CN107312305B - A kind of sprayable fire-retardant polycarbonate/polyketone alloy and its application in manufacture wall switch - Google Patents
A kind of sprayable fire-retardant polycarbonate/polyketone alloy and its application in manufacture wall switch Download PDFInfo
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- CN107312305B CN107312305B CN201710623239.8A CN201710623239A CN107312305B CN 107312305 B CN107312305 B CN 107312305B CN 201710623239 A CN201710623239 A CN 201710623239A CN 107312305 B CN107312305 B CN 107312305B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of sprayable fire-retardant polycarbonate/polyketone alloy, raw material components include: 35~95 parts by weight of polycarbonate；5~50 parts by weight of polyketone；1~50 parts by weight of silane copolymer polycarbonate；1~10 parts by weight of fire retardant；Other 0.5~10 parts by weight of auxiliary agent.The present invention provides a kind of sprayable fire-retardant polycarbonate/polyketone alloys, have good spraying property, anti-flammability and heat resistance with the material that the alloy is prepared, can be used for manufacturing wall switch.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of sprayable fire-retardant polycarbonate/polyketone alloy
And its application in manufacture wall switch.
Background technique
Polycarbonate (abbreviation PC) is a kind of thermoplastic noncrystalline engineering plastics, is in strand containing carbonate group
High molecular polymer has excellent impact strength, thermal stability, glossiness, inhibits bacteria characteristic, flame-retarding characteristic and anti-pollution
Metachromia is the optimal selection of building trade, wall switch etc., but due to the hardness of PC itself be not it is very high, cause production,
It is easily scratched by tool or nail in assembling process, and wall switch is not only functor or decorative appearance in building
Part, the damage on surface have severely impacted its dicoration and have caused certain waste so as to cause the increase of defect ware；In addition
Due to the presence of phenyl ring in PC molecular structure, cause molecule chain rigidity and steric hindrance larger, melt viscosity is big, and processing is not easy,
Product residual stress is larger during machine-shaping, under some special installations or use environment, due to the erosion pole of solvent
Stress cracking easily occurs, loses use value so as to cause finished product, causes immeasurable loss to enterprise.In addition, metope is opened
Closing most of is all white, and PC is easy to xanthochromia in the case where being irradiated with ultraviolet radiation, and this phenomenon is outdoor especially bright
It is aobvious, generally for avoiding this phenomenon, it is necessary to some special auxiliary agents are added, to cause the increase of cost.
Therefore, on PC wall switch surface, spray paint is just very significant: one, forming a protective layer on surface, prevent
Only scratch and solvent corrode caused by cracking, moreover it is possible to avoid due to UV-induced xanthochromia problem, at the same also avoid due to
The addition of special auxiliary agent and caused by cost；Two, painting color can be designed freely, substantially increase its decoration
Property.
But for PC, since melt viscosity is big, certain internal stress can be generated in forming process, and paints itself
It is exactly a kind of solvent, if product internal stress is excessive, when being processed after spray paint, product can be made due to the corrosion of paint
Stress is discharged, is easy to cause substrate to crack, influences product appearance and spray efficiency.Therefore, it is necessary to carry out special modification to PC.
As Publication No. CN103342886A Chinese patent literature in disclose a kind of spraying PC/ABS alloy material and
Preparation method is made of, wherein polycarbonate polycarbonate, ABS, SAN, antioxidant, lubricant: 30-80 parts, ABS resin:
15-65 parts, SAN resin: 5-10 parts, antioxidant: 0.1-1 parts, lubricant: 0.1-1 parts.Although the product has good flowing
Property and spray painting performance, but due to the large scale of ABS be added, the heat resistance that will cause material substantially reduces, to be unable to reach electricity
The heat resistant requirements of work standard.In addition, fire retardant is not added in the material, it is not appropriate for applying in wall switch field.
Therefore, a non-PC/ABS system is developed, it can improve the sprayable property of PC, while it is fire-retardant to reduce its again
The novel system of property and heat resistance, is current urgent problem to be solved.
Summary of the invention
The present invention provides a kind of sprayable fire-retardant polycarbonate/polyketone alloy, the material tool being prepared with the alloy
There are good spraying property, anti-flammability and heat resistance, can be used for manufacturing wall switch.
Specific technical solution is as follows:
A kind of sprayable fire-retardant polycarbonate/polyketone alloy, is made of the raw material components of following parts by weight:
Applicant of the present invention has developed a polycarbonate/polyketone alloy in previous work, it is found through experiment that,
Polycarbonate and polyketone are combined alloy, chemical resistance ability is significantly improved, while heat resistance is also preferable.But work as
PC material is in addition to needing to meet heat resistant requirements, also needing the sprayable property and anti-flammability that have excellent when manufacturing wall switch.
Based on the considerations of anti-flammability, applicant increases bromide fire retardant on the basis of having formula, but since bromide fire retardant is mostly
Small-molecule substance, certainly will will lead to the deterioration of Some Mechanical Properties after addition, especially will lead to Impact Properties of Materials variation.Together
When, the sprayable performance of polycarbonate/polyketone alloy which is prepared can not be met the requirements, this results in the formula
It not can be used directly in manufacture wall switch.Applicant has been surprisingly found that silane copolymer polycarbonate adds after a large number of experiments screens
The PC+POK+ silane copolymer PC ternary system formed after entering is prepared under the dosage of identical fire retardant and other auxiliary agents
Polycarbonate/polyketone alloy, impact strength is improved, at the same sprayable performance more preferably, spraying cracking ratio it is significant under
Drop.
Analyzing its reason may be: on the one hand, a large amount of Si-O-Si keys is contained in the strand of silane copolymer PC, make score
Subchain flexibility increases, and strand mobility enhancing, intermolecular total active force reduces, and the melt viscosity of system reduces, flowing
Property enhancing, forming process can use lower pressure and speed, and the residual stress of product reduces, and generation stress is opened after product spraying
The probability split reduces；On the other hand, the addition of silane copolymer PC makes former two-phase system become three-phase system, and in the work of compatilizer
Under, substantially reduce the regularity of strand in system, crystallinity reduces, and improves the adhesive force between material and coating, applies
Material bonds more firm.
Preferably, the polycarbonate is selected from bisphenol A polycarbonate, melt flow rate (MFR) is 5~20g/min, is surveyed
Strip part are as follows: 300 DEG C, 1.2kg.Melt flow rate (MFR) is smaller to illustrate that viscosity is bigger, and strand is longer, entanglement it is closer, resist
Cracking ability is stronger.Further preferably, the melt flow rate (MFR) of the polycarbonate is 10g/min.
Preferably, the melt flow rate (MFR) of the polyketone is 50~70g/10min, test condition are as follows: 240 DEG C,
2.16kg.Melt flow rate (MFR) is bigger, illustrates that mobility is better, and strand activity is stronger, easier in table when melt blending
Face is evenly dispersed.Further preferably, the melt flow rate (MFR) of the polyketone is 60g/10min.
Preferably, the silane copolymer polycarbonate is block type copolymer, molecular weight is 26000~32000g/
mol。
Preferably, the sprayable fire-retardant polycarbonate/polyketone alloy, by the raw material components system of following parts by weight
At:
It is found through experiment that using the polycarbonate, polyketone and silane copolymer polycarbonate of above-mentioned particular characteristic parameter in spy
The ternary system formed under certainty ratio, the polycarbonate being prepared/polyketone alloy, spraying cracking ratio can be reduced to 0, but oil
Adhesion performance after paint spraying is but at a distance of very big.
Further preferably, it is made of the raw material components of following parts by weight:
Through test it has furthermore been found that when using the ternary system of above-mentioned special ratios, particular characteristic parameter, paint spray
Adhesive force after painting is splendid, can reach 5B standard.
Preferably, the fire retardant is selected from bromide fire retardant.
Preferably, other auxiliary agents include compatilizer, impact modifier, antioxidant, stabilisers against hydrolysis and add
At least one of work auxiliary agent.
Sprayable fire-retardant polycarbonate/polyketone the alloy, is made of the raw material components of following parts by weight:
Further preferably, the compatilizer is selected from the polyolefin elastomer of maleic anhydride grafting, styrene-butadiene heat
Thermoplastic elastic, polyolefin elastomer, polyolefin graft glycidyl methacrylate copolymer, methyl methacrylate-
Polyethylene, the ethylene-propylene that styrene-butadiene terpolymer, ethylene-methyl acrylate copolymer, maleic anhydride are grafted
At least one of acid esters-glycidyl methacrylate；Further preferably polyolefin graft Glycidyl methacrylate is sweet
Grease copolymer.
The impact modifier is selected from terpolymer, the polyolefin bullet of methyl methacrylate-butadiene-styrene
At least one of property body, organosilicon toughener, ethylene-acrylate-glycidyl methacrylate；Further preferably
The terpolymer of methyl methacrylate-butadiene-styrene.
The antioxidant is selected from 1076 and 168 compound；Further preferably, described 1076 and 168 by weight
For 1:1 mixing.
The stabilisers against hydrolysis is selected from the liter SAG005 of day；
The processing aid is selected from least one of calcium stearate, pentaerythritol ester, silicone powder.
It is in terms of 100 parts by the gross mass of polycarbonate, polyketone and silane copolymer polycarbonate, other raw materials are adopted in formula
With additional mode.
On the basis of above-mentioned preferred raw material, further preferably, the sprayable fire-retardant polycarbonate/polyketone alloy,
It is made of the raw material components of following parts by weight:
Sprayable fire-retardant polycarbonate/polyketone the alloy the preparation method is as follows:
Polycarbonate, polyketone resin and silane copolymer polycarbonate are dried in advance, then press above-mentioned weight ratio for each raw material
Mixing squeezes out through extruder, obtains sprayable fire-retardant polycarbonate/polyketone alloy after granulation.
The extruder be double screw extruder, processing temperature be 200~260 DEG C, screw speed be 300~
600rpm。
Sprayable fire-retardant polycarbonate/polyketone alloy material that the above method is prepared has good sprayable property
Energy, anti-flammability and heat resistance, can be used for manufacturing wall switch.
Compared with prior art, the present invention has the advantage that
The present invention uses the ternary system being made of polycarbonate, polyketone and silane copolymer polycarbonate, has screened specific
Each raw material of performance parameter, certain content, under the synergistic effect of other components, obtain a kind of polycarbonate/polyketone and close
Gold, the alloy have good sprayable performance, anti-flammability and heat resistance, can be used for manufacturing wall switch.
Specific embodiment
The producer of each raw material used in the embodiment of the present invention 1~6 and the trade mark are listed in the table below in 1.
Table 1
Below unless otherwise instructed, the proportion of each raw material is parts by weight.
Embodiment 1
Polycarbonate, polyketone, silane copolymer PC are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone tree
Rouge, silane copolymer PC and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot abundant according to the proportion
It is specific to match using twin-screw shearing, mixing granulator after being uniformly dispersed are as follows: polycarbonate, 70；Polyketone, 25；Silane copolymer
PC, 5, compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone
Powder, 0.2；Pentaerythritol ester, 0.2.
Embodiment 2
Polycarbonate, polyketone, silane copolymer PC are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone tree
Rouge, silane copolymer PC and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot abundant according to the proportion
It is specific to match using twin-screw shearing, mixing granulator after being uniformly dispersed are as follows: polycarbonate, 60；Polyketone, 25；Silane copolymer
PC, 15, compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone
Powder, 0.2；Pentaerythritol ester, 0.2.
Embodiment 3
Polycarbonate, polyketone, silane copolymer PC are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone tree
Rouge, silane copolymer PC and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot abundant according to the proportion
It is specific to match using twin-screw shearing, mixing granulator after being uniformly dispersed are as follows: polycarbonate, 50；Polyketone, 25；Silane copolymer
PC, 25, compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone
Powder, 0.2；Pentaerythritol ester, 0.2.
Embodiment 4
Polycarbonate, polyketone, silane copolymer PC are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone tree
Rouge, silane copolymer PC and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot abundant according to the proportion
It is specific to match using twin-screw shearing, mixing granulator after being uniformly dispersed are as follows: polycarbonate, 40；Polyketone, 25；Silane copolymer
PC, 35, compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone
Powder, 0.2；Pentaerythritol ester, 0.2.
Embodiment 5
Polycarbonate, polyketone, silane copolymer PC are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone tree
Rouge, silane copolymer PC and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot abundant according to the proportion
It is specific to match using twin-screw shearing, mixing granulator after being uniformly dispersed are as follows: polycarbonate, 45；Polyketone, 30；Silane copolymer
PC, 25, compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone
Powder, 0.2；Pentaerythritol ester, 0.2.
Embodiment 6
Polycarbonate, polyketone, silane copolymer PC are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone tree
Rouge, silane copolymer PC and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot abundant according to the proportion
After being uniformly dispersed, using twin-screw shearing, mixing granulator；Specific proportion are as follows: polycarbonate, 40；Polyketone, 35；Silane copolymer
PC, 25；Compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone
Powder, 0.2；Pentaerythritol ester, 0.2.
Comparative example 1
Polycarbonate, polyketone are dried into 6h in 120 DEG C of baking ovens, then by the polycarbonate of drying, polyketone and impact modifier,
Fire retardant, antioxidant and processing aid put into according to the proportion stir pot it is fully dispersed uniformly after, using twin-screw shearing, be kneaded make
Grain；Specific proportion are as follows: polycarbonate, 75；Polyketone, 25；Compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；
168,0.2；Stabilisers against hydrolysis, 0.1；Silicone powder, 0.2；Pentaerythritol ester, 0.2.
This comparative example uses PC for LG 1201-10, melt flow index 10g/10min, and polyketone is Hyosung 330A, melts
Melting flow index is 60g/10min.
Comparative example 2
Polycarbonate, silane copolymer PC, polyketone are dried into 6h in 120 DEG C of baking ovens, then the polycarbonate of drying, silane is total
Poly- PC, polyketone and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot fully dispersed according to the proportion
After uniformly, using twin-screw shearing, mixing granulator；Specific proportion are as follows: polycarbonate, 50；Polyketone, 25；Silane copolymer PC,
25；Compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone powder,
0.2；Pentaerythritol ester, 0.2.
This comparative example uses PC for Bayer 2400, melt flow index 22g/10min, and polyketone is Hyosung 330A, melting
Flow index is 60g/10min, and silane copolymer PC is light AG1760, and molecular weight is 29000~32000g/mol.
Comparative example 3
Polycarbonate, silane copolymer PC, polyketone are dried into 6h in 120 DEG C of baking ovens, then the polycarbonate of drying, silane is total
Poly- PC, polyketone and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot fully dispersed according to the proportion
After uniformly, using twin-screw shearing, mixing granulator；Specific proportion are as follows: polycarbonate, 50；Polyketone, 25；Silane copolymer PC,
25；Compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone powder,
0.2；Pentaerythritol ester, 0.2.
This comparative example uses PC for LG 1201-10, melt flow index 10g/10min, and polyketone is Hyosung 630A, melts
Melting flow index is 5g/10min, and silane copolymer PC is light AG1760, and molecular weight is 29000~32000g/mol.
Comparative example 4
Polycarbonate, silane copolymer PC, polyketone are dried into 6h in 120 DEG C of baking ovens, then the polycarbonate of drying, silane is total
Poly- PC, polyketone and compatilizer, impact modifier, fire retardant, antioxidant and processing aid put into that stir pot fully dispersed according to the proportion
After uniformly, using twin-screw shearing, mixing granulator；Specific proportion are as follows: polycarbonate, 50；Polyketone, 25；Silane copolymer PC,
25；Compatilizer, 1.5；Impact modifier, 2；Fire retardant, 3；1076,0.2；168,0.2；Stabilisers against hydrolysis, 0.1；Silicone powder,
0.2；Pentaerythritol ester, 0.2.
This comparative example uses PC for LG 1201-10, melt flow index 10g/10min, and polyketone is Hyosung 330A, melts
Melting flow index is 60g/10min, and silane copolymer PC is light AG2530, and molecular weight is 17000~22000g/mol.
Testing method:
Physical and mechanical property: impact property test is referring to GB/T1043.1-2008 standard；
Heat distortion temperature (1.82Mpa): referring to GB/T1634.2-2004 standard；
Flame retardant property: glowing filament test is referring to GB/T5169.11-2006 standard；
Ball presses heat resistance: ball pressure test is referring to GB/T5169.21-2006 standard；
Spraying property: resulting materials in embodiment and comparative example are used for the spraying that wall opens panel；
Spray adhesive force test: referring to GB/T 9286-1998 standard；
The results are shown in Table 2 for resulting materials test performance
Table 2
Contrast and experiment is it can be found that can significantly improve the spray of PC/POK alloy system by the way that silane copolymer PC is added
Performance is applied, while improving notch impact strength, significantly reduces spraying cracking ratio；And anti-flammability, heat resistance are also not apparent from
It reduces, can press test request and flame-retardancy requirements by electrical standard ball.Since silane copolymer PC price is higher, material is comprehensively considered
The performance and cost of material, embodiment 3 are the optimum formula of this patent.
Claims (7)
1. a kind of sprayable fire-retardant polycarbonate/polyketone alloy, which is characterized in that the raw material components including following parts by weight:
Polycarbonate 40 ~ 70；
Polyketone 20 ~ 25；
Copolymeric siloxane polycarbonate 5 ~ 35；
Fire retardant 1 ~ 5；
Other auxiliary agents 0.5 ~ 10；
The polycarbonate is selected from bisphenol A polycarbonate, and melt flow rate (MFR) is 5 ~ 20g/10min；
The melt flow rate (MFR) of the polyketone is 50 ~ 70g/10min；
The copolymeric siloxane polycarbonate is block type copolymer, and molecular weight is 26000 ~ 32000g/mol.
2. sprayable fire-retardant polycarbonate/polyketone alloy according to claim 1, which is characterized in that the fire retardant choosing
From bromide fire retardant.
3. sprayable fire-retardant polycarbonate/polyketone alloy according to claim 1, which is characterized in that described other to help
Agent includes at least one of compatilizer, impact modifier, antioxidant, stabilisers against hydrolysis and processing aid.
4. sprayable fire-retardant polycarbonate/polyketone alloy, feature described in any claim exist according to claim 1 ~ 3
In being made of the raw material components of following parts by weight:
Polycarbonate 40 ~ 70；
Polyketone 20 ~ 25；
Copolymeric siloxane polycarbonate 5 ~ 35；
Fire retardant 1 ~ 5；
Compatilizer 1 ~ 5；
Impact modifier 1 ~ 5；
Antioxidant 0.2 ~ 0.6；
Stabilisers against hydrolysis 0.1 ~ 0.6；
Processing aid 0.1 ~ 0.5；
The compatilizer, impact modifier, antioxidant, stabilisers against hydrolysis and processing aid are other auxiliary agents.
5. sprayable fire-retardant polycarbonate/polyketone alloy according to claim 4, which is characterized in that the compatilizer
Polyolefin elastomer, styrene butadiene thermoplasticelastomer, ethylene-methyl acrylate copolymerization selected from maleic anhydride grafting
At least one of object, polyethylene of maleic anhydride grafting；
The impact modifier is selected from terpolymer, the polyolefin elastic of methyl methacrylate-butadiene-styrene
At least one of body, organosilicon toughener, ethylene-acrylate-glycidyl methacrylate.
6. sprayable fire-retardant polycarbonate/polyketone alloy according to claim 4, which is characterized in that the antioxidant
Selected from 1076 and 168 compound；
The stabilisers against hydrolysis is selected from the liter SAG-005 of day；
The processing aid is selected from least one of calcium stearate, pentaerythritol ester, silicone powder.
7. it is a kind of according to claim 1 ~ 6 in sprayable fire-retardant polycarbonate/polyketone alloy described in any claim making
Make the application in wall switch.
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