CN103937192B - PC/PA11 composition and method of making the same - Google Patents
PC/PA11 composition and method of making the same Download PDFInfo
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- CN103937192B CN103937192B CN201410198199.3A CN201410198199A CN103937192B CN 103937192 B CN103937192 B CN 103937192B CN 201410198199 A CN201410198199 A CN 201410198199A CN 103937192 B CN103937192 B CN 103937192B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92838—Raw material pre-treatment, e.g. drying or cleaning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a kind of PC/PA11 composition and method of making the same, belong to field of material technology.Described PC/PA11 composition is prepared from by the raw material of following weight part: polycarbonate 65 ~ 90 parts, polymeric amide 11,10 ~ 35 parts, the weight part summation of polycarbonate and polymeric amide 11 is 100 parts, tolylene diisocyanate 0.1 ~ 3 part, 2,2 ˊ-(1,3-phenylene)-bisoxazoline 0.1 ~ 3 part, styrene-maleic anhydride copolymer 0.1 ~ 6 part, anti-dripping agent 0.1 ~ 2 part, Hinered phenols antioxidant 0.1 ~ 1 part, phosphite ester kind antioxidant 0.1 ~ 1 part, lubricant 0.1 ~ 1 part.The present invention prepared by the method for in situ reactive compatibilization have that mechanical property is good, flame retardant resistance is high, the PC/PA11 composition of chemical resistant properties and good processability, can be applicable to the industry such as automobile (front and rear baffle, post cover, wheel cover, instrument mask) and electronic apparatus (electric power tool shell, distribution apparatus, rly.).
Description
Technical field
The present invention relates to Material Field, particularly relate to a kind of PC/PA11 composition and method of making the same.
Background technology
The develop rapidly of China in Recent Years industry, the application surface of polycarbonate (PC) is constantly expanded, and its demand also constantly increases.But along with science and technology make rapid progress progress, the continuous renewal of Industrial products is regenerated, more and more harsh to the requirement of material property, the polycarbonate of conventional model can not meet all types of requirement of product in product performance, and PC exists, and melt viscosity is large, poor fluidity, high temperature facile hydrolysis, poor solvent resistance, high to the susceptibility of breach, swelling and the stress cracking of easy generation, and the shortcomings such as frictional coefficient is large, higher, the special trade mark price height of melt temperature, thus directly affect its further deeply application and promote.
Polymeric amide, also known as nylon (PA), is that in five large general engineering plastic, purposes is the widest, kind is maximum, output is maximum, the base resin of high comprehensive performance.Polymeric amide 11 (PA11) take Viscotrol C as the soft polymeric amide of Long carbon chain of Material synthesis, and as compared to PA6 with PA66, it has low water-absorbent, good dimensional stability and the advantage such as lower temperature resistance, excellent electrical insulation capability; And there is elastic memory, when external force removes, PA11 can return to original shape; Stress cracking resistance is good, can embed metal parts wherein and not easy to crack; The injection moulding of various melt viscosity scope can be met and extrude processing; The erosion of termite-proof moth, harmless, be a kind of bio-based materials.Thus PA11 is widely used in the fields such as automobile, machinery, electronics, military project, medical treatment, food and physical culture.
PC and PA11 is blended, the mobility of PC can be significantly improved, improve its processing characteristics, stress crack resistance performance and chemical resistance, thermotolerance that PC is higher and shock-resistance etc. can be kept simultaneously.PC/PA11 blend has excellent solvent resistance, wear resistance, dimensional stability and stress cracking resistance, and processing characteristics is better, heat-drawn wire is high, can be applicable to the industry such as automobile (front and rear baffle, post cover, wheel cover, instrument mask) and electronic apparatus (electric power tool shell, distribution apparatus, rly.).
But because in PC/PA11 co-mixing system, two kinds of component crystallizes performances also exist greatest differences, compatibility performance is not good enough, have impact on the performance and application of co-mixing system.Although some performance of alloy adopting simple blend method to prepare improves, because two-phase interface adhesiveproperties is bad, can cause unstable properties, some performance also can decline.In PC/PA11 co-mixing system, add three components expanding material, the performance of blend can be improved further, obtain the alloy material had compared with stability.At present, in prior art, some researchs are done to the modification of PC, all add compatilizer in PC/PA11 co-mixing system, patent CN200910048187.1 discloses a kind of polycarbonate/polyamide alloy and preparation method thereof, its compatilizer is the compound of the ABS-g-GMA of vinylbenzene (ST)-maleic anhydride (MAH) binary polymer and reactive extrursion, or contains vinylbenzene (ST) ter-polymers of glycidyl methacrylate (GMA) and maleic anhydride (MAH) bi-functional monomer; Patent CN201080033771.0 discloses polycarbonate/polyester or the polycarbonate/daiamid composition of impact modification, it comprises a kind of blend polymer of polycarbonate and polyester and/or polymeric amide, adds a kind of anti-impact modifier blend of coker/shell and Functional Polyolefine anti-impact modifier; Patent CN201310300517.8 discloses anti-aging PA/PC polyblend, and its compatilizer is SEBS-g-MAH; Patent CN201310687754.4 discloses rat-and-ant proof PA/PC environmentally-friendly plastic, and its compatilizer is PP-g-MAH.
The preparation method that the PC/PA11 of prior art is blended all adopts two step method, its essence is that first preparation is containing the compatilizer of polar functional group, as: ABS-g-GMA, MAH-g-ST-g-GMA, SEBS-g-MAH, PP-g-MAH etc.Then by PC, PA11, carry out blending extrusion containing the compatilizer of polar functional group and toughner, thus reach the object of toughness reinforcing increase-volume then.
Summary of the invention
For the deficiency that prior art exists, the object of the invention is to prepare have that mechanical property is good, flame retardant resistance is high, the PC/PA11 composition of chemical resistant properties and good processability, can be applicable to the industry such as automobile (front and rear baffle, post cover, wheel cover, instrument mask) and electronic apparatus (electric power tool shell, distribution apparatus, rly.).
The present invention specifically adopts following scheme:
A kind of PC/PA11 composition, is prepared from by the raw material of following weight part:
Described anti-dripping agent is fluoropolymer;
Described Hinered phenols antioxidant is β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid; Described phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Wherein in some embodiments, PC/PA11 composition, is prepared from by the raw material of following weight part:
Wherein in some embodiments, PC/PA11 composition, is prepared from by the raw material of following weight part:
Wherein in some embodiments, described polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, and number-average molecular weight is 15000 ~ 30000; The number-average molecular weight of described polymeric amide 11 is 20000 ~ 30000; In described styrene-maleic anhydride copolymer, the content of maleic anhydride is 15% ~ 20%.
Wherein in some embodiments, the number-average molecular weight of described polycarbonate is for being 18000 ~ 27000; The number-average molecular weight of described polymeric amide 11 is 22000 ~ 26000.
Wherein in some embodiments, described lubricant is pentaerythritol stearate; Described anti-dripping agent is tetrafluoroethylene.
Another object of the present invention is to provide the preparation method of PC/PA11 composition.
The preparation method of above-mentioned PC/PA11 composition, concrete technical scheme, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 100 ~ 120 DEG C, dry 4 ~ 12 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 220 ~ 240 DEG C, two district's temperature: 230 ~ 250 DEG C, three district's temperature are 230 ~ 250 DEG C, four district's temperature: 230 ~ 250 DEG C, five district's temperature are 230 ~ 250 DEG C, six district's temperature: 230 ~ 250 DEG C, die head temperature: 230 ~ 250 DEG C, driving screw rotating speed is: 100 ~ 400rpm.
Wherein in some embodiments, in described step (1), polycarbonate and polymeric amide 11 are placed in 110 DEG C, dry 4 ~ 6 hours; Processing parameter in described step (3) is: district's temperature is 220 ~ 230 DEG C, two district's temperature: 230 ~ 240 DEG C, three district's temperature are 230 ~ 240 DEG C, four district's temperature: 230 ~ 240 DEG C, five district's temperature are 230 ~ 240 DEG C, six district's temperature: 230 ~ 240 DEG C, die head temperature: 230 ~ 240 DEG C, driving screw rotating speed is: 150 ~ 250rpm.
Wherein in some embodiments, the screw configuration of described parallel double-screw extruder is single thread; The ratio L/D of spiro rod length L and diameter D is 35 ~ 60; Described screw rod is provided with the gear block district of more than 1 and the left-hand thread district of more than 1.
Wherein in some embodiments, the ratio L/D of described spiro rod length L and diameter D is 40 ~ 55; Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Principle of the present invention is as follows:
In situ reactive compatibilization mechanism of the present invention is two kinds of superpolymer, puts in the lump in parallel double-screw extruder containing the monomer of double reactive functional group, react at two-phase interface place in the extrusion of melt blending, generate random, grafting or segmented copolymer, produce compatilizer on the spot, namely should react with these two kinds of superpolymer respectively containing the monomer of double reactive functional group, form the compatilizer of superpolymer-co-containing the monomer-co-superpolymer of double reactive functional group.
The present invention adopts the method for in situ reactive compatibilization, in parallel double-screw extruder, the terminal hydroxy group of polycarbonate can respectively with the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, the Amino End Group of polymeric amide 11, end carboxyl can respectively with the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, form compatilizer PC-co-TDI-co-PA11, compatilizer PC-co-PBO-co-PA11, thus improve the consistency of PC/PA11 system, obtain that there is mechanical property good, flame retardant resistance is high, the PC/PA11 composition of chemical resistant properties and good processability.
The styrene-maleic anhydride copolymer (SMA) that the present invention adds plays the effect of auxiliary compatilizer, its principle is that anhydride group in styrene-maleic anhydride copolymer can react with the Amino End Group of PA11 and forms SMA-g-PA11, and the consistency of styrol structural unit in SMA-g-PA11 and polycarbonate is fabulous, thus further improve the consistency of PC/PA11 system.
Compared with prior art, the present invention has following beneficial effect:
1, PC/PA11 composition of the present invention, have that mechanical property is good, flame retardant resistance is high, the advantage such as chemical resistant properties and good processability, can be applicable to the industry such as automobile (front and rear baffle, post cover, wheel cover, instrument mask) and electronic apparatus (electric power tool shell, distribution apparatus, rly.).
2, adopt method of the present invention to prepare PC/PA11 composition, belong to single stage method (In Situ Compatibilization reaction), it has minimizing operation compared to two step method, shortens flow process, reduces costs, the advantage boosted productivity.And this preparation method's technique is simple, be easy to control, not high to equipment requirements, the equipment used is general polymer-processing equipment, invests not high.
Accompanying drawing explanation
Figure 1 shows that preparation technology's schema of PC/PA11 composition of the present invention.
Embodiment
For understanding feature of the present invention, technique means and the specific purposes reached, function further, resolve the advantages and spirit of the present invention, by following examples, the present invention is further elaborated.
The reaction mechanism following (preparation technology's schema asks for an interview Fig. 1) of PC/PA11 composition of the present invention:
Reaction mechanism
From upper reaction formula, the terminal hydroxy group of polycarbonate can respectively with the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, the Amino End Group of polymeric amide 11, end carboxyl can respectively with the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, form compatilizer PC-co-TDI-co-PA11, compatilizer PC-co-PBO-co-PA11, thus improve the consistency of PC/PA11 system, obtain that there is mechanical property good, flame retardant resistance is high, the PC/PA11 composition of chemical resistant properties and good processability.
The raw material that the embodiment of the present invention uses is as follows:
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Dow Chemical company, and number-average molecular weight is 15000.
Polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Japanese Supreme Being people and changes into company, and number-average molecular weight is 23000.
Polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Korea S three and supports company, and number-average molecular weight is 30000.
Polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Korea S three and supports company, and number-average molecular weight is 50000.
Polymeric amide 11, is selected from Lian Zenong Chemical Co., Ltd. in Taiyuan, and number-average molecular weight is 20000.
Polymeric amide 11, is selected from Lian Zenong Chemical Co., Ltd. in Taiyuan, and number-average molecular weight is 24000.
Polymeric amide 11, is selected from Lian Zenong Chemical Co., Ltd. in Taiyuan, and number-average molecular weight is 30000.
Tolylene diisocyanate, is selected from Shanghai Sheng Yu Chemical Co., Ltd..
2,2'-(1,3-phenylene)-bisoxazoline, is selected from colon, Nanjing medication chemistry company limited.
Styrene-maleic anhydride copolymer A, is selected from Sheyang Ketong Plastic Co., Ltd., maleic anhydride content 15% ~ 18%.
Styrene-maleic anhydride copolymer B, is selected from Rizhisheng New Technology Development Co., Ltd., Shanghai, maleic anhydride content 18% ~ 20%.
Anti-dripping agent (tetrafluoroethylene), is selected from Minnesota ,USA mines and production company (3M), trade mark TF-1645.
β-positive octadecanol ester (antioxidant 1076) of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, as primary antioxidant, is selected from Switzerland's vapour Bagong department.
Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), as auxiliary antioxidant, is selected from Switzerland's vapour Bagong department.
Pentaerythritol stearate, is selected from Clariant Corporation of the U.S..
Comparative example 1:
A kind of In situ Reactive Compatibility of this comparative example prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 225 DEG C, two district's temperature: 235 DEG C, three district's temperature are 235 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 200rpm.
The screw configuration of described parallel double-screw extruder is double thread, and the ratio L/D of spiro rod length L and diameter D is 20, and described screw rod is provided with 1 gear block district, without left-hand thread district.
Comparative example 2:
A kind of In situ Reactive Compatibility of this comparative example prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant are joined in another homogenizer mix, then the mixture obtained is joined in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 225 DEG C, two district's temperature: 235 DEG C, three district's temperature are 235 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 200rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Comparative example 3:
A kind of In situ Reactive Compatibility of this comparative example prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 225 DEG C, two district's temperature: 235 DEG C, three district's temperature are 235 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 200rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 1:
A kind of In situ Reactive Compatibility of the present embodiment prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 240 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 240 DEG C, die head temperature: 240 DEG C, driving screw rotating speed is: 400rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 60, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 2:
A kind of In situ Reactive Compatibility of the present embodiment prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer A (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 220 DEG C, two district's temperature: 230 DEG C, three district's temperature are 230 DEG C, four district's temperature: 230 DEG C, five district's temperature are 230 DEG C, six district's temperature: 230 DEG C, die head temperature: 230 DEG C, driving screw rotating speed is: 100rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 35, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 3:
A kind of In situ Reactive Compatibility of the present embodiment prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 225 DEG C, two district's temperature: 240 DEG C, three district's temperature are 240 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 230 DEG C, driving screw rotating speed is: 150rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 4:
A kind of In situ Reactive Compatibility of the present embodiment prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 225 DEG C, two district's temperature: 235 DEG C, three district's temperature are 235 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 200rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 5:
A kind of In situ Reactive Compatibility of the present embodiment prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer A (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 235 DEG C, three district's temperature are 235 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 250rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 45, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 6:
A kind of In situ Reactive Compatibility of the present embodiment prepares PC/PA11 composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PA11 composition, comprises the following steps:
(1) described polycarbonate (PC) and polymeric amide 11 (PA11) are placed in 110 DEG C, dry 4 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), styrene-maleic anhydride copolymer B (SMA), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 225 DEG C, two district's temperature: 235 DEG C, three district's temperature are 235 DEG C, four district's temperature: 240 DEG C, five district's temperature are 240 DEG C, six district's temperature: 235 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 250rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 55, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Be below comparative example and embodiment table look-up:
Table 1 comparative example and embodiment raw material form weight part table look-up
The anti-dripping agent of above comparative example and embodiment, primary antioxidant, auxiliary antioxidant and lubricant are respectively 0.3 part, 0.1 part, 0.1 part, 0.1 part.
Above-mentioned comparative example and the made sample of embodiment are carried out following performance test:
Tensile property: by GB/T1042-1992 standard testing, rate of extension 50mm/min.
Impact property: by GB/T1843-1996 standard testing, batten thickness is 3.2mm.
Flame retardant resistance: the XZT-100A oxygen index measurer test oxygen index that the batten of 130mm × 6.5mm × 3.0mm is produced with Chengde great Hua trier company limited.
Chemical resistant properties: after tensile bars being put into Glacial acetic acid 3min, tests its elongation at break.The elongation at break of the tensile bars after Glacial acetic acid process is not with larger by the ratio of the elongation at break of the tensile bars of Glacial acetic acid process, and its chemical resistant properties is better.
Melting index: test by ASTM D1238, probe temperature 250 DEG C, load 5kg.
Table 2 comparative example and embodiment performance table look-up
Comparative example 1 for screw configuration be double thread, the ratio L/D of spiro rod length L and diameter D is 20, and screw rod is provided with 1 gear block district, the PC/PA11 composition that the twin screw extruder without left-hand thread district prepares; Embodiment 4 for screw configuration be single thread, the ratio L/D of spiro rod length L and diameter D is 50, the PC/PA11 composition that the twin screw extruder that screw rod is provided with 2 gear block districts and 2 left-hand thread districts prepares.Can be found out by contrast, screw configuration of the present invention is adopted to be single thread, the ratio L/D of spiro rod length L and diameter D is 50, when screw rod is provided with 2 gear block districts and 2 left-hand thread districts, the tensile strength of PC/PA11 composition, notched Izod impact strength, oxygen index, chemical resistant properties and melting index are greatly improved, and obtain that mechanical property is good, flame retardant resistance is high, the beneficial effect of the PC/PA11 composition of chemical resistant properties and good processability.
Comparative example 2 is the PC/PA11 composition of the monomer do not added containing double reactive functional group; Embodiment 4 is for adding the PC/PA11 composition of tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO).Can be found out by contrast, add the tensile strength of the PC/PA11 composition of the monomer containing double reactive functional group, notched Izod impact strength, oxygen index, chemical resistant properties and melting index and be better than the PC/PA11 composition of the monomer do not added containing double reactive functional group.
Comparative example 3 to be the number-average molecular weight of polycarbonate be 50000 PC/PA11 composition; Embodiment 4 to be the number-average molecular weight of polycarbonate be 23000 PC/PA11 composition.Can be found out by contrast, the number-average molecular weight that the number-average molecular weight of polycarbonate is the tensile strength of the PC/PA11 composition of 50000, notched Izod impact strength and chemical resistant properties outline are better than polycarbonate is the PC/PA11 composition of 23000, and the melting index that the number-average molecular weight of polycarbonate is the PC/PA11 composition of 50000 only has 7g/10min, its processing characteristics is poor.
Embodiment 1 ~ 6 is the weight part of adjustment PC and PA11, and as can be seen from Table 2, along with the addition of PA11 increases, the tensile strength of PC/PA11 composition and notched Izod impact strength present the variation tendency of minimizing; The chemical resistant properties of PC/PA11 composition and melting index present the variation tendency of increase.Wherein, the over-all properties of embodiment 4 is best.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a PC/PA11 composition, is characterized in that, is prepared from by the raw material of following weight part:
Described anti-dripping agent is fluoropolymer;
Described Hinered phenols antioxidant is β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid;
Described phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester;
The preparation method of described PC/PA11 composition comprises the following steps:
(1) described polycarbonate and polymeric amide 11 are placed in 100 ~ 120 DEG C, dry 4 ~ 12 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate, 2,2'-(1,3-phenylene)-bisoxazoline, styrene-maleic anhydride copolymer, anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 220 ~ 240 DEG C, two district's temperature: 230 ~ 250 DEG C, three district's temperature are 230 ~ 250 DEG C, four district's temperature: 230 ~ 250 DEG C, five district's temperature are 230 ~ 250 DEG C, six district's temperature: 230 ~ 250 DEG C, die head temperature: 230 ~ 250 DEG C, driving screw rotating speed is: 100 ~ 400rpm.
2. PC/PA11 composition according to claim 1, is characterized in that, is prepared from by the raw material of following weight part:
3. PC/PA11 composition according to claim 2, is characterized in that, is prepared from by the raw material of following weight part:
4. the PC/PA11 composition according to any one of claims 1 to 3, is characterized in that, described polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, and number-average molecular weight is 15000 ~ 30000; The number-average molecular weight of described polymeric amide 11 is 20000 ~ 30000; In described styrene-maleic anhydride copolymer, the content of maleic anhydride is 15% ~ 20%.
5. PC/PA11 composition according to claim 4, is characterized in that, the number-average molecular weight of described polycarbonate is for being 18000 ~ 27000; The number-average molecular weight of described polymeric amide 11 is 22000 ~ 26000.
6. PC/PA11 composition according to claim 4, is characterized in that, described lubricant is pentaerythritol stearate; Described anti-dripping agent is tetrafluoroethylene.
7. a preparation method for the PC/PA11 composition described in any one of claim 1 ~ 6, is characterized in that, comprise the following steps:
(1) described polycarbonate and polymeric amide 11 are placed in 100 ~ 120 DEG C, dry 4 ~ 12 hours, after cooling, polycarbonate and polymeric amide 11 are joined in homogenizer and carries out pre-mixing;
(2) by tolylene diisocyanate, 2,2'-(1,3-phenylene)-bisoxazoline, styrene-maleic anhydride copolymer, anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then joined by the mixture obtained in the homogenizer in step (1) and mix;
(3) premixture that step (2) mixes is placed in parallel double-screw extruder to melt extrude, granulation, processing parameter is as follows: district's temperature is 220 ~ 240 DEG C, two district's temperature: 230 ~ 250 DEG C, three district's temperature are 230 ~ 250 DEG C, four district's temperature: 230 ~ 250 DEG C, five district's temperature are 230 ~ 250 DEG C, six district's temperature: 230 ~ 250 DEG C, die head temperature: 230 ~ 250 DEG C, driving screw rotating speed is: 100 ~ 400rpm.
8. preparation method according to claim 7, is characterized in that, in described step (1), polycarbonate and polymeric amide 11 are placed in 110 DEG C, dry 4 ~ 6 hours; Processing parameter in described step (3) is: district's temperature is 220 ~ 230 DEG C, two district's temperature: 230 ~ 240 DEG C, three district's temperature are 230 ~ 240 DEG C, four district's temperature: 230 ~ 240 DEG C, five district's temperature are 230 ~ 240 DEG C, six district's temperature: 230 ~ 240 DEG C, die head temperature: 230 ~ 240 DEG C, driving screw rotating speed is: 150 ~ 250rpm.
9. preparation method according to claim 7, is characterized in that, the screw configuration of described parallel double-screw extruder is single thread; The ratio L/D of spiro rod length L and diameter D is 35 ~ 60; Described screw rod is provided with the gear block district of more than 1 and the left-hand thread district of more than 1.
10. preparation method according to claim 9, is characterized in that, the ratio L/D of described spiro rod length L and diameter D is 40 ~ 55; Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
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| CN106633836A (en) * | 2016-11-30 | 2017-05-10 | 宁波仁慈新材料科技有限公司 | High-intensity deformation-resistant PA/PC alloy fixing frame material |
| CN107057341B (en) * | 2017-01-09 | 2019-07-19 | 广东中塑新材料有限公司 | High heat conductive insulating polyamide compoiste material and preparation method thereof |
| CN107400356A (en) * | 2017-09-15 | 2017-11-28 | 安徽江淮汽车集团股份有限公司 | A kind of high-performance PA12 PC composites and preparation method thereof |
| CN112724659A (en) * | 2020-12-25 | 2021-04-30 | 深圳力越新材料有限公司 | Bio-based nylon/polycarbonate alloy and preparation method thereof |
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