 ℃; Eight districts: 260～270 ℃; Head temperature: 250～260 ℃; Melt temperature: 250～260 ℃;
C, screw speed are controlled at 200～400rPm.
The present invention has set up bridge owing to having selected appropriate compatilizer to make between polycarbonate (PC) and nylon 6 (PA6) two-phase, reduce demixing phenomenon, improved the performance of alloy, can bring into play the advantage separately of polycarbonate (PC) and nylon 6 (PA6), overcome its shortcoming separately, on each side's performances such as tensile strength, elongation at break, modulus in flexure, flexural strength, notched Izod impact strength, heat-drawn wire, all obtained optimization, and along with the difference of the ratio of PC/PA6, its performance also changes thereupon, has widened its Application Areas.This alloy can be selected PC and the PA6 and the corresponding adjuvants of different ratios, to draw the alloy that meets customer demand according to client's demand.
Embodiment
PC/PA6 alloy material of the present invention is to be made of following components in percentage by weight:
Polycarbonate (PC) 22～58.5%;
Nylon 6 (PA6) 22～70%;
Oxidation inhibitor 0.5～1%;
Compatilizer 5～20%;
Fire retardant 0～15%;
Processing aid 2～6%.
Wherein:
Optional ethylene-acrylate-the copolymer-maleic anhydride of compatilizer also can select propylene ester-maleic anhydride copolymerization, as long as it is just passable to reach the compatible result of two kinds of materials.Optimal ethylene-acrylate-maleic anhydride terpolymer.Whether suitable compatilizer is, directly influences the performance of this alloy.PC/PA6 is under the situation that no compatilizer exists, tangible demixing phenomenon appears in the material bar, the transamination reflection takes place simultaneously, make the molecular weight of two kinds of materials reduce, directly influence the performance of alloy, add after ethylene-acrylate-copolymer-maleic anhydride, make in this system PC and PA6 set up bridge between mutually, reduce demixing phenomenon, improved the performance of alloy.
Polycarbonate (PC) is meant aromatic bisphenol A polycarbonate, can require according to the rerum natura of PC/PA6 alloy to select as for the model of polycarbonate;
The selection of PA6 also is to select according to the requirement of alloy, is to select low viscosity, medium viscosity, high viscosity to require to determine according to the rerum natura of alloy.
Oxidation inhibitor can be selected
1,1076: β (3,5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester,
2,1098:N, N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine;
3,1,010 four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
4,168 tricresyl phosphites (24-di-tert-butyl-phenyl) ester
Mix and match uses.
Fire retardant can be halogenous, also can be Halogen, and concrete kind and consumption come to determine as requested.
Processing aid comprises lubricant, toughner etc., comes as the case may be to select.
The preparation method of PC/PA6 alloy material of the present invention is:
1, the pre-treatment of raw material
The all easy moisture absorption of PC and PA6, hydrolysis takes place in the PC of the moisture absorption and PA6 easily under molten state, therefore, must carry out drying treatment to PC and PA6 before blending and modifying, and the exsiccant temperature is controlled at 100～120 ℃, and time of drying is more than 6 hours.PA6 is flavescence easily in drying process, and vacuum condition is dry down; If survey its water-content, can moistly directly carry out weigh batching in the ratio of prescription below 0.02%.
2, batching and premix
Put in the high-speed mixer together by load weighted raw material of formula rate requirement and auxiliary agent and to mix, stir 5～15min at normal temperatures.
3, blender extruding pelletization
A, equipment adopt parallel double-screw extruder, screw diameter 35-75MM;
The temperature of B, forcing machine is set to: a district: 200～210 ℃; Two districts: 210～220 ℃; Three districts: 220～230 ℃; Four districts: 230～240 ℃; Five districts: 240～250 ℃; Six districts: 250～260 ℃; Seven districts: 260～270 ℃; Eight districts: 260～270 ℃; Head temperature: 250～260 ℃; Melt temperature: 250～260 ℃;
C, screw speed are controlled at 200～400rPm.Suitably the rotating speed of control feed screw is extruded through double-screw melt blending, and through water-cooled, air-dry, pelletizing, last bag becomes the PC/PA6 alloy resin.
Further describe the present invention below in conjunction with specific embodiment, the component of each embodiment sees Table 1.
Table 1 embodiment component
Embodiment one
Be ready to following raw material and auxiliary agent at first by weight percentage: 58.5% PC, 22% PA6,5% compatilizer, 12% fire retardant, 0.5% oxidation inhibitor, 2% processing aid.Wherein compatilizer is selected ethylene-acrylate-maleic anhydride terpolymer for use, and fire retardant is a TDE, and oxidation inhibitor is β (3,5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester, and processing aid is EBS (ethylene bis stearic acid amide).
Earlier above-mentioned PC and PA6 are carried out drying respectively, drying temperature carries out under 100～200 ℃.Time of drying is more than 6 hours.As measure its moisture below 0.02%, can moist direct batching.PA6 is flavescence easily in drying process, and is preferably dry under vacuum state.But when water content reaches requirement, carry out weigh batching by prescription.The material for preparing is put into mixing machine together and is carried out batch mixing.Mixing time was at 5～15 minutes, and concrete mixing time will see whether batch mixing is even.The material that mixes joins in the hopper of twin screw extruder, each section temperature of twin screw extruder is controlled at: 200～210 ℃ in a district, 210～220 ℃ in two districts, 220～230 ℃ in three districts, 230～240 ℃ in four districts, 240～250 ℃ in five districts, 250～260 ℃ in six districts, 260～270 ℃ in seven districts, 260～270 ℃ in eight districts, head temperature is generally at 250～260 ℃, screw speed is controlled at 200～400rPm, and suitably the rotating speed of the reinforced screw rod of control is extruded through the twin screw extruder melt blending, through water-cooled, air-dry, pelletizing, last bag becomes PC/PA6 alloy material finished product.
Embodiment two
Be ready to following raw material and auxiliary agent at first by weight percentage: 50% PC, 39.6% PA6,5% compatilizer, 12% fire retardant, 1% oxidation inhibitor, 2.% processing aid.Wherein compatilizer is selected ethylene-acrylate-maleic anhydride terpolymer for use, and fire retardant is a TDE, and oxidation inhibitor is 1076 to mix with 1098, and processing aid is EBS and look mother.
Then said components is processed finished product by embodiment one described preparation method.
Embodiment three
Be ready to following raw material and auxiliary agent at first by weight percentage: 39.75% PC, 39.75% PA6,5% compatilizer, 12% fire retardant, 0.5% oxidation inhibitor, 3% processing aid.Wherein compatilizer is selected ethylene-acrylate-maleic anhydride terpolymer for use, and fire retardant is a TDE, and oxidation inhibitor is 1076 and 1098,1610,168 to mix, and processing aid is EBS and look mother.
Then said components is processed finished product by embodiment one described preparation method.
Embodiment four
Be ready to following raw material and auxiliary agent at first by weight percentage: 31% PC, 46% PA6,5% compatilizer, 15% fire retardant, 0.5% oxidation inhibitor, 2.5% processing aid.Wherein compatilizer is selected ethylene-acrylate-maleic anhydride terpolymer for use, and fire retardant is a TDE, and oxidation inhibitor is 1076 to mix with 1098, and processing aid is EBS and look mother.
Then said components is processed finished product by embodiment one described preparation method.
Embodiment five
Be ready to following raw material and auxiliary agent at first by weight percentage: 36.75% PC, 36.75% PA6,20% compatilizer, 0.5% oxidation inhibitor, 6% processing aid.Wherein compatilizer is selected propylene ester-copolymer-maleic anhydride for use, and oxidation inhibitor is 1076 to mix with 1098, and processing aid is EBS and look mother.
Then said components is processed finished product by embodiment one described preparation method.
Table 2 performance synthesis table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Density (g/cm2) | 1.257 | 1.255 | 1.266 | 1.258 | 1.216 | 1.10 |
| Tensile strength (MPa) | 60 | 48 | 46 | 46 | 48 | 49 |
| Elongation at break (%) | 22 | 11 | 13 | 12 | 12 | 11 |
| Modulus in flexure (MPa) | 2200 | 1570 | 1480 | 1520 | 1440 | 1340 |
| Flexural strength (MPa) | 64 | 52 | 51 | 53 | 52 | 48 |
| Notched Izod impact strength (KJ/m2) | 12 | 8 | 7 | 7.5 | 6.4 | 8.7 |
| Heat-drawn wire (1.8MPa) | 115 | 106 | 105 | 90 | 80 | 90 |
| Flame retardant resistance UL94 (3.2MM) | V-0 | V-0 | V-0 | V-0 | V-2 | V-2 |
Embodiment six
Be ready to following raw material and auxiliary agent at first by weight percentage: 22% PC, 70% PA6,5% compatilizer, 0.5% oxidation inhibitor, 2.5% processing aid.Wherein compatilizer is selected propylene ester-maleic anhydride copolymerization for use, and oxidation inhibitor is 1076 and 1098,1610,168 to mix, and processing aid is EBS and look mother.
Then said components is processed finished product by embodiment one described preparation method.
The product performance of the various embodiments described above see Table 2.
As can be seen from Table 2, the performance of PC/PA6 alloy is along with the ratio of PC and PA6 is different, and its performance also changes thereupon.Stretching and bending property change little, and impact property and heat resistance are all between PC and PA6.Select to fill a prescription or the methods such as proportioning, auxiliary agent of regulating are made the alloy that meets the requirements of the customers according to client's specific requirement.
The above only is a preferable possible embodiments of the present invention, and non-so limitation protection scope of the present invention so the equivalence techniques that uses specification sheets of the present invention and diagramatic content to do such as changes, all is contained in protection scope of the present invention.
Claims (5)
1. polycarbonate/nylon 6 alloy material is made of following components in percentage by weight:
Polycarbonate 22～58.5%;
Nylon 6 22～70%;
Oxidation inhibitor 0.5～1%;
Compatilizer 5～20%;
Fire retardant 0～15%;
Processing aid 2～6%;
Described compatilizer is ethylene-acrylate-copolymer-maleic anhydride or propylene ester-copolymer-maleic anhydride.
2. polycarbonate/nylon 6 alloy material as claimed in claim 1 is characterized in that: described polycarbonate is meant aromatic bisphenol A polycarbonate.
3. polycarbonate/nylon 6 alloy material as claimed in claim 1 or 2; it is characterized in that: described oxidation inhibitor is β (3; 5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester, N; N '-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl] any mixing in four of hexanediamine, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (24-di-tert-butyl-phenyl) esters.
4. polycarbonate/nylon 6 alloy material as claimed in claim 1 or 2 is characterized in that: described processing aid comprises lubricant, toughner.
5. the preparation method of polycarbonate/nylon 6 alloy material as claimed in claim 1 is:
A, to polycarbonate and nylon 6 drying treatment, temperature is controlled at 100～120 ℃, the time is more than 6 hours, to water-content below 0.02%; Nylon 6 is dry under vacuum condition;
B, batching and premix: put in the high-speed mixer together by load weighted dried raw material of formula rate requirement and auxiliary agent and to mix, stir 5～15min at normal temperatures;
C, blender extruding pelletization:
A, employing parallel double-screw extruder, screw diameter 35-75MM;
The temperature of b, forcing machine is set to: a district: 200～210 ℃; Two districts: 210～220 ℃; Three districts: 220～230 ℃; Four districts: 230～240 ℃; Five districts: 240～250 ℃; Six districts: 250～260 ℃; Seven districts: 260～270 ℃; Eight districts: 260～270 ℃; Head temperature: 250～260 ℃; Melt temperature: 250～260 ℃;
C, screw speed are controlled at 200～400rPm.
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