CN110003632A - A kind of halogen-free and flame-retardant polycarbonate and preparation method thereof - Google Patents
A kind of halogen-free and flame-retardant polycarbonate and preparation method thereof Download PDFInfo
- Publication number
- CN110003632A CN110003632A CN201910279260.XA CN201910279260A CN110003632A CN 110003632 A CN110003632 A CN 110003632A CN 201910279260 A CN201910279260 A CN 201910279260A CN 110003632 A CN110003632 A CN 110003632A
- Authority
- CN
- China
- Prior art keywords
- parts
- flame
- dopmi
- retardant
- free
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 64
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 55
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 51
- 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 40
- 238000002360 preparation method Methods 0.000 title claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000007493 shaping process Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000012757 flame retardant agent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- NJNWCIAPVGRBHO-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[(oxo-$l^{5}-phosphanylidyne)methyl]azanium Chemical group OCC[N+](C)(C)C#P=O NJNWCIAPVGRBHO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of halogen-free and flame-retardant polycarbonate, using a kind of novel halogen-free flame-retardant agent DOPMI, such DOPMI has suitable fusing point and excellent thermal stability, it is easy to be dispersed in thermoplastic polymer by melt blending, and meet the machine-shaping requirement of many flame-retardant polymers, be individually used for PC or with phosphor-containing flame-proof PET, MPS composite usage is into PC, excellent flame retardant effect can be obtained, it can be applied to industrial production fire-retardant polycarbonate, the invention discloses DOPMI, and the flame retardant rating of addition raising PC in PC can be applied to UL94V-0, and disclose the composition proportion and production method of such fire-retardant polycarbonate.
Description
Technical field
The present invention relates to a kind of halogen-free and flame-retardant polycarbonates and preparation method thereof, belong to Polycarbonate flame retardant Material Field.
Background technique
Polycarbonate (PC) is a kind of thermoplastic engineering plastic of excellent combination property, with impact resistance outstanding, thoroughly
Bright property, dimensional stability, excellent mechanical property and electrical insulation capability, wider use temperature range (- 60-120 DEG C), well
Creep resistant, weatherability and self-extinguishment, therefore have a wide range of applications in the fields such as electronics, electrical, automobile, building, packaging,
It has been rapidly spread to the new technical fields such as Aeronautics and Astronautics, computer in recent years.Charring rate is higher when PC material combustion, energy self-extinguishment,
UL94V-2 grades of flame retardant rating, though there is preferable anti-flammability compared with common thermoplastic, but still it is flammable, and have when burning
Hot melt drips, and easily causes material kindling nearby, is still difficult to meet fire-retardant fireproof requirement in above-mentioned application field, therefore permitted
In more practical applications flame retardant treatment must be carried out to PC material.
The today for using bittern-free flame-proof material, DOPO(9, the miscellaneous -10- phosphorus of 10- dihydro-9-oxy are increasingly advocated in the whole society
Miscellaneous phenanthrene -10- oxide) it is used as a kind of fire-retardant intermediate of New Phosphorus system, also increasingly obtain extensive concern, DOPO molecular structure
In P-H key, it is all active to alkenyl, epoxy bond and carbonyl, a variety of derivatives can be prepared.DOPO and its derivative due to
It is introduced in a manner of ring-type 0=P-O key in molecular structure containing cyclohexyl biphenyl and phenanthrene ring structure, especially side phosphorylcholine group, it is more cyclic than not
Organophosphorus ester thermal stability and chemical stability improve, flame retardant property is more preferable.DOPO and its derivative make as fire retardant
With can be used for the fire-retardant of a variety of high molecular materials such as polyester, polyamide, epoxy resin, polyurethane and phenolic resin.
Summary of the invention
DOPO has been synthesized a kind of nitrogenous Phosphaphenanthrene fire retardant DOPMI of New-type halide-free in N-PMI reaction by the present invention,
With suitable fusing point and excellent thermal stability, it is easy to be dispersed in thermoplastic polymer by melt blending, and meets and permitted
The machine-shaping requirement of more flame-retardant polymers, is individually used for PC or with phosphor-containing flame-proof PET, MPS composite usage into PC,
Excellent flame retardant effect can be obtained.
Technical solution of the present invention:
A kind of halogen-free and flame-retardant polycarbonate, the raw material comprising following parts by weight: 70-90 parts of polycarbonate, 3-9 parts of DOPMI,
0-24 parts of PET, 0-2 parts of phosphor-containing flame-proof of MPS, 0-1 parts other auxiliary agents.
Further, the raw material comprising following parts by weight: 70 parts of polycarbonate, 3 parts of DOPMI, 24 parts of phosphorous resistance
Fire PET, 2 parts of MPS, 1 part other auxiliary agents.
Further, the raw material comprising following parts by weight: 90 parts of polycarbonate, 9 parts of DOPMI, other of 1 part help
Agent.
Further, the raw material comprising following parts by weight: 72 parts of polycarbonate, 3 parts of DOPMI, 24 parts of phosphorous resistance
Fire PET, 1 part other auxiliary agents.
A kind of preparation method of such as above-mentioned halogen-free and flame-retardant polycarbonate comprising the steps of:
(1) it is synthesized in organic solvent tetrahydrofuran by DOPO and N-PMI, sand-like white is obtained after suction filtration, washing, drying
Solid halogen-free flame retardants DOPMI；
(2) DOPMI solid is added to after being crushed in pulverizer, is put into the air dry oven that temperature is 100-110 DEG C and dries
6-8 hours；
(3) it after mixing the DMPMI powder and polycarbonate of drying and other auxiliary agent ratios, squeezes out, make in extruser
Grain is to get halogen-free and flame-retardant polycarbonate of the present invention.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
It is fire-retardant using DOPO and N-PMI as a kind of nitrogenous Phosphaphenanthrene fire retardant DOPMI of New-type halide-free high thermal stability of Material synthesis
The structure of agent is confirmed by FT-IR, LC-MS characterization, TG and dsc analysis the result shows that, which has be suitable for molten
Melt temperature and excellent thermal stability, be easy to be dispersed in thermoplastic polymer by melt blending, and meets many fire-retardant poly-
The machine-shaping requirement for closing object, is individually used for PC or with phosphor-containing flame-proof PET, MPS composite usage into PC, can be obtained excellent
Good flame retardant effect；Individually addition DOPMI can improve the flame retardant property of PC, and when adding 9%, limit oxygen index is improved by 25.6%
To 29.3%, vertical combustion performance reaches UL94V-1 grades, when the phosphor-containing flame-proof PET for adding 3% DOPMI, 2% MPS and 24% is arrived
When in PC, the flame retardant property of PC can be greatly improved, limit oxygen index can be improved to 30.4%, and vertical combustion performance passes through
UL94V-0 test.
Detailed description of the invention
Fig. 1 is the FT-IR spectrogram of DOPO, N-PMI and DOPMI；
Fig. 2 is the LC liquid chromatogram of DOPMI；
Fig. 3 is the MS spectrogram of DOPMI；
Fig. 4 is the DSC curve and TG curve graph of DOPMI.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below.
Embodiment 1:
The synthesis of halogen-free flame retardants DOPMI, synthetic route are as follows:
。
(1) DOPO and tetrahydrofuran are added in four-hole boiling flask, are warming up to 80-100 DEG C of stirring；
(2) it is passed through nitrogen into four-hole boiling flask, after DOPO is entirely molten, the triphenyl phosphorus of 10-20% mass parts is added；
(3) N-PMI is added in tetrahydrofuran and is modulated into N-PMI solvent, for use；
(4) under the conditions of certain 120-160 takes the photograph DEG C, the N-PMI solution of configuration is slowly dropped in four-hole boiling flask, is added dropwise
Afterwards, the reaction was continued 2-3 hours；
(5) after the reaction was completed, sand-like white solid, halogen-free flameproof as of the invention are obtained after suction filtration, washing, drying
Agent.
In clean four-hole boiling flask, 15ml tetrahydrofuran is added and is added to as organic solvent, then by the DOPO of 2.16g
In 100ml four-hole boiling flask, 90 DEG C of stirrings is warming up to, and be passed through nitrogen into four-hole boiling flask and protected, is completely dissolved to DOPO
Afterwards, the triphenyl phosphorus of 0.393g is added into four-hole boiling flask, in computer heating control temperature between 120-160 DEG C, to four-hole boiling flask
The middle N-PMI solvent (tetrahydrofuran of the N-PMI and 15ml of 1.73g are deployed) that N-PMI and tetrahydrofuran is added dropwise and is modulated into,
After being added dropwise, the reaction was continued 2-3 hours, then sand-like white solid is obtained after suction filtration, washing, drying, is weighed as
3.1122g, halogen-free flame retardants DOPMI as of the invention.
The halogen-free flame retardants DOPMI structural formula is as follows:
。
Embodiment 2:
The structural characterization and thermal performance analysis of halogen-free flame retardants DOPMI:
Fig. 1 is the FT-IR spectrogram of DOPO, N-PMI and DOPMI.It can regard as from Fig. 1, the strong feature of the P-H key in DOPO is inhaled
It receives peak 2437cm-1 to disappear in DOPMI middle and advanced stage, while the strong conjugated double bond absorption peak 832cm-1 of N-PMI is in DOPMI spectrogram
Also do not occur, show that the two is reacted.It it can be seen that, is the absorption peak of Ar-H at 3060cm-1 in DOPMI spectrogram,
It is C=O characteristic peak at 1712cm-1, is P-Ph absorption peak at 1594cm-1, is P-OP-Ph absorption peak, each feature at 1196cm-1
Peak characterizes the structure of DOPMI, and infrared gap is the results show that desired react has occurred with N-PMI in DOPO.
Fig. 2 and Fig. 3 is respectively the LC spectrogram and MS spectrogram of DOPMI.Figure it is seen that liquid chromatogram only exists
Occur a strong absorption peak when 1.037min, analyzed by program, the purity of DOPMI has reached 99.64%, then composes from MS
Learnt in figure, the relative molecular mass of the product is 390(M+), it can determine to have obtained expected substance.
Fig. 4 is the DSC curve and TG curve graph of DOPMI.Figure 4, it is seen that the fusing point of DOPMI is 201.7 DEG C, heat
Decomposition temperature shows that the fire retardant of synthesis has suitable melting temperature and good thermal stability, is easy to logical at 300 DEG C or more
It crosses melt blending to be dispersed in thermoplastic polymer well, is able to satisfy the application requirement of many flame-retardant polymers.
Embodiment 3:
(1) it is synthesized in organic solvent tetrahydrofuran by DOPO and N-PMI, sand-like white is obtained after suction filtration, washing, drying
Solid halogen-free flame retardants DOPMI；
(2) DOPMI solid is added to after being crushed in pulverizer, is put into the air dry oven that temperature is 100-110 DEG C and dries
6-8 hours；
(3) by the DMPMI powder I of 3 parts of parts by weight of drying, the phosphor-containing flame-proof PET of 24 parts by weight, the MPS of 2 parts by weight, 1 weight
After other auxiliary agent ratios mixing of part, squeezes out, is granulated to get halogen-free and flame-retardant polycarbonate of the present invention in extruser.
Embodiment 4:
(1) it is synthesized in organic solvent tetrahydrofuran by DOPO and N-PMI, sand-like white is obtained after suction filtration, washing, drying
Solid halogen-free flame retardants DOPMI；
(2) DOPMI solid is added to after being crushed in pulverizer, is put into the air dry oven that temperature is 100-110 DEG C and dries
6-8 hours；
(3) by the DMPMI powder of 3 parts of parts by weight of drying, the polycarbonate of 90 parts by weight, other auxiliary agent ratios of 1 parts by weight
It after mixing, squeezes out, be granulated to get halogen-free and flame-retardant polycarbonate of the present invention in extruser.
Embodiment 5:
(1) it is synthesized in organic solvent tetrahydrofuran by DOPO and N-PMI, sand-like white is obtained after suction filtration, washing, drying
Solid halogen-free flame retardants DOPMI；
(2) DOPMI solid is added to after being crushed in pulverizer, is put into the air dry oven that temperature is 100-110 DEG C and dries
6-8 hours；
(3) by the DMPMI powder of 3 parts of parts by weight of drying, the polycarbonate of 72 parts by weight, the phosphor-containing flame-proof PET of 24 parts by weight,
After other auxiliary agent ratios mixing of 1 parts by weight, squeezes out, is granulated to get halogen-free anti-flaming polycarbonate of the present invention in extruser
Ester.
The quality of 1 parts by weight is 100g in above-described embodiment.
The flame retardant property for adding different flame-retardant formulations PC is listed in table 1.Pure PC has solution drippage after combustion with air,
UL94V-2 grades of tests, limit oxygen index 25.6% are passed through；There is apparent fire retardation to system after 9% DOPMI is added,
It can also inhibit the generation of dissolved drip simultaneously and slow down flame transmission speed, so that the limit oxygen index of system is increased to 29.3%, vertically
Combustibility reaches UL94V-1 grades；Only into PC add phosphor-containing flame-proof PET after, find its flame retardant property almost without promotion, and
After 3% DOPMI is added into PC/ Flame-retardant PET system, flame retardant rating has reached UL94V-1 grades, and limit oxygen index also improves
To 28.8%；The fire-retardant PE/DOPMI/MPS system flame retardant effect of PC/ is best, as long as the MPS of 3% DOPMI and 2% is added in system,
Vertical combustion performance can reach UL94V-0 grades, while limit oxygen index can also reach 30.4%, not have dissolved drip phenomenon, be added
After MPS, due to introducing element silicon, it is fire-retardant to form the triple synergistics of P-Si-N, makes flame retardant effect more preferably.
The PC flame retardant property of 1. different formulations of table.
In conclusion being hindered by a kind of nitrogenous Phosphaphenanthrene of New-type halide-free high thermal stability of Material synthesis of DOPO and N-PMI
Agent DOPMI is fired, the structure of yield 79.8%, fire retardant is confirmed by FT-IR, LC-MS characterization, TG and dsc analysis result
Show that the fire retardant has suitable melting temperature and excellent thermal stability, is easy to be dispersed in thermoplasticity by melt blending
In polymer, and meet the machine-shaping requirement of many flame-retardant polymers, be individually used for PC or with phosphor-containing flame-proof PET, MPS
Composite usage can obtain excellent flame retardant effect into PC；Individually addition DOPMI can improve the flame retardant property of PC, work as addition
When 9%, limit oxygen index is increased to 29.3% by 25.6%, and vertical combustion performance reaches UL94V-1 grades, when addition 3% DOPMI,
When in phosphor-containing flame-proof PET to the PC of 2% MPS and 24%, the flame retardant property of PC can be greatly improved, limit oxygen index can be improved
30.4%, and vertical combustion performance is tested by UL94V-0.
The basic principles, main features and advantages of the present invention have been shown and described above.The present invention is not by upper
The limitation of embodiment is stated, the above embodiments and description only illustrate the principle of the present invention, is not departing from the present invention
Various changes and improvements may be made to the invention under the premise of spirit and scope, these changes and improvements both fall within claimed
In the range of invention.The claimed scope of the invention is defined by appended claims and its equivalent.
Claims (5)
1. a kind of halogen-free and flame-retardant polycarbonate, it is characterised in that: the raw material comprising following parts by weight: 70-90 parts of polycarbonate,
3-9 parts of DOPMI, 0-24 parts of PET, 0-2 parts of phosphor-containing flame-proof of MPS, 0-1 parts other auxiliary agents.
2. a kind of halogen-free and flame-retardant polycarbonate as described in claim 1, it is characterised in that: the raw material comprising following parts by weight:
70 parts of polycarbonate, 3 parts of DOPMI, 24 parts of phosphor-containing flame-proof PET, 2 parts of MPS, 1 part other auxiliary agents.
3. a kind of halogen-free and flame-retardant polycarbonate as described in claim 1, it is characterised in that: the raw material comprising following parts by weight:
90 parts of polycarbonate, 9 parts of DOPMI, 1 part other auxiliary agents.
4. a kind of halogen-free and flame-retardant polycarbonate as described in claim 1, it is characterised in that: the raw material comprising following parts by weight:
72 parts of polycarbonate, 3 parts of DOPMI, 24 parts of phosphor-containing flame-proof PET, 1 part other auxiliary agents.
5. a kind of preparation method of the halogen-free and flame-retardant polycarbonate as described in above-mentioned any claim, it is characterised in that: include
Following steps:
(1) it is synthesized in organic solvent tetrahydrofuran by DOPO and N-PMI, sand-like white is obtained after suction filtration, washing, drying
Solid halogen-free flame retardants DOPMI；
(2) DOPMI solid is added to after being crushed in pulverizer, is put into the air dry oven that temperature is 100-110 DEG C and dries
6-8 hours；
(3) it after mixing the DMPMI powder and polycarbonate of drying and other auxiliary agent ratios, squeezes out, make in extruser
Grain is to get halogen-free and flame-retardant polycarbonate of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910279260.XA CN110003632A (en) | 2019-04-09 | 2019-04-09 | A kind of halogen-free and flame-retardant polycarbonate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910279260.XA CN110003632A (en) | 2019-04-09 | 2019-04-09 | A kind of halogen-free and flame-retardant polycarbonate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110003632A true CN110003632A (en) | 2019-07-12 |
Family
ID=67170424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910279260.XA Pending CN110003632A (en) | 2019-04-09 | 2019-04-09 | A kind of halogen-free and flame-retardant polycarbonate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110003632A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112695539A (en) * | 2020-12-18 | 2021-04-23 | 温州职业技术学院 | Preparation method of flame-retardant ink-absorbing polyamide coated fabric without solid powder filler |
-
2019
- 2019-04-09 CN CN201910279260.XA patent/CN110003632A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 汤俊杰等: "无卤磷氮阻燃剂的合成及在PC阻燃中的应用", 《中国塑料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112695539A (en) * | 2020-12-18 | 2021-04-23 | 温州职业技术学院 | Preparation method of flame-retardant ink-absorbing polyamide coated fabric without solid powder filler |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104403128B (en) | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO | |
| CN101838538B (en) | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof | |
| Zhao et al. | A novel halogen-free flame retardant for glass-fiber-reinforced poly (ethylene terephthalate) | |
| CN103113619B (en) | Triazine ring containing caged organic phosphate flame retardant and preparation method thereof | |
| Wang et al. | Synthesis and properties of epoxy resins containing bis (3-hydroxyphenyl) phenyl phosphate | |
| CN106009038A (en) | Halogen-free phosphorus-containing flame retardant, flame-retardant transparent polycarbonate material, and preparation and application of halogen-free phosphorus-containing flame retardant and flame-retardant transparent polycarbonate material | |
| CN103554497B (en) | A kind of preparation method of flame retardant type thermoplastic polyimide resin | |
| CN104371116A (en) | Preparation method and application of lignin-based intumescent flame retardant | |
| CN104558684A (en) | DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof | |
| CN103289084B (en) | Melamine polymer type intumescent flame retardant and preparation method and application thereof | |
| CN104086593A (en) | DOPO derivatives as well as preparation method and application thereof | |
| CN113861241B (en) | Bridged DOPO phosphorus nitrogen flame retardant, and preparation method and application thereof | |
| CN106633189A (en) | High-efficiency water-resistant intumescent flame retardant and application thereof in polypropylene | |
| CN110746646B (en) | Biomass-based flame retardant and preparation method thereof | |
| CN110511554A (en) | Halogen-free flameproof nitrogen phosphorus Si modification graphene/polycarbonate/ABS alloy material and preparation method thereof | |
| CN107868281A (en) | A kind of preparation of hypo-aluminum orthophosphate doping vario-property palygorskite and the application as fire retardant | |
| CN106928490B (en) | A kind of inorganic-organic hybridization nano compound, preparation method and its flame-proof polylactic acid with the fire-retardant synergistic effect of chain extension- | |
| CN104292504A (en) | Phosphonitrile fire retardant and preparation method and application thereof | |
| WO2020207042A1 (en) | Lignin intumescent flame retardant and preparation method therefor | |
| Ba et al. | Synthesis and characterization of a novel charring agent and its application in intumescent flame retardant polyethylene system | |
| CN102329488A (en) | Extrusion-grade low-smoke halogen-free flame-retardant PC (polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof | |
| CN110003632A (en) | A kind of halogen-free and flame-retardant polycarbonate and preparation method thereof | |
| CN108929524A (en) | A kind of increasing reaction flame-retardant polyester material and preparation method thereof | |
| CN113372695A (en) | Environment-friendly flame-retardant polyester composite material and preparation method thereof | |
| CN110003524A (en) | A kind of halogen-free flame retardants and its synthetic method and its application in Polycarbonate flame retardant material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190712 |
|
| RJ01 | Rejection of invention patent application after publication |