CN115537010A - Flame retardant modified polycarbonate material and preparation process thereof - Google Patents
Flame retardant modified polycarbonate material and preparation process thereof Download PDFInfo
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- CN115537010A CN115537010A CN202211379077.5A CN202211379077A CN115537010A CN 115537010 A CN115537010 A CN 115537010A CN 202211379077 A CN202211379077 A CN 202211379077A CN 115537010 A CN115537010 A CN 115537010A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 117
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 117
- 239000003063 flame retardant Substances 0.000 title claims abstract description 58
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims abstract description 7
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 238000005469 granulation Methods 0.000 claims abstract description 7
- 230000003179 granulation Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012856 weighed raw material Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- QKORWYWGMJCFAW-UHFFFAOYSA-N 2-phenyl-3h-1,3,2-benzoxazaphosphinin-4-one Chemical compound O1C2=CC=CC=C2C(=O)NP1C1=CC=CC=C1 QKORWYWGMJCFAW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VVVXQOYTNUBLCZ-UHFFFAOYSA-N C(CCCCCCCCCCCCC)C1=C(C=CC=C1)OC(C1=CC=CC=C1)=O Chemical compound C(CCCCCCCCCCCCC)C1=C(C=CC=C1)OC(C1=CC=CC=C1)=O VVVXQOYTNUBLCZ-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame retardant modified polycarbonate material and a preparation process thereof, wherein the flame retardant modified polycarbonate material comprises the following components in parts by weight: 20-30 parts of polycarbonate, 1.5-3 parts of phenoxy cyclophosphazene, 1.2-2.4 parts of silane coupling agent, 1.6-3.5 parts of inorganic flame retardant, 15-25 parts of modified polycarbonate, 3-6 parts of butadiene-acrylonitrile rubber and 2-4 parts of pentaerythritol stearate; wherein; the weight average molecular weight of the matrix is 103-105 g/moL; the number average molecular weight of the matrix is 2 multiplied by 103 to 105g/moL; the modified polycarbonate is prepared by the following method: 1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, and then standing the mixture for 5 to 8 hours at a temperature of between 15 ℃ below zero and 10 ℃ below zero; 2) Taking out the product obtained in the step 1), placing at room temperature, adding polyethylene glycol methacrylate, heating to 70-90 ℃, stirring for 2-5 h, and cooling for later use; 3) Adding the product obtained in the step 2) into a double-screw extruder for extrusion and granulation to obtain the modified polycarbonate.
Description
Technical Field
The invention belongs to the technical field of polycarbonate materials, and particularly relates to a flame retardant modified polycarbonate material and a preparation process thereof.
Background
Although the flame retardance of Polycarbonate (PC) is better than that of common thermoplastic polymers, the requirement of certain application fields on flame retardance is still difficult to meet, for example, the PC is widely applied to electronic appliances, indoor buildings and household products, and generally has a flame retardance requirement on materials, but the existing PC cannot meet the requirement of the products, so that the PC is required to be subjected to flame retardance modification. The flame retardant for PC at present comprises tetrabromobisphenol A (TBBPA), decabromodiphenyl oxide (DBDPO), polydibromophenyl ether (PDBPO), tetradecylbenzoyloxybenzene (DBDPOB) and the like. However, many european countries and the united states have controversial issues regarding toxicity and environmental issues of halogen-based flame retardants such as polybromodiphenyl ether, and corrosive gases generated during the decomposition of halogen-based flame retardants are liable to cause the failure of key parts of electronic and electrical equipment.
In addition, PC is prone to stress cracking. Various modified varieties such as high-toughness anti-cracking PC, flame-retardant PC and the like appear on the market, but no polycarbonate product with halogen-free, flame-retardant and high-toughness functions is available in the market at present, because the realization of the functions is mutually contradictory according to the conventional traditional modification means, the realization of one function usually needs to reduce the realization of the other function, and the phenomenon of the trade-off is formed. A common toughening means to improve PC toughness is toughening with rubber particles such as butadiene or acrylonitrile. However, the PC toughened by the olefin rubber not only easily causes the rapid reduction of the heat deformation temperature of the PC and influences the use of products with heat resistance requirements, but also influences the flame retardant performance of the material. If the toughening agent of the type is added, the flame retardant property of the PC material is also obviously reduced, so that the difficulty of preparing a flame retardant material is increased, and particularly the difficulty of preparing a halogen-free flame retardant material is increased.
In general, a matte or dull surface gives a soft feel without glare. For extinction modification, inorganic fillers are also used as main materials in China at present. These inorganic fillers have a wide variety of effects on gloss. CaCO has been studied 3 The extinction effect of the filled PP, when the filling amount of calcium carbonate is 5 percent, the surface gloss of the filled product is 50 percent; at a calcium carbonate loading of 415%, the surface gloss of the article was 32%, all as described above for the inorganic filler matte PC modification. The advantage of this method is that it is cost-effective, but the greatest disadvantage is that the mechanical strength, in particular the notched impact strength, of the product is very low, the product is particularly brittle and cannot be used in many cases.
Disclosure of Invention
The invention aims to provide a flame retardant modified polycarbonate material which comprises the following components in parts by weight: 20 to 30 parts of polycarbonate, 1.5 to 3 parts of phenoxy cyclophosphazene, 1.2 to 2.4 parts of silane coupling agent, 1.6 to 3.5 parts of inorganic flame retardant, 15 to 25 parts of modified polycarbonate, 3 to 6 parts of butadiene-acrylonitrile rubber and 2 to 4 parts of pentaerythritol stearate.
Wherein the substrate of the modified polycarbonate is selected from any one of aliphatic polycarbonate, alicyclic polycarbonate and aromatic polycarbonate; and the weight average molecular weight of the matrix is 10 3 ～10 5 g/moL; the number average molecular weight of the matrix is 2 x 10 3 ～10 5 g/moL。
The modified polycarbonate is prepared by the following method:
1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, wherein the mass ratio of the modified polycarbonate substrate to the polyvinyl alcohol to the flame retardant is (1.2-2.5): (0.48 to 0.78): (0.22-0.43), and then standing the mixture for 5-8 h at the temperature of-15 to-10 ℃.
2) Taking out the product obtained in the step 1), placing at room temperature, adding polyethylene glycol methacrylate, heating to 70-90 ℃, stirring for 2-5 h, and cooling for later use.
3) Adding the product obtained in the step 2) into a single-screw extruder, and extruding and granulating at 100-120 ℃ to obtain the modified polycarbonate.
The flame retardant is:
further, the polycarbonate is selected from bisphenol a type polycarbonates.
Further, the silane coupling agent is selected from any one of aminopropyltriethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.
Further, the inorganic flame retardant is prepared from the following components in percentage by weight (0.45-0.86): (0.55-0.95): (0.64 to 1.12) magnesium hydroxide, aluminum hydroxide and flaky zinc borate.
Another object of the present invention is a process for preparing a flame retardant modified polycarbonate material, the process comprising the steps of:
s1: weighing the raw materials according to the proportion for later use.
S2: adding the weighed raw materials into a high-speed stirrer, stirring for 1-2 h at low speed, and then stirring for 0.5-1 h at high speed, wherein the temperature of a machine barrel is 160-200 ℃.
S3: and (3) adding the product obtained in the step (S2) into an open mill, and mixing for 15-20 min.
S4: and (4) adding the product obtained in the step (S3) into a double-screw extruder, and performing extrusion granulation to obtain the modified polycarbonate material.
Preferably, the low-speed stirring speed in the step S2 is 200 to 400r/min, and the high-speed stirring speed is 800 to 1000r/min.
Preferably, the mixing temperature of the open mill is 100-120 ℃.
Preferably, in the step S4, the temperature of the first zone of the double-screw extruder is 130-140 ℃, the temperature of the second zone is 160-170 ℃, the temperature of the third zone is 190-200 ℃, the temperature of the fourth zone is 220-230 ℃, the temperature of the fifth zone is 180-190 ℃, and the temperature of the head is 165-170 ℃.
The invention also has the following beneficial effects:
1. in the invention, a modified polycarbonate matrix of any one of aliphatic polycarbonate, alicyclic polycarbonate and aromatic polycarbonate is modified, wherein the flame retardant used for modification is a sulfur-phosphorus flame retardant and polyvinyl alcohol, and then the modified polycarbonate matrix is prepared by mixing with bisphenol A polycarbonate, wherein the obtained polycarbonate material has excellent mechanical and flame retardant properties, and the organic flame retardant and the electrodeless flame retardant are used for respectively modifying the polycarbonate without mutually influencing the properties of the modified polycarbonate, so that the obtained material has better flame retardant property.
2. In the invention, when the matrix of the modified polycarbonate is modified, a low-temperature dynamic volume method is adopted to ensure that the growth direction of fiber crystals in substances in the mixed raw materials is controlled, so that the polycarbonate and the organic flame retardant can be better crosslinked and fully mixed, and the polycarbonate material obtained later can exert better performance.
Drawings
FIG. 1 is a process flow diagram of a flame retardant modified polycarbonate material of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for the purpose of illustration, and the detailed implementation and specific operation procedures are given, it should be noted that those skilled in the art can make various modifications and amendments without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Example 1
A flame retardant modified polycarbonate material comprises the following components in parts by weight: 20 parts of polycarbonate, 1.5 parts of phenoxy cyclophosphazene, 1.2 parts of silane coupling agent, 1.6 parts of inorganic flame retardant, 15 parts of modified polycarbonate, 3 parts of butadiene-acrylonitrile rubber and 2 parts of pentaerythritol stearate.
Wherein the matrix of the modified polycarbonate is selected from aliphatic polycarbonate; and the weight average molecular weight of the matrix is 10 3 g/moL; the number average molecular weight of the matrix is 2 x 10 3 g/moL。
The modified polycarbonate is prepared by the following method:
1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, wherein the mass ratio of the modified polycarbonate substrate to the polyvinyl alcohol to the flame retardant is 1.2:0.48:0.22, and then left to stand at-15 ℃ for 5 hours.
2) Taking out the product obtained in the step 1), standing at room temperature, adding polyethylene glycol methacrylate, heating to 70 ℃, stirring for 2h, and cooling for later use.
3) Adding the product obtained in the step 2) into a single-screw extruder, and extruding and granulating at 100 ℃ to obtain the modified polycarbonate.
The flame retardant is:
the polycarbonate is selected from bisphenol A polycarbonate; the silane coupling agent is selected from aminopropyltriethoxysilane; the inorganic flame retardant is prepared from the following components in a weight ratio of 0.45:0.55:0.64 parts of magnesium hydroxide, aluminum hydroxide and flaky zinc borate.
The preparation process comprises the following steps:
s1: weighing the raw materials according to the proportion for later use.
S2: the weighed raw materials are added into a high-speed stirrer, and the mixture is stirred for 1 hour at a low speed and then for 0.5 hour at a high speed, wherein the temperature of a machine barrel is 160 ℃.
S3: and (3) adding the product obtained in the step (S2) into an open mill, and mixing for 15min.
S4: and (4) adding the product obtained in the step (S3) into a double-screw extruder, and performing extrusion granulation to obtain the modified polycarbonate material.
Wherein the low-speed stirring speed in the step S2 is 200r/min, and the high-speed stirring speed is 800r/min; the mixing temperature of the open mill is 100 ℃; in the step S4, the first zone temperature of the double-screw extruder is 130 ℃, the second zone temperature is 160 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 220 ℃, the fifth zone temperature is 180 ℃, and the head temperature is 165 ℃.
Example 2
A flame retardant modified polycarbonate material comprises the following components in parts by weight: 30 parts of polycarbonate, 3 parts of phenoxy cyclophosphazene, 2.4 parts of silane coupling agent, 3.5 parts of inorganic flame retardant, 25 parts of modified polycarbonate, 6 parts of butadiene-acrylonitrile rubber and 4 parts of pentaerythritol stearate.
Wherein the substrate of the modified polycarbonate is selected from alicyclic polycarbonate; and the weight average molecular weight of the matrix is 10 5 g/moL; the number average molecular weight of the matrix is 2 x 10 5 g/moL。
The modified polycarbonate is prepared by the following method:
1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, wherein the mass ratio of the modified polycarbonate substrate to the polyvinyl alcohol to the flame retardant is 2.5:0.78:0.43, and then left to stand at-10 ℃ for 8 hours.
2) Taking out the product obtained in the step 1), standing at room temperature, adding polyethylene glycol methacrylate, heating to 90 ℃, stirring for 5 hours, and cooling for later use.
3) Adding the product obtained in the step 2) into a single-screw extruder, and extruding and granulating at 120 ℃ to obtain the modified polycarbonate.
The flame retardant is as follows:
the polycarbonate is selected from bisphenol A polycarbonate; the silane coupling agent is selected from vinyl triethoxysilane; the inorganic flame retardant is prepared from the following components in a weight ratio of 0.86:0.95:1.12 parts of magnesium hydroxide, aluminum hydroxide and zinc borate flakes.
The preparation process comprises the following steps:
s1: weighing the raw materials according to the proportion for later use.
S2: the weighed raw materials are added into a high-speed stirrer, and the mixture is stirred at low speed for 2 hours and then at high speed for 1 hour, wherein the temperature of a cylinder is 200 ℃.
S3: and (3) adding the product obtained in the step (S2) into an open mill, and mixing for 20min.
S4: and (4) adding the product obtained in the step (S3) into a double-screw extruder, and performing extrusion granulation to obtain the modified polycarbonate material.
Wherein the low-speed stirring speed in the step S2 is 400r/min, and the high-speed stirring speed is 1000r/min; the mixing temperature of the open mill is 120 ℃; in the step S4, the temperature of the first zone of the double-screw extruder is 140 ℃, the temperature of the second zone is 170 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 190 ℃, and the temperature of the head is 170 ℃.
Example 3
The flame retardant modified polycarbonate material comprises the following components in parts by weight: 24 parts of polycarbonate, 2 parts of phenoxy cyclophosphazene, 1.8 parts of silane coupling agent, 2 parts of inorganic flame retardant, 20 parts of modified polycarbonate, 4 parts of butadiene-acrylonitrile rubber and 3 parts of pentaerythritol stearate.
Wherein the matrix of the modified polycarbonate is selected from aromatic polycarbonate; and the weight average molecular weight of the matrix is 10 4 g/moL; the number average molecular weight of the matrix is 2 x 10 4 g/moL。
The modified polycarbonate is prepared by the following method:
1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, wherein the mass ratio of the modified polycarbonate substrate to the polyvinyl alcohol to the flame retardant is 1.8:0.56:0.28, and then left to stand at-12 ℃ for 6 hours.
2) Taking out the product obtained in the step 1), standing at room temperature, adding polyethylene glycol methacrylate, heating to 80 ℃, stirring for 3h, and cooling for later use.
3) Adding the product obtained in the step 2) into a single-screw extruder, and extruding and granulating at 110 ℃ to obtain the modified polycarbonate.
The flame retardant is as follows:
the polycarbonate is selected from bisphenol A polycarbonate; the silane coupling agent is selected from methacryloxypropyl trimethoxy silane; the inorganic flame retardant is prepared from the following components in a weight ratio of 0.58:0.67:0.88 magnesium hydroxide, aluminum hydroxide, and flaky zinc borate.
The preparation process comprises the following steps:
s1: weighing the raw materials according to the proportion for later use.
S2: the weighed raw materials are added into a high-speed stirrer, and the mixture is stirred for 1.5 hours at a low speed and then for 0.7 hour at a high speed, wherein the temperature of a machine barrel is 170 ℃.
S3: and (3) adding the product obtained in the step (S2) into an open mill, and mixing for 16min.
S4: and (4) adding the product obtained in the step (S3) into a double-screw extruder, and performing extrusion granulation to obtain the modified polycarbonate material.
Wherein the low-speed stirring speed in the step S2 is 300r/min, and the high-speed stirring speed is 900r/min; the mixing temperature of the open mill is 110 ℃; in the step S4, the temperature of the first zone, the temperature of the second zone, the temperature of the third zone, the temperature of the fourth zone, the temperature of the fifth zone, the temperature of the 185 ℃ and the temperature of the head of the double-screw extruder are 135 ℃, 165 ℃, 195 ℃, 225 ℃, 168 ℃.
Example 4
A flame retardant modified polycarbonate material comprises the following components in parts by weight: 28 parts of polycarbonate, 2.5 parts of phenoxy cyclophosphazene, 2.2 parts of a silane coupling agent, 3.2 parts of an inorganic flame retardant, 23 parts of modified polycarbonate, 5 parts of butadiene-acrylonitrile rubber and 3.5 parts of pentaerythritol stearate.
Wherein the substrate of the modified polycarbonate is selected from alicyclic polycarbonate; and the weight average molecular weight of the matrix is 10 5 g/moL; the number average molecular weight of the matrix is 10 5 g/moL。
The modified polycarbonate is prepared by the following method:
1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, wherein the mass ratio of the modified polycarbonate substrate to the polyvinyl alcohol to the flame retardant is 2.3:0.73:0.41, and then left to stand at-11 ℃ for 7 hours.
2) Taking out the product obtained in the step 1), standing at room temperature, adding polyethylene glycol methacrylate, heating to 85 ℃, stirring for 4 hours, and cooling for later use.
3) Adding the product obtained in the step 2) into a single-screw extruder, and extruding and granulating at 115 ℃ to obtain the modified polycarbonate.
The flame retardant is:
the polycarbonate is selected from bisphenol a polycarbonate; the silane coupling agent is selected from vinyl tri (beta-methoxy ethoxy) silane; the inorganic flame retardant is prepared from the following components in a weight ratio of 0.84:0.92:1.07 magnesium hydroxide, aluminum hydroxide, and flaky zinc borate.
The preparation process comprises the following steps:
s1: weighing the raw materials according to the proportion for later use.
S2: the weighed raw materials were added to a high speed stirrer and stirred at low speed for 1.5h and then at high speed for 0.9h, wherein the barrel temperature was 190 ℃.
S3: and (3) adding the product obtained in the step (S2) into an open mill, and mixing for 18min.
S4: and (4) adding the product obtained in the step (S3) into a double-screw extruder, and performing extrusion granulation to obtain the modified polycarbonate material.
Wherein the low-speed stirring speed in the step S2 is 350r/min, and the high-speed stirring speed is 950r/min; the mixing temperature of the open mill is 115 ℃; in the step S4, the temperature of the first zone, the temperature of the second zone, the temperature of the third zone, the temperature of the fourth zone, the temperature of the fifth zone and the temperature of the head of the double-screw extruder are 138 ℃, 167 ℃, 198 ℃, 227 ℃, 186 ℃ and 169 ℃.
And (4) performance testing:
after drying the flame retardant modified polycarbonate materials prepared in examples 1 to 4 for 4 hours, the materials were injection molded into standard physical property sample strips and flame retardant sample strips under the same injection molding conditions according to ISO527, ISO180, ISO178, ISO180, ISO80, GB8807, IEC60695 and UL94 standards, and the performance was tested, the test results are shown in Table 1,
table 1. Test results:
as can be seen from Table 1, the flame retardant modified polycarbonate materials prepared in examples 1 to 4 of the present invention have excellent flame retardant properties and mechanical properties.
Claims (8)
1. The flame retardant modified polycarbonate material is characterized by comprising the following components in parts by weight: 20-30 parts of polycarbonate, 1.5-3 parts of phenoxy cyclophosphazene, 1.2-2.4 parts of silane coupling agent, 1.6-3.5 parts of inorganic flame retardant, 15-25 parts of modified polycarbonate, 3-6 parts of butadiene-acrylonitrile rubber and 2-4 parts of pentaerythritol stearate;
wherein the substrate of the modified polycarbonate is selected from any one of aliphatic polycarbonate, alicyclic polycarbonate and aromatic polycarbonate; the weight average molecular weight of the matrix is 103-105 g/moL; the number average molecular weight of the matrix is 2 multiplied by 103 to 105g/moL;
the modified polycarbonate is prepared by the following method:
1) Uniformly mixing and stirring a modified polycarbonate substrate, polyvinyl alcohol and a flame retardant, wherein the mass ratio of the modified polycarbonate substrate to the polyvinyl alcohol to the flame retardant is (1.2-2.5): (0.48 to 0.78): (0.22-0.43), then standing the mixture for 5-8 h at the temperature of-15 to-10 ℃;
2) Taking out the product obtained in the step 1), placing at room temperature, adding polyethylene glycol methacrylate, heating to 70-90 ℃, stirring for 2-5 h, and cooling for later use;
3) Adding the product obtained in the step 2) into a single-screw extruder, and extruding and granulating at 100-120 ℃ to obtain the modified polycarbonate;
the flame retardant is:
2. the flame retardant modified polycarbonate material of claim 1, wherein the polycarbonate is selected from bisphenol a polycarbonate.
3. The flame retardant modified polycarbonate material of claim 1, wherein the silane coupling agent is selected from any one of aminopropyltriethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, and vinyltris (β -methoxyethoxy) silane.
4. The flame retardant modified polycarbonate material of claim 1, wherein the inorganic flame retardant is present in an amount of (0.45 to 0.86): (0.55-0.95): (0.64 to 1.12) magnesium hydroxide, aluminum hydroxide and flaky zinc borate.
5. The preparation process of the flame retardant modified polycarbonate material according to any one of claims 1 to 4, wherein the preparation process comprises the following steps:
s1: weighing the raw materials according to the proportion for later use;
s2: adding the weighed raw materials into a high-speed stirrer, stirring for 1-2 h at low speed, and then stirring for 0.5-1 h at high speed, wherein the temperature of a machine barrel is 160-200 ℃;
s3: adding the product obtained in the step S2 into an open mill, and mixing for 15-20 min;
s4: and (4) adding the product obtained in the step (S3) into a double-screw extruder, and performing extrusion granulation to obtain the modified polycarbonate material.
6. The preparation process of the flame retardant modified polycarbonate material as claimed in claim 5, wherein the low-speed stirring rate in step S2 is 200-400 r/min, and the high-speed stirring rate is 800-1000 r/min.
7. The preparation process of the flame retardant modified polycarbonate material of claim 5, wherein the mixing temperature of the open mill is 100-120 ℃.
8. The process according to claim 5, wherein the temperature of the first zone in the twin-screw extruder in the step S4 is 130-140 ℃, the temperature of the second zone is 160-170 ℃, the temperature of the third zone is 190-200 ℃, the temperature of the fourth zone is 220-230 ℃, the temperature of the fifth zone is 180-190 ℃, and the temperature of the head is 165-170 ℃.
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